U.S. patent application number 13/810819 was filed with the patent office on 2013-06-06 for semiconductor materials prepared from bridged bithiazole copolymers.
This patent application is currently assigned to Polyera Corporation. The applicant listed for this patent is Johan Sebastian Basuki, Florian Doetz, Ashok Kumar Mishra, Hiroyoshi Noguchi, Subramanian Vaidyanathan, Bo Zhu. Invention is credited to Johan Sebastian Basuki, Florian Doetz, Ashok Kumar Mishra, Hiroyoshi Noguchi, Subramanian Vaidyanathan, Bo Zhu.
Application Number | 20130144065 13/810819 |
Document ID | / |
Family ID | 43466510 |
Filed Date | 2013-06-06 |
United States Patent
Application |
20130144065 |
Kind Code |
A1 |
Mishra; Ashok Kumar ; et
al. |
June 6, 2013 |
SEMICONDUCTOR MATERIALS PREPARED FROM BRIDGED BITHIAZOLE
COPOLYMERS
Abstract
The present invention provides semiconducting compounds,
oligomers and polymers of formula wherein A.sup.1 and A.sup.2 can
be the same or different and are S or Se, E is selected from the
group consisting of The compounds, oligomers and polymers of
formula of formula (1) are suitable for use in electronic devices
such as organic field effect transistors. ##STR00001##
Inventors: |
Mishra; Ashok Kumar;
(Singapore, SG) ; Vaidyanathan; Subramanian;
(Basel, CH) ; Noguchi; Hiroyoshi; (Singapore,
SG) ; Doetz; Florian; (Singapore, SG) ; Zhu;
Bo; (Shanghai, CN) ; Basuki; Johan Sebastian;
(Sydney, AU) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Mishra; Ashok Kumar
Vaidyanathan; Subramanian
Noguchi; Hiroyoshi
Doetz; Florian
Zhu; Bo
Basuki; Johan Sebastian |
Singapore
Basel
Singapore
Singapore
Shanghai
Sydney |
|
SG
CH
SG
SG
CN
AU |
|
|
Assignee: |
Polyera Corporation
Skokie
IL
BASF SE
Ludwigshafen
|
Family ID: |
43466510 |
Appl. No.: |
13/810819 |
Filed: |
July 29, 2011 |
PCT Filed: |
July 29, 2011 |
PCT NO: |
PCT/EP2011/063109 |
371 Date: |
January 17, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61370857 |
Aug 5, 2010 |
|
|
|
Current U.S.
Class: |
548/151 |
Current CPC
Class: |
C08G 2261/414 20130101;
H01L 51/0071 20130101; C08G 61/124 20130101; H01L 51/0508 20130101;
C08G 2261/596 20130101; C08G 2261/92 20130101; C07D 513/14
20130101; C08G 61/126 20130101; C08G 2261/228 20130101; C08G
2261/3246 20130101; C07D 495/04 20130101; H01L 51/0545 20130101;
C08G 2261/344 20130101; C07D 513/04 20130101; C08G 2261/226
20130101; H01L 51/0036 20130101; C08G 2261/364 20130101; C08G
61/123 20130101; H01L 51/0074 20130101; C08G 2261/3327 20130101;
C08G 2261/3243 20130101; H01L 51/0068 20130101; C08G 2261/124
20130101; C08G 2261/3223 20130101 |
Class at
Publication: |
548/151 |
International
Class: |
H01L 51/00 20060101
H01L051/00 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 5, 2010 |
EP |
10172083.7 |
Claims
1. A compound of formula ##STR00120## wherein A.sup.1 and A.sup.2
are independently S or Se, E is selected from the group consisting
of ##STR00121## wherein R.sup.1 and R.sup.2 are independently H,
halogen, --CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12
membered aliphatic heterocyclic residue, --X.sup.1--R.sup.6,
--X.sup.2--Ar.sup.1, --X.sup.2--Ar.sup.2--Ar.sup.1,
--X.sup.2--Ar.sup.2--R.sup.7 or
--X.sup.2--Ar.sup.2--Ar.sup.3--R.sup.7, wherein X.sup.1 is --O--,
--[Z.sup.1--O].sub.a--, --[O--Z.sup.1].sub.a--O--, --S--,
--[Z.sup.1--S--].sub.a--, --[S--Z.sup.1].sub.a--S--, --S(O),
--C(O)--, --C(O)O--, --C(O)NR.sup.8--, C(O)S--, --O(CO)--,
--S(CO)--, --NR.sup.8C(O)-- or --NR.sup.8--, wherein Z.sup.1 is
C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene,
a is an integer of from 1 to 10, and R.sup.8 is H,
C.sub.1-20-alkyl, or --Z.sup.2--C.sub.6-14-aryl, wherein Z.sup.2 is
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, R.sup.6 is C.sub.1-30-alkyl, C.sub.2-30-alkenyl or
C.sub.1-30-haloalkyl, X.sup.2 is --Z.sup.3--O--Z.sup.4--,
--Z.sup.3--S--Z.sup.4--, --S(O)--, --C(O)--, --C(O)O--,
--(CO)NR.sup.9, --C(O)S--, --O(CO)--, --S(CO)--, --NR.sup.9C(O)--,
--NR.sup.9--, --Z.sup.3--SiR.sup.9.sub.2--Z.sup.4--,
C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene
or a covalent bond, wherein Z.sup.3 and Z.sup.4 are independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, and R.sup.9 is H, C.sub.1-20-alkyl, or
--Z.sup.5--C.sub.6-14-aryl, wherein Z.sup.5 is C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
Ar.sup.1 is C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic
hetrocyclic residue, each optionally substituted with 1 to 5
substituents R.sup.a, wherein R.sup.a is selected from the group
consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, Ar.sup.2 and Ar.sup.3
are independently C.sub.6-14-arylene or bivalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 4 substituents R.sup.b, wherein R.sup.b is selected from the
group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, and R.sup.7 is
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl,
C.sub.1-20-alkoxy, --X.sup.3--Ar.sup.4,
--X.sup.3--Ar.sup.5--Ar.sup.4, --X.sup.3--Ar.sup.5--R.sup.10, or
--X.sup.3--Ar.sup.5--Ar.sup.6--R.sup.10, wherein X.sup.3 is
--Z.sup.6--O--Z.sup.7--, --Z.sup.6--S--Z.sup.7, --S(O)--, --C(O)--,
--C(O)O--, --(CO)NR.sup.11, --C(O)S--, --O(CO)--, --S(CO)--,
--NR.sup.11C(O)--, --NR.sup.11--,
--Z.sup.6--SiR.sup.11.sub.2--Z.sup.7--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
wherein Z.sup.6 and Z.sup.7 are independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
and R.sup.11 is H, C.sub.1-20-alkyl or --Z.sup.8--C.sub.6-14-aryl,
wherein Z.sup.8 is C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.4 is
C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 5
substituents R.sup.c, wherein R.sup.c is independently selected
from the group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, Ar.sup.5 and Ar.sup.6
at are independently C.sub.6-14-arylene or bivalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 4 substituents R.sup.d, wherein R.sup.d is selected from
the group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, and R.sup.10 is
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or
C.sub.1-20-alkoxy, R.sup.3, R.sup.4 and R.sup.5 are independently
H, halogen, --CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12
membered aliphatic heterocyclic residue, --X.sup.4--R.sup.12,
--X.sup.5--Ar.sup.7, --X.sup.5--Ar.sup.8--Ar.sup.7,
--X.sup.5--Ar.sup.8--R.sup.13 or
--X.sup.5--Ar.sup.8--Ar.sup.9--R.sup.13, wherein X.sup.4 is
--[Z.sup.9--O].sub.b--, --[Z.sup.9--S--].sub.b--, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.14-- or C(O)S--, wherein Z.sup.9
is C.sub.1-6-alkylene, C.sub.2-6-alkenylene or
C.sub.1-6-haloalkylene, b is an integer of from 1 to 10, and
R.sup.14 is H, C.sub.1-20-alkyl, or --Z.sup.10--C.sub.6-14-aryl,
wherein Z.sup.10 is C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, R.sup.12 is
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
X.sup.5 is --Z.sup.11--O--Z.sup.12, --Z.sup.11--S--Z.sup.12--,
--S(O)--, --C(O)--, --C(O)O--, --(CO)NR.sup.15, --C(O)S--,
--Z.sup.11--SiR.sup.15.sub.2--Z.sup.12--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
wherein Z.sup.11 is C.sub.1-6-alkylene, C.sub.2-6-alkenylene or
C.sub.1-6-haloalkylene, Z.sup.12 is C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
and R.sup.15 is H, C.sub.1-20-alkyl, or
--Z.sup.13--C.sub.6-14-aryl, wherein Z.sup.13 is
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, Ar.sup.7 is C.sub.6-14-aryl or monovalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 5 substituents R.sup.e, wherein R.sup.e is selected from
the group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, Ar.sup.8 and Ar.sup.9
are independently C.sub.6-14-arylene or bivalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 4 substituents R.sup.f, wherein R.sup.f is selected from the
group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, and R.sup.13 is
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl,
C.sub.1-20-alkoxy, --X.sup.6--Ar.sup.10,
--X.sup.6--Ar.sup.11--Ar.sup.10, --X.sup.6--Ar.sup.11--R.sup.16, or
--X.sup.6--Ar.sup.11--Ar.sup.12--R.sup.17, wherein X.sup.6 is
--Z.sup.14--O--Z.sup.15--, --Z.sup.14--S--Z.sup.15, --S(O)--,
--C(O)--, --C(O)O--, --(CO)NR.sup.18, --C(O)S--, --O(CO)--,
--S(CO)--, --NR.sup.18C(O)--, --NR.sup.18--,
--Z.sup.14--SiR.sup.18.sub.2--Z.sup.15--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
wherein Z.sup.14 and Z.sup.15 are independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
and R.sup.18 is H, C.sub.1-20-alkyl or --Z.sup.16--C.sub.6-14-aryl,
wherein Z.sup.16 is C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.10 is
C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 5
substituents R.sup.g, wherein R.sup.g is selected from the group
consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, Ar.sup.11 and Ar.sup.12
are independently C.sub.6-14-arylene or bivalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 4 substituents R.sup.h, wherein R.sup.h is selected from the
group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, and R.sup.17 is
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or
C.sub.1-20-alkoxy, R.sup.19 is O or C(CN).sub.2, and R.sup.20 and
R.sup.21 are independently R.sup.22 or CN, wherein R.sup.22 has the
same meaning as R.sup.1, G.sup.1 and G.sup.2 are independently
phenylene or a monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.i, wherein R.sup.i is selected from the group
consisting of a halogen, a --CN, a --NO.sub.2, a OH, a
C.sub.1-30-alkyl, a C.sub.2-30-alkenyl, a C.sub.2-30-alkynyl, a
--Z.sup.17--O--C.sub.1-30-alkyl, a --Z.sup.17--S--C.sub.1-30-alkyl,
a --Z.sup.17--C.sub.3-10-cycloalkyl, a
--Z.sup.17--C.sub.5-10-cycloalkenyl, a
--Z.sup.17--C.sub.8-10-cycloalkynyl, a --Z.sup.17--C.sub.6-14-aryl,
a --Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic
residue and a --Z.sup.17-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-30-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12
membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue are optionally substituted
with 1 to 4 substituents R.sup.j, wherein R.sup.j is selected from
the group consisting of a halogen, a --CN, a --NO.sub.2, a *.dbd.O,
a --OH, a --NH.sub.2, a --NH(C.sub.1-20-alkyl), a
--N(C.sub.1-20-alkyl).sub.2, a
--N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, a
--N(C.sub.6-14-aryl).sub.2, a --S(O).sub.mH, a
--S(O).sub.m--C.sub.1-20-alkyl, a --S(O).sub.2OH, a
--S(O).sub.m--OC.sub.1-20-alkyl, a --S(O).sub.m--OC.sub.6-14-aryl,
a --CHO, a --C(O)--C.sub.1-20-alkyl, a --C(O)--C.sub.6-14-aryl, a
--C(O)OH, a --C(O)--OC.sub.1-20-alkyl, a --C(O)--OC.sub.6-14-aryl,
a --C(O)NH.sub.2, a --C(O)NH--C.sub.1-20-alkyl, a
--C(O)N(C.sub.1-20-alkyl).sub.2, a --C(O)NH--C.sub.6-14-aryl, a
--C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, a
--C(O)N(C.sub.6-14-aryl).sub.2, a --C(S)NH.sub.2,
--C(S)NH--C.sub.1-20-alkyl, a --C(S)N(C.sub.1-20-alkyl).sub.2, a
--C(S)N(C.sub.6-14-aryl).sub.2, a
--C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, a
--C(S)NH--C.sub.6-14-aryl, a --S(O).sub.mNH.sub.2, a
--S(O).sub.mNH(C.sub.1-20-alkyl), a
--S(O).sub.mN(C.sub.1-20-alkyl).sub.2, a
--S(O).sub.mNH(C.sub.6-14-aryl), a
--S(O).sub.mN(C.sub.1-20-alkyl)-C.sub.6-14-aryl, a
--S(O).sub.mN(C.sub.6-14-aryl).sub.2, a SiH.sub.3, a
SiH(C.sub.1-20-alkyl).sub.2, a SiH.sub.2(C.sub.1-20-alkyl) and a
Si(C.sub.1-20-alkyl).sub.3, wherein m is an integer of 0, 1 or 2,
wherein C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
--C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12
membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue is optionally substituted
with 1 to 4 substituents R.sup.k, wherein R.sup.k is selected from
the group consisting of a C.sub.1-20-alkyl, a C.sub.2-20-alkenyl, a
C.sub.2-20-alkynyl, a C.sub.1-20-alkoxy, a --S--C.sub.1-20-alkyl,
and a C.sub.1-20-haloalkyl, and Z.sup.17 is C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, L
is C.sub.6-24-arylene or a bivalent 5 to 18 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.l, wherein R.sup.l is selected from the group
consisting of a halogen, a --CN, a --NO.sub.2, a *.dbd.O, a OH, a
*.dbd.C(C.sub.1-30-alkyl).sub.2, a C.sub.1-30-alkyl, a
C.sub.2-30-alkenyl, a C.sub.2-30-alkynyl, a
--Z.sup.18--O--C.sub.1-30-alkyl, a --Z.sup.18--S--C.sub.1-30-alkyl,
a --Z.sup.18--C.sub.3-10-cycloalkyl, a
--Z.sup.18--C.sub.5-10-cycloalkenyl, a
--Z.sup.18--C.sub.8-10-cycloalkynyl, a --Z.sup.18--C.sub.6-14-aryl,
a --Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic
residue and a --Z.sup.18-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-30-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12
membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue are optionally substituted
with 1 to 4 substituents R.sup.m, wherein R.sup.m is selected from
the group consisting of a halogen, a --CN, a --NO.sub.2, a *.dbd.O,
a --OH, a --NH.sub.2, a --NH(C.sub.1-20-alkyl), a
--N(C.sub.1-20-alkyl).sub.2, a
--N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, a
--N(C.sub.6-14-aryl).sub.2, a --S(O).sub.mH, a
--S(O).sub.o--C.sub.1-20-alkyl, a --S(O).sub.2OH, a
--S(O).sub.o--OC.sub.1-20-alkyl, a --S(O).sub.o--OC.sub.6-14-aryl,
a --CHO, a --C(O)--C.sub.1-20-alkyl, a --C(O)--C.sub.6-14-aryl, a
--C(O)OH, a --C(O)--OC.sub.1-20-alkyl, a --C(O)--OC.sub.6-14-aryl,
a --C(O)NH.sub.2, a --C(O)NH--C.sub.1-20-alkyl, a
--C(O)N(C.sub.1-20-alkyl).sub.2, a --C(O)NH--C.sub.6-14-aryl, a
--C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, a
--C(O)N(C.sub.6-14-aryl).sub.2, a --C(S)NH.sub.2, a
--C(S)NH--C.sub.1-20-alkyl, a --C(S)N(C.sub.1-20-alkyl).sub.2, a
--C(S)N(C.sub.6-14-aryl).sub.2, a
--C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, a
--C(S)NH--C.sub.6-14-aryl, a --S(O).sub.oNH.sub.2, a
--S(O).sub.oNH(C.sub.1-20-alkyl), a
--S(O).sub.oN(C.sub.1-20-alkyl).sub.2, a
--S(O).sub.oNH(C.sub.6-14-aryl), a
--S(O).sub.oN(C.sub.1-20-alkyl)-C.sub.6-14-aryl, a
--S(O).sub.oN(C.sub.6-14-aryl).sub.2, a SiH.sub.3, a
SiH(C.sub.1-20-alkyl).sub.2, a SiH.sub.2(C.sub.1-20-alkyl) and a
Si(C.sub.1-20-alkyl).sub.3, wherein o is an integer of 0, 1 or 2,
C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
--C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12
membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue are optionally substituted
with 1 to 4 substituents R.sup.n, wherein R.sup.n is selected from
the group consisting of a C.sub.1-20-alkyl, a C.sub.2-20-alkenyl, a
C.sub.2-20-alkynyl, a C.sub.1-20-alkoxy, a --S--C.sub.1-20-alkyl,
and a C.sub.1-20-haloalkyl, and Z.sup.18 is C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, or
L is ##STR00122## wherein R.sup.23 and R.sup.24 are independently
H, halogen, --CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12
membered aliphatic heterocyclic residue, --X.sup.7--R.sup.25,
--X.sup.8--Ar.sup.13, --X.sup.8--Ar.sup.14--Ar.sup.13,
--X.sup.8--Ar.sup.14--R.sup.26 or
--X.sup.8--Ar.sup.14--Ar.sup.15--R.sup.26, wherein X.sup.7 is
--O--, --[Z.sup.19--O].sub.c--, --[O--Z.sup.19].sub.c--O--, --S--,
--[Z.sup.19--S--].sub.c--, --[S--Z.sup.19].sub.c--S--, --S(O),
--C(O)--, --C(O)O--, --C(O)NR.sup.27--, C(O)S--, --O(CO)--,
--S(CO)--, --NR.sup.27C(O)-- or --NR.sup.27--, wherein Z.sup.19 is
C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene,
c is an integer of from 1 to 10, and R.sup.27 is H,
C.sub.1-20-alkyl, or --Z.sup.20--C.sub.6-14-aryl, wherein Z.sup.20
is C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene
or a covalent bond, R.sup.25 is C.sub.1-30-alkyl,
C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl, X.sup.8 is
--Z.sup.21--O--Z.sup.22, --Z.sup.21--S--Z.sup.22--, --S(O)--,
--C(O)--, --C(O)O--, --(CO)NR.sup.28, --C(O)S--, --O(CO)--,
--S(CO)--, --NR.sup.28C(O)--, --NR.sup.28--,
--Z.sup.21--SiR.sup.28.sub.2--Z.sup.22--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
wherein
Z.sup.21 and Z.sup.22 are C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and R.sup.28 is H,
C.sub.1-20-alkyl, or --Z.sup.23--C.sub.6-14-aryl, wherein Z.sup.23
at each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
Ar.sup.13 is C.sub.6-14-aryl or monovalent 5 to 14 membered
aromatic hetrocyclic residue, each optionally substituted with 1 to
5 substituents R.sup.o, wherein R.sup.o is selected from the group
consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, Ar.sup.14 and Ar.sup.15
are C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.p, wherein R.sup.p is selected from the group
consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, and R.sup.26 is
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl,
C.sub.1-20-alkoxy, --X.sup.9--Ar.sup.16,
--X.sup.9--Ar.sup.17--Ar.sup.16, --X.sup.9--Ar.sup.17--R.sup.29, or
X.sup.9--Ar.sup.17--Ar.sup.18--R.sup.29, wherein X.sup.9 is
--Z.sup.24--O--Z.sup.25--, --Z.sup.24--S--Z.sup.25, --S(O)--,
--C(O)--, --C(O)O--, --(CO)NR.sup.30, --C(O)S--, --O(CO)--,
--S(CO)--, --NR.sup.30C(O)--, --NR.sup.30--,
--Z.sup.24--SiR.sup.30.sub.2--Z.sup.25--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
wherein Z.sup.24 and Z.sup.25 are independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
and R.sup.30 is H, C.sub.1-20-alkyl or --Z.sup.26--C.sub.6-14-aryl,
wherein Z.sup.26 is C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.16 is
C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 5
substituents R.sup.q, wherein R.sup.q is selected from the group
consisting of a halogen, CN, a C.sub.1-6-alkyl, a C.sub.1-6-alkoxy
and a C.sub.1-6-haloalkyl, Ar.sup.17 and Ar.sup.18 are
independently C.sub.6-14-arylene or bivalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 4 substituents R.sup.r, wherein R.sup.r is selected from the
group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, and R.sup.29 is
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or
C.sub.1-20-alkoxy, q and s are independently an integer of 0, 1, 2,
3, 4 or 5, r is an integer of 0, 1 or 2, and n is an integer of
from 1 to 10,000.
2. The compound of claim 1, wherein A.sup.1 and A.sup.2 are S.
3. The compound of claim 1, wherein E is selected from the group
consisting of ##STR00123##
4. The compound of claim 1, wherein E is ##STR00124##
5. The compound of claim 1, wherein E is ##STR00125##
6. The compound of claim 1, wherein R.sup.1 and R.sup.2 are
independently H, C.sub.1-30-alkyl, C.sub.1-30-haloalkyl,
--X.sup.1--R.sup.6 or --X.sup.2--Ar.sup.1, wherein X.sup.1 is
--[Z.sup.1--O].sub.a--, --[Z.sup.1--S--].sub.a--, or
--[S--Z.sup.1].sub.a--S--, wherein Z.sup.1 is C.sub.1-6-alkylene or
C.sub.1-6-haloalkylene, and a is an integer of from 1 to 10,
R.sup.6 is C.sub.1-30-alkyl or C.sub.1-30-haloalkyl, X.sup.2 is
--Z.sup.3--O--Z.sup.4--, --Z.sup.3--S--Z.sup.4--,
C.sub.1-30-alkylene or C.sub.1-30-haloalkylene, wherein Z.sup.3 and
Z.sup.4 are independently C.sub.1-6-alkylene or
C.sub.1-6-haloalkylene, and Ar.sup.1 is C.sub.6-14-aryl, optionally
substituted with 1 to 5 substituents R.sup.a, wherein R.sup.a is
selected from the group consisting of a halogen, a C.sub.1-6-alkyl,
and a C.sub.1-6-alkoxy.
7. The compound of claim 1, wherein R.sup.1 and R.sup.2 are
independently a C.sub.1-30-alkyl.
8. The compound of claim 1, wherein R.sup.3 is --X.sup.5--Ar.sup.7,
--X.sup.5--Ar.sup.8--Ar.sup.7, --X.sup.5--Ar.sup.8--R.sup.13 or
--X.sup.5--Ar.sup.8--Ar.sup.9--R.sup.13, wherein X.sup.5 is a
covalent bond, Ar.sup.7 is C.sub.6-14-aryl or monovalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 5 substituents R.sup.e, wherein R.sup.e is selected from
the group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, Ar.sup.8 and Ar.sup.9
are independently C.sub.6-14-arylene or bivalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 4 substituents R.sup.f, wherein R.sup.f is selected from the
group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, and R.sup.13 is
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or
C.sub.1-20-alkoxy.
9. The compound of claim 1, wherein R.sup.3 is
--X.sup.5--Ar.sup.8--R.sup.13, wherein X.sup.5 is a covalent bond,
Ar.sup.8 is C.sub.6-14-arylene, and R.sup.13 is
C.sub.1-20-alkyl.
10. The compound of claim 1, wherein G.sup.1 and G.sup.2 are
independently a phenylene or, a monocyclic bivalent 5 to 8 membered
aromatic heterocyclic residue selected from the group consisting of
##STR00126## wherein phenylene or monocyclic bivalent 5 to 8
membered aromatic heterocyclic residue are optionally substituted
with 1 to 2 substituents R.sup.i, wherein R.sup.i is selected from
the group consisting of a C.sub.1-30-alkyl, a
--Z.sup.17--O--C.sub.1-30-alkyl, a --Z.sup.17--S--C.sub.1-30-alkyl,
a --Z.sup.17--C.sub.3-10-cycloalkyl, a --Z.sup.17--C.sub.6-14-aryl,
a --Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic
residue and a --Z.sup.17-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue are optionally substituted with 1 to
4 substituents wherein is independently selected from the group
consisting of a halogen, a --CN and a *.dbd.O,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue are optionally substituted with 1 to
4 substituents R.sup.k, wherein R.sup.k is independently selected
from the group consisting of a C.sub.1-20-alkyl, a
C.sub.1-20-alkoxy, and a C.sub.1-20-haloalkyl, and Z.sup.17 is
C.sub.1-6-alkylene, C.sub.1-6-haloalkylene or a covalent bond.
11. The compound of claim 1, wherein G.sup.1 and G.sup.2 are
independently a monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue ##STR00127## which is substituted with 1 to 2
substituents R.sup.i, wherein R.sup.i is selected from the group
consisting of a C.sub.1-30-alkyl and a --Z.sup.17--C.sub.6-14-aryl,
wherein C.sub.1-30-alkyl and C.sub.6-14-aryl are optionally
substituted with 1 to 4 substituents R.sup.j, wherein R.sup.j is
selected from the group consisting of a halogen, a --CN and a
*.dbd.O, C.sub.6-14-aryl is optionally substituted with 1 to 4
substituents R.sup.k, wherein R.sup.k is selected from the group
consisting of a C.sub.1-20-alkyl and a C.sub.1-20-alkoxy, and
Z.sup.17 is a covalent bond.
12. The compound of claim 1, wherein R.sup.i is
C.sub.1-30-alkyl.
13. The compound of claim 1, wherein L is a bivalent 5 to 18
membered aromatic heterocyclic residue optionally substituted with
1 to 4 substituents R.sup.l, wherein R.sup.l is selected from the
group consisting of a C.sub.1-30-alkyl, a
--Z.sup.18--O--C.sub.1-30-alkyl, a --Z.sup.18--S--C.sub.1-30-alkyl,
a --Z.sup.18--C.sub.3-10-cycloalkyl, a --Z.sup.18--C.sub.6-14-aryl,
a --Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic
residue and a --Z.sup.18-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue is optionally substituted with 1 to 4
substituents R.sup.m, wherein R.sup.m is selected from the group
consisting of a halogen, a --CN and a *.dbd.O,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue is optionally substituted with 1 to 4
substituents R.sup.n, wherein R.sup.n is selected from the group
consisting of a C.sub.1-20-alkyl, a C.sub.1-20-alkoxy, and a
C.sub.1-20-haloalkyl, and Z.sup.18 is C.sub.1-6-alkylene,
C.sub.1-6-haloalkylene or a covalent bond, or L is ##STR00128##
wherein R.sup.23 and R.sup.24 are independently H, halogen, --CN,
C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.1-30-haloalkyl,
--X.sup.7--R.sup.25, --X.sup.8--Ar.sup.13,
--X.sup.8--Ar.sup.14--Ar.sup.13, --X.sup.8--Ar.sup.14--R.sup.26 or
--X.sup.8--Ar.sup.14--Ar.sup.15--R.sup.26, wherein X.sup.7 is
--O--, --[Z.sup.19--O].sub.c--, --[O--Z.sup.19].sub.c--O--, --S--,
--[Z.sup.19--S].sub.c-- or --[S--Z.sup.19].sub.c--S--, wherein
Z.sup.19 is C.sub.1-6-alkylene, C.sub.2-6-alkenylene or
C.sub.1-6-haloalkylene, and c is an integer of from 1 to 10,
R.sup.25 is C.sub.1-30-alkyl, C.sub.2-30-alkenyl or
C.sub.1-30-haloalkyl, X.sup.8 is Z.sup.21--O--Z.sup.22--,
--Z.sup.21--S--Z.sup.22--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
wherein Z.sup.21 and Z.sup.22 re independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
Ar.sup.13 is C.sub.6-14-aryl or monovalent 5 to 14 membered
aromatic hetrocyclic residue, each optionally substituted with 1 to
5 substituents R.sup.o, wherein R.sup.o is selected from the group
consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, Ar.sup.14 and Ar.sup.15
are independently C.sub.6-14-arylene or bivalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 4 substituents R.sup.p, wherein R.sup.p is selected from the
group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, and R.sup.26 is
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or
C.sub.1-20-alkoxy.
14. The compound of claim 1, wherein L is a bivalent 5 to 18
membered aromatic heterocyclic residue selected from the group
consisting of ##STR00129## ##STR00130## wherein the bivalent 5 to
18 membered aromatic heterocyclic residue is optionally substituted
with 1 to 4 substituents wherein R.sup.l is selected from the group
consisting of a C.sub.1-30-alkyl, a
--Z.sup.18--O--C.sub.1-30-alkyl, a --Z.sup.18--S--C.sub.1-30-alkyl,
a --Z.sup.18--C.sub.3-10-cycloalkyl, a --Z.sup.18--C.sub.6-14-aryl,
a --Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic
residue and a --Z.sup.18-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue is optionally substituted with 1 to 4
substituents R.sup.m, wherein R.sup.m is selected from the group
consisting of a halogen, a --CN and a *.dbd.O,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue is optionally substituted with 1 to 4
substituents R.sup.n, wherein R.sup.n is selected from the group
consisting of a C.sub.1-20-alkyl, a C.sub.1-20-alkoxy, and a
C.sub.1-20-haloalkyl, and Z.sup.18 is C.sub.1-6-alkylene,
C.sub.1-6-haloalkylene or a covalent bond, and R.sup.t is hydrogen
or C.sub.1-30-alkyl, or L is ##STR00131## wherein R.sup.23 and
R.sup.24 are independently H, halogen, --CN, C.sub.1-30-alkyl,
C.sub.2-30-alkenyl, C.sub.1-30-haloalkyl, --X.sup.7--R.sup.25,
--X.sup.8--Ar.sup.13, --X.sup.8--Ar.sup.14--Ar.sup.13,
--X.sup.8--Ar.sup.14--R.sup.26 or
--X.sup.8--Ar.sup.14--Ar.sup.15--R.sup.26, wherein X.sup.7 is
--O--, --[Z.sup.19--O].sub.c--, --[O--Z.sup.19].sub.c--O--, --S--,
--[Z.sup.19--S--].sub.c-- or --[S--Z.sup.19].sub.c--S--, wherein
Z.sup.19 is C.sub.1-6-alkylene, C.sub.1-6-alkenylene or
C.sub.1-6-haloalkylene, and c is an integer of from 1 to 10,
R.sup.25 is C.sub.1-30-alkyl, C.sub.2-30-alkenyl or
C.sub.1-30-haloalkyl, X.sup.8 is --Z.sup.21--O--Z.sup.22--,
--Z.sup.21--S--Z.sup.22--, C.sub.1-30-alkylene,
C.sub.1-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
wherein Z.sup.21 and Z.sup.22 are independently C.sub.1-6-alkylene,
C.sub.1-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
Ar.sup.13 is C.sub.6-14-aryl or monovalent 5 to 14 membered
aromatic hetrocyclic residue, each optionally substituted with 1 to
5 substituents R.sup.o, wherein R.sup.o is selected from the group
consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, Ar.sup.14 and Ar.sup.15
are independently C.sub.6-14-arylene or bivalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 4 substituents R.sup.p, wherein R.sup.p is selected from the
group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, and R.sup.26 is
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or
C.sub.1-20-alkoxy.
15. The compound of claim 1, wherein L is ##STR00132## wherein
R.sup.1 is selected from the group consisting of a
C.sub.1-30-alkyl, a --Z.sup.18--O--C.sub.1-30-alkyl, a
--Z.sup.18--S--C.sub.1-30-alkyl, a
--Z.sup.18--C.sub.3-10-cycloalkyl, a --Z.sup.18--C.sub.6-14-aryl, a
--Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic
residue and a --Z.sup.18-monovalent 5 to 14 membered aromatic
heterocyclic residue. wherein C.sub.1-30-alkyl,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue is optionally substituted with 1 to 4
substituents R.sup.m, wherein R.sup.m is selected from the group
consisting of a halogen, a --CN and a *.dbd.O,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue is optionally substituted with 1 to 4
substituents R.sup.n, wherein R.sup.n is selected from the group
consisting of a C.sub.1-20-alkyl, a C.sub.1-20-alkoxy, and a
C.sub.1-20-haloalkyl, and Z.sup.18 is C.sub.1-6-alkylene,
C.sub.1-6-haloalkylene or a covalent bond, or L is ##STR00133##
wherein R.sup.23 and R.sup.24 are independently H, halogen, --CN,
C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.1-30-haloalkyl,
--X.sup.7--R.sup.25, --X.sup.8--Ar.sup.13,
--X.sup.8--Ar.sup.14--Ar.sup.13, --X.sup.8--Ar.sup.14--R.sup.26 or
--X.sup.8--Ar.sup.14--Ar.sup.15--R.sup.26, wherein X.sup.7 is
--O--, --[Z.sup.19--O].sub.c--, --[O--Z.sup.19].sub.c--O--, --S--,
--[Z.sup.19--S--].sub.c-- or --[S--Z.sup.19].sub.c--S--, wherein
Z.sup.19 is C.sub.1-6-alkylene, C.sub.2-6-alkenylene or
C.sub.1-6-haloalkylene, and c is an integer of from 1 to 10,
R.sup.25 is C.sub.3-30-alkyl, C.sub.2-30-alkenyl or
C.sub.1-30-haloalkyl. X.sup.8 is Z.sup.21--O--Z.sup.22--,
--Z.sup.21--S--Z.sup.22--, C.sub.1-30-alkylene,
C.sub.1-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
wherein Z.sup.21 and Z.sup.22 are independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
Ar.sup.13 is C.sub.6-14-aryl or monovalent 5 to 14 membered
aromatic hetrocyclic residue, each optionally substituted with 1 to
5 substituents R.sup.o, wherein R.sup.o is selected from the group
consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, Ar.sup.14 and Ar.sup.15
are independently C.sub.6-14-arylene or bivalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 4 substituents R.sup.p, wherein R.sup.p is selected from the
group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a
C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, and R.sup.26 is
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or
C.sub.1-20-alkoxy.
16. The compound of claim 1, wherein R.sup.l is selected from the
group consisting of a C.sub.1-30-alkyl and a
--Z.sup.18--C.sub.6-14-aryl, wherein C.sub.1-30-alkyl and
C.sub.6-14-aryl are optionally substituted with 1 to 4 substituents
R.sup.m, wherein R.sup.m is selected from the group consisting of a
halogen, a --CN and a *.dbd.O, C.sub.6-14-aryl is optionally
substituted with 1 to 4 substituents R.sup.n, wherein R.sup.n is
selected from the group consisting of a C.sub.1-20-alkyl and a
C.sub.1-20-alkoxy, and Z.sup.18 is a covalent bond, and R.sup.23
and R.sup.24 are independently H, C.sub.1-30-alkyl,
C.sub.1-30-haloalkyl, --X.sup.7--R.sup.25 or --X.sup.8--Ar.sup.13,
wherein X.sup.7 is --[Z.sup.19--O].sub.c--,
--[Z.sup.19--S--].sub.c--, or --[S--Z.sup.19].sub.c--S--, wherein
Z.sup.19 is C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, and c is
an integer of from 1 to 10, R.sup.25 is C.sub.1-30-alkyl or
C.sub.1-30-haloalkyl, X.sup.8 is --Z.sup.21--O--Z.sup.22--,
--Z.sup.21--S--Z.sup.22--, C.sub.1-30-alkylene or
C.sub.1-30-haloalkylene, wherein Z.sup.21 and Z.sup.22 are
independently C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, and
Ar.sup.13 is C.sub.6-14-aryl, optionally substituted with 1 to 5
substituents R.sup.o, wherein R.sup.o is selected from the group
consisting of a halogen C.sub.1-6-alkyl and a C.sub.1-6-alkoxy.
17. The compound of claim 1, wherein R.sup.l is C.sub.1-30-alkyl,
and R.sup.23 and R.sup.24 are independently H, C.sub.1-30-alkyl or
C.sub.1-30-haloalkyl.
18. The compound of claim 1, wherein q, r and s are an integer of 0
or 1, and q, r and s are not all 0 at the same time.
19. The compound of claim 1, wherein n is an integer of from 1 to
5000.
20. An electronic device comprising the compound of claim 1.
21. The electronic device of claim 20, wherein the electronic
device is an organic field effect transistor.
22. An organic semiconducting material comprising the compound of
claim 1.
Description
[0001] Organic semiconducting materials can be used in electronic
devices such as organic photovoltaic (OPV) cells, organic
field-effect transistors (OFETs) and organic light emitting diodes
(OLEDs).
[0002] It is desirable that the organic semiconducting materials
are compatible with liquid processing techniques such as spin
coating, solution casting or printing. Liquid processing techniques
are convenient from the point of processability, and can also be
applied to plastic substrates. Thus, organic semiconducting
materials which are compatible with liquid processing techniques
allow the production of low cost, light weight and, optionally also
flexible, electronic devices, which is a clear advantage of these
organic semiconducting materials compared to inorganic
semiconducting materials.
[0003] Furthermore, it is desirable that the organic semiconducting
materials are stable, in particular towards oxidation.
[0004] When used in organic field-effect transistors (OFETs), the
organic semiconducting materials should show a high charge carrier
mobility and a high on/off ratio.
[0005] The use of organic semiconducting materials in electronic
devices, in particular in organic field effect transistors (OFETs)
is known in the art.
[0006] Fuchigami, H.; Tsumura, A.; Koezuka, H. Appl. Phys. Lett.
1993, 63, 1372-1374 describes the use of
poly(2,5-thienylenevinylene) in field-effect transistors.
[0007] Bao, Z.; Dobadalapur, A.; Lovinger, A. J. Appl. Phys. Lett.
1996, 69, 4108-4110 describes the use of regioregular
poly(3-hexylthiophene) in field-effect transistors.
[0008] Zhang, M.; Tsao, H. N.; Pisula, W.; Yang, C.; Mishra, A. K.;
Mullen, K. J. Am. Chem. Soc. 2007, 129, 3472-3473 describes
polymers of formula
##STR00002##
for use in organic field effect transistors (OFETs).
[0009] Xiao, S; Zhou H.; You, W. Macromolecules 2008, 41, 5688-5696
describes the following polymers
##STR00003##
as donor materials for use in photovoltaic devices.
[0010] Scharber, M. C.; Koppe, M.; Gao, J.; Cordella, F.; Loi, M.
A.; Denk, P.; Morana, M.; Egelhaaf, H.-J.; Forberich, K.; Dennler,
G.; Gaudiana, R.; Waller, D.; Zhu, Z.; Shi, X.; Brabec, C. J. Adv.
Mater. 2009, 21, 1-4 describes the following polymers
##STR00004##
as donor materials for use in solar cells.
[0011] Rieger, R.; Beckmann, D.; Pisula, W.; Steffen, W.; Kastler,
M.; Mullen K. Adv. Mater. 2010, 22, 83-86 describes the following
polymers
##STR00005##
for use in organic field-effect transistor (OFET).
[0012] Kim, D. H.; Lee, B.-L-; Moon, H.; Kang, H. M.; Jeong, E. J.;
Park, J.; Han, K.-M.; Lee, S.; Yoo, B. W.; Koo, B. W.; Kim, J. Y.;
Lee, W. H.; Cho, K.; Becerril, H. A.; Z. Bao Z. J. Am. Chem. Soc.
2009, 131, 6124-6132 describes the polymer
##STR00006##
for use in organic field effect transistors (OFETs).
[0013] Osaka, I.; Sauve, G.; Zhang, R.; Kowalewski, T.; McCullough
R. D. Adv. Mater. 2007, 19, 4160-4165 describes the polymers
##STR00007##
for use in organic field effect transistors (OFETs).
[0014] EP 2 085 401 A1 describes benzobisthiazole polymers
comprising a unit having the following formula
##STR00008##
wherein each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represents a
hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl
group, a substituted or unsubstituted alkoxy group or a substituted
or unsubstituted thioalkoxy group, wherein at least one of R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 is not a hydrogen atom, and n is a
positive integer, wherein when n is 2 or more, each of R.sup.3 is
the same as or different from the others and each of R.sup.4 is the
same or different from the others, for use in transistors.
[0015] US 2008/0121281 A1 describes photovoltaic cells with
thiazole-containing polymers such as bithiazole-containing
polymers, cyclopentadithiazole-containing polymers or
thiazolothiazole-containing polymers.
Cyclopentadithiazole-containing polymers can be polymers which
include a first comonomer repeat unit comprising a
cyclopentadithiazole moiety, and a second comonomer repeat unit
different from the first comonomer repeat unit. In some
embodiments, the first comonomer repeat unit includes a
cyclopentadithiazole moiety of formula
##STR00009##
in which each of R.sup.1 and R.sup.2, independently, is H,
C.sub.1-20-alkyl, C.sub.1-20-alkoxy, C.sub.3-20-cycloalkyl,
C.sub.1-20-heterocycloalkyl, aryl, heteroaryl, halo, CN, OR, C(O)R,
C(O)OR, or SO.sub.2R; R being H, C.sub.1-20-alkyl,
C.sub.1-20-alkoxy, C.sub.3-20-cycloalkyl,
C.sub.1-20-heterocycloalkyl, aryl, or heteroaryl.
[0016] WO 2009/069687 describes a polymer represented by the
general formula
##STR00010##
wherein Z.sup.21 and Z.sup.22 independently represent, for example,
--S--.
[0017] It is the object of the present invention to provide organic
semiconducting materials suitable for use in electronic devices, in
particular in organic field effect transistors (OFETs), where the
organic semiconducting materials show a high oxidative stability,
particularly in ambient conditions, and are compatible with liquid
processing techniques. The organic field effect transistors
comprising the organic semiconducting materials should show an
acceptable charge carrier mobility and current on/off ratio.
[0018] This object is solved by the compound, oligomer or polymer
of claim 1 and the electronic device of claim 19.
[0019] The compound, oligomer or polymer of the present invention
are of formula
##STR00011##
wherein A.sup.1 and A.sup.2 can be the same or different and are S
or Se, E is selected from the group consisting of
##STR00012## [0020] wherein [0021] R.sup.1 and R.sup.2 can be the
same or different and are H, halogen, --CN, C.sub.1-30-alkyl,
C.sub.2-30-alkenyl, C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl,
C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl,
C.sub.1-30-haloalkyl, monovalent 3 to 12 membered aliphatic
heterocyclic residue, --X.sup.1--R.sup.6, --X.sup.2--Ar.sup.1,
--X.sup.2--Ar.sup.2--Ar.sup.1, --X.sup.2--Ar.sup.2--R.sup.7 or
--X.sup.2--Ar.sup.2--Ar.sup.3--R.sup.7, [0022] wherein [0023]
X.sup.1 at each occurrence is independently --O--,
--[Z.sup.1--O].sub.a--, --[O--Z.sup.1].sub.a--O--, --S--,
--[Z.sup.1--S--].sub.a--, --[S--Z.sup.1].sub.a--S--, --S(O),
--C(O)--, --C(O)O--, --C(O)NR.sup.8--, C(O)S--, --O(CO)--,
--S(CO)--, --NR.sup.8C(O)-- or --NR.sup.8--, [0024] wherein [0025]
Z.sup.1 at each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, [0026] a at each
occurrence is independently an integer from 1 to 10 and [0027]
R.sup.8 at each occurrence is independently H, C.sub.1-20-alkyl, or
--Z.sup.2--C.sub.6-14-aryl, [0028] wherein [0029] Z.sup.2 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0030] R.sup.6 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0031] X.sup.2 at each occurrence is independently
--Z.sup.3--O--Z.sup.4--, --Z.sup.3--S--Z.sup.4--, --S(O)--,
--C(O)--, --C(O)O--, --(CO)NR.sup.9, --C(O)S--, --C(O)--, --S(O)--,
--NR.sup.9C(O)--, --NR.sup.9--,
--Z.sup.3--SiR.sup.9.sub.2--Z.sup.4--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0032] wherein [0033] Z.sup.3 and Z.sup.4 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0034] R.sup.9 at
each occurrence is independently H, C.sub.1-20-alkyl, or
--Z.sup.5--C.sub.6-14-aryl, [0035] wherein [0036] Z.sup.5 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0037] Ar.sup.1 at each occurrence is independently C.sub.6-14-aryl
or monovalent 5 to 14 membered aromatic hetrocyclic residue, each
optionally substituted with 1 to 5 substituents R.sup.a, wherein
each R.sup.a is independently selected from the group consisting of
halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and
C.sub.1-6-haloalkyl, [0038] Ar.sup.2 and Ar.sup.3 at each
occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 4 substituents R.sup.b, wherein each R.sup.b is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and
[0039] R.sup.7 at each occurrence is independently
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl,
C.sub.1-20-alkoxy, --X.sup.3--Ar.sup.4,
--X.sup.3--Ar.sup.5--Ar.sup.4, --X.sup.3--Ar.sup.5--R.sup.10, or
--X.sup.3--Ar.sup.5--Ar.sup.6--R.sup.10, [0040] wherein [0041]
X.sup.3 at each occurrence is independently
--Z.sup.6--O--Z.sup.7--, --Z.sup.6--S--Z.sup.7, --S(O)--, --C(O)--,
--C(O)O--, --(CO)NR.sup.11, --C(O)S--, --C(O)--, --S(O)--,
--NR.sup.11C(O)--, --NR.sup.11--,
--Z.sup.6--SiR.sup.11.sub.2--Z.sup.7--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0042] wherein [0043] Z.sup.6 and Z.sup.7 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0044] R.sup.11 at
each occurrence is independently H, C.sub.1-20-alkyl or
--Z.sup.8--C.sub.6-14-aryl, wherein Z.sup.8 at each occurrence is
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, [0045] Ar.sup.4 at each
occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 5 substituents R.sup.c, wherein each R.sup.c is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0046]
Ar.sup.5 and Ar.sup.6 at each occurrence are independently
C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.d, wherein each R.sup.d is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and [0047] R.sup.10 at
each occurrence is independently C.sub.1-20-alkyl,
C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy,
[0048] R.sup.3, R.sup.4 and R.sup.5 can be the same or different
and are H, halogen, --CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12
membered aliphatic heterocyclic residue, --X.sup.4--R.sup.12,
--X.sup.5--Ar.sup.7, --X.sup.5--Ar.sup.8--Ar.sup.7,
--X.sup.5--Ar.sup.8--R.sup.13 or
--X.sup.5--Ar.sup.8--Ar.sup.9--R.sup.13, [0049] wherein [0050]
X.sup.4 at each occurrence is independently --[Z.sup.9--O].sub.b--,
--[Z.sup.9--S--].sub.b--, --S(O)--, --C(O)--, --C(O)O--,
--C(O)NR.sup.14-- or C(O)S--, [0051] wherein [0052] Z.sup.9 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, [0053] b at each
occurrence is independently an integer from 1 to 10 and [0054]
R.sup.14 at each occurrence is independently H, C.sub.1-20-alkyl,
or --Z.sup.10--C.sub.6-14-aryl, [0055] wherein [0056] Z.sup.10 at
each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0057] R.sup.12 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0058] X.sup.5 at each occurrence is independently
--Z.sup.11--O--Z.sup.12, --Z.sup.11--S--Z.sup.12--, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.15, --C(O)S--,
--Z.sup.11--SiR.sup.15.sub.2--Z.sup.12--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0059] wherein [0060] Z.sup.11 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene,
[0061] Z.sup.12 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, and [0062] R.sup.15 at each occurrence is
independently H, C.sub.1-20-alkyl, or --Z.sup.13--C.sub.6-14-aryl,
[0063] wherein [0064] Z.sup.13 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, [0065] Ar.sup.7 at each occurrence is
independently C.sub.6-14-aryl or monovalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 5 substituents R.sup.e, wherein each R.sup.e is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0066] Ar.sup.8 and
Ar.sup.9 at each occurrence are independently C.sub.6-14-arylene or
bivalent 5 to 14 membered aromatic heterocyclic residue, each
optionally substituted with 1 to 4 substituents R.sup.f, wherein
each R.sup.f is independently selected from the group consisting of
halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and
C.sub.1-6-haloalkyl and [0067] R.sup.13 at each occurrence is
independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.1-20-haloalkyl, C.sub.1-20-alkoxy, --X.sup.6--Ar.sup.10,
--X.sup.6--Ar.sup.11--Ar.sup.10, --X.sup.6--Ar.sup.11--R.sup.16, or
--X.sup.6--Ar.sup.11--Ar.sup.12--R.sup.17, [0068] wherein [0069]
X.sup.6 at each occurrence is independently
--Z.sup.1--O--Z.sup.15--, --Z.sup.14--S--Z.sup.15, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.18, --C(O)S--, --C(O)--,
--S(O)--, --NR.sup.18C(O)--, --NR.sup.18--,
--Z.sup.14--SiR.sup.18.sub.2--Z.sup.15--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0070] wherein [0071] Z.sup.14 and Z.sup.15 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0072] R.sup.18 at
each occurrence is independently H, C.sub.1-20-alkyl or
--Z.sup.16--C.sub.6-14-aryl, wherein Z.sup.16 at each occurrence is
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, [0073] Ar.sup.10 at each
occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 5 substituents R.sup.g, wherein each R.sup.g is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0074]
Ar.sup.11 and Ar.sup.12 at each occurrence are independently
C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.h, wherein each R.sup.h is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl and [0075] R.sup.17 at
each occurrence is independently C.sub.1-20-alkyl,
C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy,
[0076] R.sup.19 is O or C(CN).sub.2, and [0077] R.sup.20 and
R.sup.21 are the same or different and are R.sup.22 or CN, [0078]
wherein R.sup.22 has the same meaning as R.sup.1, G.sup.1 and
G.sup.2 are the same or different and are phenylene or a monocyclic
bivalent 5 to 8 membered aromatic heterocyclic residue, which
phenylene and monocyclic bivalent to 8 membered aromatic
heterocyclic residue are optionally substituted with 1 to 4
substituents R, wherein each R is independently selected from the
group consisting of halogen, --CN, --NO.sub.2, --OH,
C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl,
Z.sup.17--O--C.sub.1-30-alkyl, --Z.sup.17--S--C.sub.1-30-alkyl,
--Z.sup.17--C.sub.3-10-cycloalkyl,
--Z.sup.17--C.sub.5-10-cycloalkenyl,
--Z.sup.17--C.sub.8-10-cycloalkynyl, --Z.sup.17--C.sub.6-14-aryl,
--Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.17-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-30-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12
membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue is optionally substituted
with 1 to 4 substituents R, wherein each R is independently
selected from the group consisting of halogen, --CN, --NO.sub.2,
*.dbd.O, --OH, --NH.sub.2, --NH(C.sub.1-20-alkyl),
--N(C.sub.1-20-alkyl).sub.2, --N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--N(C.sub.6-14-aryl).sub.2, --S(O).sub.mH,
--S(O).sub.m--C.sub.1-20-alkyl, --S(O).sub.2OH,
--S(O).sub.m--OC.sub.1-20-alkyl, --S(O).sub.m--OC.sub.1-14-aryl,
--CHO, --C(O)--C.sub.1-20-alkyl, --C(O)--C.sub.6-14-aryl, --C(O)OH,
--C(O)--OC.sub.1-20-alkyl, --C(O)--CO.sub.6-14-aryl,
--C(O)NH.sub.2, --C(O)NH--C.sub.1-20-alkyl,
--C(O)N(C.sub.1-20-alkyl).sub.2, --C(O)NH--C.sub.6-14-aryl,
--C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(O)N(C.sub.6-14-aryl).sub.2, --C(S)NH.sub.2,
--C(S)NH--C.sub.1-20-alkyl, --C(S)N(C.sub.1-20-alkyl).sub.2,
--C(S)N(C.sub.6-14-aryl).sub.2,
--C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(S)NH--C.sub.6-14-aryl, --S(O).sub.mNH.sub.2,
--S(O).sub.mNH(C.sub.1-20-alkyl),
--S(O).sub.mN(C.sub.1-20-alkyl).sub.2,
--S(O).sub.mNH(C.sub.6-14-aryl),
--S(O).sub.mN(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--S(O).sub.mN(C.sub.6-14-aryl).sub.2, SiH.sub.3,
SiH(C.sub.1-20-alkyl).sub.2, SiH.sub.2(C.sub.1-20-alkyl) and
Si(C.sub.1-20-alkyl).sub.3, and wherein C.sub.3-10-cycloalkyl,
C.sub.5-10-cycloalkenyl, --C.sub.8-10-cycloalkynyl,
C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic
residue and monovalent 5 to 14 membered aromatic heterocyclic
residue is optionally substituted with 1 to 4 substituents R.sup.k,
wherein each R.sup.k is independently selected from the group
consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.2-20-alkynyl, C.sub.1-20-alkoxy, C.sub.1-20-haloalkyl, [0079]
wherein [0080] Z.sup.17 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, and [0081] m at each occurrence is independently
0, 1 or 2, L is C.sub.6-24-arylene or a bivalent 5 to 18 membered
aromatic heterocyclic residue, wherein C.sub.6-24-arylene and
bivalent 5 to 18 membered aromatic heterocyclic residue are
optionally substituted with 1 to 4 substituents R.sup.l, wherein
each R.sup.l is independently selected from the group consisting of
halogen, --CN, --NO.sub.2, *.dbd.O, OH,
*.dbd.C(C.sub.1-30-alkyl).sub.2, C.sub.1-30-alkyl,
C.sub.2-30-alkenyl, C.sub.2-30-alkynyl,
--Z.sup.18--O--C.sub.1-30-alkyl, --Z.sup.18--S--C.sub.1-30-alkyl,
--Z.sup.18--C.sub.3-10-cycloalkyl,
--Z.sup.18--C.sub.5-10-cycloalkenyl,
--Z.sup.18--C.sub.8-10-cycloalkynyl, --Z.sup.18--C.sub.6-14-aryl,
--Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.18-monovalent to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-30-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12
membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue is optionally substituted
with 1 to 4 substituents R.sup.m, wherein each R.sup.m is
independently selected from the group consisting of halogen, --CN,
--NO.sub.2, *.dbd.O, --OH, --NH.sub.2, --NH(C.sub.1-20-alkyl),
--N(C.sub.1-20-alkyl).sub.2, --N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--N(C.sub.6-14-aryl).sub.2, --S(O).sub.oH,
--S(O).sub.o--C.sub.1-20-alkyl, --S(O).sub.2OH,
--S(O).sub.o--C.sub.1-20-alkyl, --S(O).sub.o--OC.sub.6-14-aryl,
--CHO, --C(O)--C.sub.1-20-alkyl, --C(O)--C.sub.6-14-aryl, --C(O)OH,
--C(O)--OC.sub.1-20-alkyl, --C(O)--OC.sub.6-14-aryl,
--C(O)NH.sub.2, --C(O)NH--C.sub.1-20-alkyl,
--C(O)N(C.sub.1-20-alkyl).sub.2, --C(O)NH--C.sub.6-14-aryl,
--C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(O)N(C.sub.6-14-aryl).sub.2, --C(S)NH.sub.2,
--C(S)NH--C.sub.1-20-alkyl, --C(S)N(C.sub.1-20-alkyl).sub.2,
--C(S)N(C.sub.6-14-aryl).sub.2,
--C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(S)NH--C.sub.6-14-aryl, --S(O).sub.oNH.sub.2,
--S(O)ONH(C.sub.1-20-alkyl), --S(O).sub.oN(C.sub.1-20-alkyl).sub.2,
--S(O)ONH(C.sub.6-14-aryl),
--S(O).sub.oN(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--S(O).sub.oN(C.sub.6-14-aryl).sub.2, SiH.sub.3,
SiH(C.sub.1-20-alkyl).sub.2, SiH.sub.2(C.sub.1-20-alkyl) and
Si(C.sub.1-20-alkyl).sub.3, and wherein C.sub.3-10-cycloalkyl,
C.sub.5-10-cycloalkenyl, --C.sub.8-10-cycloalkynyl,
C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic
residue and monovalent 5 to 14 membered aromatic heterocyclic
residue is optionally substituted with 1 to 4 substituents R.sup.n,
wherein each R
.sup.n is independently selected from the group consisting of
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl,
C.sub.1-20-alkoxy, --S--C.sub.1-20-alkyl, C.sub.1-20-haloalkyl,
wherein Z.sup.18 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, and o at each occurrence is independently 0, 1 or
2, or
L is
[0082] ##STR00013## [0083] wherein [0084] R.sup.23 and R.sup.24 can
be the same or different and are H, halogen, --CN, C.sub.1-30
alkyl, C.sub.2-30-alkenyl, C.sub.2-20-alkynyl,
C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12
membered aliphatic heterocyclic residue, --X.sup.7--R.sup.25,
--X.sup.8--Ar.sup.13, --X.sup.8--Ar.sup.14--Ar.sup.13,
--X.sup.8--Ar.sup.14--R.sup.26 or
--X.sup.8--Ar.sup.14--Ar.sup.15--R.sup.26, [0085] wherein [0086]
X.sup.7 at each occurrence is independently --O--,
--[Z.sup.19--O].sub.c--, [O--Z.sup.19].sub.c--O--, --S--,
--[Z.sup.19--S--].sub.c--, --[S--Z.sup.19].sub.c--S--, --S(O),
--C(O)--, --C(O)O--, --C(O)NR.sup.27--, C(O)S--, --C(O)--,
--S(O)--, --NR.sup.27C(O)-- or --NR.sup.27--, [0087] wherein [0088]
Z.sup.19 at each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, [0089] c at each
occurrence is independently an integer from 1 to 10 and [0090]
R.sup.27 at each occurrence is independently H, C.sub.1-20-alkyl,
or --Z.sup.20--C.sub.6-14-aryl, [0091] wherein [0092] Z.sup.20 at
each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0093] R.sup.25 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0094] X.sup.8 at each occurrence is independently
--Z.sup.21--O--Z.sup.22, --Z.sup.21--S--Z.sup.22--, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.28, --C(O)S--, --C(O)--,
--S(O)--, --NR.sup.28C(O)--, --NR.sup.28--,
--Z.sup.21--SiR.sup.28.sub.2--Z.sup.22--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0095] wherein [0096] Z.sup.21 and Z.sup.22 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0097] R.sup.28 at
each occurrence is independently H, C.sub.1-20-alkyl, or
--Z.sup.23--C.sub.6-14-aryl, [0098] wherein [0099] Z.sup.23 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0100] Ar.sup.13 at each occurrence is independently
C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic
residue, each optionally substituted with 1 to 5 substituents
R.sup.o, wherein each R.sup.o is independently selected from the
group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy
and C.sub.1-6-haloalkyl, [0101] Ar.sup.14 and Ar.sup.15 at each
occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 4 substituents R.sup.p, wherein each R.sup.p is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and
[0102] R.sup.26 at each occurrence is independently
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl,
C.sub.1-20-alkoxy, --X.sup.9--Ar.sup.16,
--X.sup.9--Ar.sup.17--Ar.sup.16, --X.sup.9--Ar.sup.17--R.sup.29, or
--X.sup.9--Ar.sup.17--Ar.sup.18--R.sup.29, [0103] wherein [0104]
X.sup.9 at each occurrence is independently
--Z.sup.24--O--Z.sup.25--, --Z.sup.24--S--Z.sup.25, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.30, --C(O)S--, --C(O)--,
--S(O)--, --NR.sup.30C(O)--, --NR.sup.30--,
--Z.sup.24--SiR.sup.30.sub.2--Z.sup.25--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0105] wherein [0106] Z.sup.24 and Z.sup.25 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0107] R.sup.30 at
each occurrence is independently H, C.sub.1-20-alkyl or
--Z.sup.26--C.sub.6-14-aryl, wherein Z.sup.26 at each occurrence is
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, [0108] Ar.sup.16 at each
occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 5 substituents R.sup.q, wherein each R.sup.q is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0109]
Ar.sup.17 and Ar.sup.18 at each occurrence are independently
C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.r, wherein each R.sup.r is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and [0110] R.sup.29 at
each occurrence is independently C.sub.1-20-alkyl,
C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy, q
and s are the same or different and are 0, 1, 2, 3, 4 or 5, r is 0,
1 or 2, and n is an integer from 1 to 10'000.
[0111] Preferred are oligomers or polymers of formula
##STR00014##
wherein A.sup.1 and A.sup.2 can be the same or different and are S
or Se, E is selected from the group consisting of
##STR00015## [0112] wherein [0113] R.sup.1 and R.sup.2 can be the
same or different and are H, halogen, --CN, C.sub.1-30-alkyl,
C.sub.2-30-alkenyl, C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl,
C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl,
C.sub.1-30-haloalkyl, monovalent 3 to 12 membered aliphatic
heterocyclic residue, --X.sup.1--R.sup.6, --X.sup.2--Ar.sup.1,
--X.sup.2--Ar.sup.2--Ar.sup.1, --X.sup.2--Ar.sup.2--R.sup.7 or
--X.sup.2--Ar.sup.2--Ar.sup.3--R.sup.7, [0114] wherein [0115]
X.sup.1 at each occurrence is independently --O--,
--[Z.sup.1--O].sub.a--, --[O--Z.sup.1].sub.a--O--, --S--,
--[Z.sup.1--S].sub.a--, --[S--Z.sup.1].sub.a--S--, --S(O),
--C(O)--, --C(O)O--, --C(O)NR.sup.8--, C(O)S--, --O(CO)--,
--S(CO)--, --NR.sup.8C(O)-- or --NR.sup.8--, [0116] wherein [0117]
Z' at each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, [0118] a at each
occurrence is independently an integer from 1 to 10 and [0119]
R.sup.8 at each occurrence is independently H, C.sub.1-20-alkyl, or
--Z.sup.2--C.sub.6-14-aryl, [0120] wherein [0121] Z.sup.2 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0122] R.sup.6 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0123] X.sup.2 at each occurrence is independently
--Z.sup.3--O--Z.sup.4--, --S(O)--, --C(O)--, --C(O)O--,
--(CO)NR.sup.9, --C(O)S--, --O(CO)--, --S(CO)--, --NR.sup.9C(O)--,
--NR.sup.9--, --Z.sup.3--SiR.sup.9.sub.2--Z.sup.4--,
C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene
or a covalent bond, [0124] wherein [0125] Z.sup.3 and Z.sup.4 at
each occurrence are independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
and [0126] R.sup.9 at each occurrence is independently H,
C.sub.1-20-alkyl, or --Z.sup.5--C.sub.6-14-aryl, [0127] wherein
[0128] Z.sup.5 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, [0129] Ar.sup.1 at each occurrence is
independently C.sub.6-14-aryl or monovalent 5 to 14 membered
aromatic hetrocyclic residue, each optionally substituted with 1 to
5 substituents R.sup.a, wherein each R.sup.a is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0130] Ar.sup.2 and
Ar.sup.3 at each occurrence are independently C.sub.6-14-arylene or
bivalent 5 to 14 membered aromatic heterocyclic residue, each
optionally substituted with 1 to 4 substituents R.sup.b, wherein
each R.sup.b is independently selected from the group consisting of
halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and
C.sub.1-6-haloalkyl, and [0131] R.sup.7 at each occurrence is
independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.1-20-haloalkyl, C.sub.1-20-alkoxy, --X.sup.3--Ar.sup.4,
--X.sup.3--Ar.sup.5--Ar.sup.4, --X.sup.3--Ar.sup.5--R.sup.10, or
--X.sup.3--Ar.sup.5--Ar.sup.6--R.sup.10, [0132] wherein [0133]
X.sup.3 at each occurrence is independently
--Z.sup.6--O--Z.sup.7--, --Z.sup.6--S--Z.sup.7, --S(O)--, --C(O)--,
--C(O)O--, --C(O)NR.sup.11, --C(O)S--, --C(O)--, --S(O)--,
--NR.sup.11C(O)--, --NR.sup.11--,
--Z.sup.6--SiR.sup.11.sub.2--Z.sup.7--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0134] wherein [0135] Z.sup.6 and Z.sup.7 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0136] R.sup.11 at
each occurrence is independently H, C.sub.1-20-alkyl or
--Z.sup.8--C.sub.6-14-aryl, wherein Z.sup.8 at each occurrence is
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, [0137] Ar.sup.4 at each
occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 5 substituents R.sup.c, wherein each R.sup.c is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0138]
Ar.sup.5 and Ar.sup.6 at each occurrence are independently
C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.d, wherein each R.sup.d is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and [0139] R.sup.10 at
each occurrence is independently C.sub.1-20-alkyl,
C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy,
[0140] R.sup.3, R.sup.4 and R.sup.5 can be the same or different
and are H, halogen, --CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl, C.sub.6-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12
membered aliphatic heterocyclic residue, --X.sup.4--R.sup.12,
--X.sup.5--Ar.sup.7, --X.sup.5--Ar.sup.8--Ar.sup.7,
--X.sup.5--Ar.sup.8--R.sup.13 or
--X.sup.5--Ar.sup.8--Ar.sup.9--R.sup.13, [0141] wherein [0142]
X.sup.4 at each occurrence is independently --[Z.sup.9--O].sub.b--,
--[Z.sup.9--S--].sub.b--, --S(O)--, --C(O)--, --C(O)O--,
--C(O)NR.sup.14-- or C(O)S--, [0143] wherein [0144] Z.sup.9 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, [0145] b at each
occurrence is independently an integer from 1 to 10 and [0146]
R.sup.14 at each occurrence is independently H, C.sub.1-20-alkyl,
or --Z.sup.10--C.sub.6-14-aryl, [0147] wherein [0148] Z.sup.10 at
each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0149] R.sup.12 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0150] X.sup.5 at each occurrence is independently
--Z.sup.11--O--Z.sup.12, --Z.sup.11--S--Z.sup.12--, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.15, --C(O)S--,
--Z.sup.11--SiR.sup.15.sub.2--Z.sup.12--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0151] wherein [0152] Z.sup.11 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene,
[0153] Z.sup.12 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, and [0154] R.sup.15 at each occurrence is
independently H, C.sub.1-20-alkyl, or --Z.sup.13--C.sub.6-14-aryl,
[0155] wherein [0156] Z.sup.13 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, [0157] Ar.sup.7 at each occurrence is
independently C.sub.6-14-aryl or monovalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 5 substituents R.sup.e, wherein each R.sup.e is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0158] Ar.sup.8 and
Ar.sup.9 at each occurrence are independently C.sub.6-14-arylene or
bivalent 5 to 14 membered aromatic heterocyclic residue, each
optionally substituted with 1 to 4 substituents R.sup.f, wherein
each R.sup.f is independently selected from the group consisting of
halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and
C.sub.1-6-haloalkyl and [0159] R.sup.13 at each occurrence is
independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.1-20-haloalkyl, C.sub.1-20-alkoxy, --X.sup.6--Ar.sup.10,
--X.sup.6--Ar.sup.11--Ar.sup.10, --X.sup.6--Ar.sup.11--R.sup.16, or
--X.sup.6--Ar.sup.11--Ar.sup.12--R.sup.17, [0160] wherein [0161]
X.sup.6 at each occurrence is independently
--Z.sup.14--O--Z.sup.15--, --Z.sup.14--S--Z.sup.15, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.18, --C(O)S--, --C(O)--,
--S(O)--, --NR.sup.18C(O)--, --NR.sup.18--, [0162]
--Z.sup.14--SiR.sup.18.sub.2--Z.sup.15--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0163] wherein [0164] Z.sup.14 and Z.sup.15 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0165] R.sup.18 at
each occurrence is independently H, C.sub.1-20-alkyl or
--Z.sup.16--C.sub.6-14-aryl, wherein Z.sup.16 at each occurrence is
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, [0166] Ar.sup.10 at each
occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 5 substituents R.sup.g, wherein each R.sup.g is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0167]
Ar.sup.11 and Ar.sup.12 at each occurrence are independently
C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.h, wherein each R.sup.h is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl and [0168] R.sup.17 at
each occurrence is independently C.sub.1-20-alkyl,
C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy,
[0169] R.sup.19 is O or C(CN).sub.2, and [0170] R.sup.20 and
R.sup.21 are the same or different and are R.sup.22 or CN, [0171]
wherein R.sup.22 has the same meaning as R.sup.1, G.sup.1 and
G.sup.2 are the same or different and are phenylene or a monocyclic
bivalent 5 to 8 membered aromatic heterocyclic residue, which
phenylene and monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue are optionally substituted with 1 to 4
substituents R, wherein each R is independently selected from the
group consisting of halogen, --CN, --NO.sub.2, --OH,
C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl,
Z.sup.17--O--C.sub.1-30-alkyl, --Z.sup.17--S--C.sub.1-30-alkyl,
--Z.sup.17--C.sub.3-10-cycloalkyl,
--Z.sup.17--C.sub.6-10-cycloalkenyl,
--Z.sup.17--C.sub.8-10-cycloalkynyl, --Z.sup.17--C.sub.6-14-aryl,
--Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.17-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-30-alkynyl, C.sub.3-10-cycloalkyl, C.sub.6-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12
membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue is optionally substituted
with 1 to 4 substituents R, wherein each R is independently
selected from the group consisting of halogen, --CN, --NO.sub.2,
*.dbd.O, --OH, --NH.sub.2, --NH(C.sub.1-20-alkyl),
--N(C.sub.1-20-alkyl).sub.2, --N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--N(C.sub.6-14-aryl).sub.2, --S(O).sub.mH,
--S(O).sub.m--C.sub.1-20-alkyl, --S(O).sub.2OH,
--S(O).sub.m--OC.sub.1-20-alkyl, --S(O).sub.m--OC.sub.6-14-aryl,
--CHO, --C(O)--C.sub.1-20-alkyl, --C(O)--C.sub.6-14-aryl, --C(O)OH,
--C(O)--OC.sub.1-20-alkyl, --C(O)--OC.sub.6-14-aryl,
--C(O)NH.sub.2, --C(O)NH--C.sub.1-20-alkyl,
--C(O)N(C.sub.1-20-alkyl).sub.2, --C(O)NH--C.sub.6-14-aryl,
--C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(O)N(C.sub.6-14-aryl).sub.2, --C(S)NH.sub.2,
--C(S)NH--C.sub.1-20-alkyl, --C(S)N(C.sub.1-20-alkyl).sub.2,
--C(S)N(C.sub.6-14-aryl).sub.2,
--C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(S)NH--C.sub.6-14-aryl, --S(O).sub.mNH.sub.2,
--S(O).sub.mNH(C.sub.1-20-alkyl),
--S(O).sub.mN(C.sub.1-20-alkyl).sub.2,
--S(O).sub.mNH(C.sub.6-14-aryl),
--S(O).sub.mN(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--S(O).sub.mN(C.sub.6-14-aryl).sub.2, SiH.sub.3,
SiH(C.sub.1-20-alkyl).sub.2, SiH.sub.2(C.sub.1-20-alkyl) and
Si(C.sub.1-20-alkyl).sub.3, and wherein C.sub.3-10-cycloalkyl,
C.sub.5-10-cycloalkenyl, --C.sub.8-10-cycloalkynyl,
C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic
residue and monovalent 5 to 14 membered aromatic heterocyclic
residue is optionally substituted with 1 to 4 substituents R.sup.k,
wherein each R.sup.k is independently selected from the group
consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.2-20-alkynyl, C.sub.1-20-alkoxy, --S--C.sub.1-20-alkyl,
C.sub.1-20-haloalkyl, [0172] wherein [0173] Z.sup.17 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
and [0174] m at each occurrence is independently 0, 1 or 2, L is
C.sub.6-24-arylene or a bivalent 5 to 18 membered aromatic
heterocyclic residue, wherein C.sub.6-24-arylene and bivalent 5 to
18 membered aromatic heterocyclic residue are optionally
substituted with 1 to 4 substituents R.sup.l, wherein each R.sup.l
is independently selected from the group consisting of halogen,
--CN, --NO.sub.2, *.dbd.O, OH, *.dbd.C(C.sub.1-30-alkyl).sub.2,
C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl,
--Z.sup.18--O--C.sub.1-30-alkyl, --Z.sup.18--S--C.sub.1-30-alkyl,
--Z.sup.18--C.sub.3-10-cycloalkyl,
--Z.sup.18--C.sub.5-10-cycloalkenyl,
--Z.sup.18--C.sub.8-10-cycloalkynyl, --Z.sup.18--C.sub.6-14-aryl,
--Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.18-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-30-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12
membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue is optionally substituted
with 1 to 4 substituents R.sup.m, wherein each R.sup.m is
independently selected from the group consisting of halogen, --CN,
--NO.sub.2, *.dbd.O, --OH, --NH.sub.2, --NH(C.sub.1-20-alkyl),
--N(C.sub.1-20-alkyl).sub.2, --N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--N(C.sub.6-14-aryl).sub.2, --S(O).sub.oH,
--S(O).sub.o--C.sub.1-20-alkyl, --S(O).sub.2OH,
--S(O).sub.o--OC.sub.1-20-alkyl, --S(O).sub.o--OC.sub.6-14-aryl,
--CHO, --C(O)--C.sub.1-20-alkyl, --C(O)--C.sub.6-14-aryl, --C(O)OH,
--C(O)--OC.sub.1-20-alkyl, --C(O)--OC.sub.6-14-aryl,
--C(O)NH.sub.2, --C(O)NH--C.sub.1-20-alkyl,
--C(O)N(C.sub.1-20-alkyl).sub.2, --C(O)NH--C.sub.6-14-aryl,
--C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(O)N(C.sub.6-14-aryl).sub.2, --C(S)NH.sub.2,
--C(S)NH--C.sub.1-20-alkyl, --C(S)N(C.sub.1-20-alkyl).sub.2,
--C(S)N(C.sub.6-14-aryl).sub.2,
--C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(S)NH--C.sub.6-14-aryl, --S(O).sub.oNH.sub.2,
--S(O)ONH(C.sub.1-20-alkyl), --S(O).sub.oN(C.sub.1-20-alkyl).sub.2,
--S(O)ONH(C.sub.6-14-aryl),
--S(O).sub.oN(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--S(O).sub.oN(C.sub.6-14-aryl).sub.2, SiH.sub.3,
SiH(C.sub.1-20-alkyl).sub.2, SiH.sub.2(C.sub.1-20-alkyl) and
Si(C.sub.1-20-alkyl).sub.3, and wherein C.sub.3-10-cycloalkyl,
C.sub.5-10-cycloalkenyl, --C.sub.8-10-cycloalkynyl,
C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic
residue and monovalent 5 to 14 membered aromatic heterocyclic
residue is optionally substituted with 1 to 4 substituents
R.sup.n
, wherein each R.sup.n is independently selected from the group
consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.2-20-alkynyl, C.sub.1-20-alkoxy, C.sub.1-20-haloalkyl,
wherein Z.sup.18 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.1-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, and o at each occurrence is independently 0, 1 or
2, or
L is
[0175] ##STR00016## [0176] wherein [0177] R.sup.23 and R.sup.24 can
be the same or different and are H, halogen, --CN,
C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-20-alkynyl,
C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12
membered aliphatic heterocyclic residue, --X.sup.7--R.sup.25,
--X.sup.8--Ar.sup.13, --X.sup.8--Ar.sup.14--Ar.sup.13,
--X.sup.8--Ar.sup.14--R.sup.26 or
--X.sup.8--Ar.sup.14--Ar.sup.15--R.sup.26, [0178] wherein [0179]
X.sup.7 at each occurrence is independently --O--,
--[Z.sup.19--O].sub.c--, [O--Z.sup.19].sub.c--O--, --S--,
--[Z.sup.19--S--].sub.c--, --[S--Z.sup.19].sub.c--S--, --S(O),
--C(O)--, --C(O)O--, --C(O)NR.sup.27--, C(O)S--, --O(CO)--,
--S(CO)--, --NR.sup.27C(O)-- or --NR.sup.27--, [0180] wherein
[0181] Z.sup.19 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene,
[0182] c at each occurrence is independently an integer from 1 to
10 and [0183] R.sup.27 at each occurrence is independently H,
C.sub.1-20-alkyl, or --Z.sup.20--C.sub.6-14-aryl, [0184] wherein
[0185] Z.sup.2 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, [0186] R.sup.25 at each occurrence is
independently C.sub.1-30-alkyl, C.sub.2-30-alkenyl or
C.sub.1-30-haloalkyl, [0187] X.sup.8 at each occurrence is
independently --Z.sup.21--O--Z.sup.22--, --Z.sup.21--S--Z.sup.22--,
--S(O)--, --C(O)--, --C(O)O--, --C(O)NR.sup.28, --C(O)S--,
--C(O)--, --S(O)--, --NR.sup.28C(O)--, --NR.sup.28--,
--Z.sup.21--SiR.sup.28.sub.2--Z.sup.22--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0188] wherein [0189] Z.sup.21 and Z.sup.22 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0190] R.sup.28 at
each occurrence is independently H, C.sub.1-20-alkyl, or
--Z.sup.23--C.sub.6-14-aryl, [0191] wherein [0192] Z.sup.23 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0193] Ar.sup.13 at each occurrence is independently
C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic
residue, each optionally substituted with 1 to 5 substituents
R.sup.o, wherein each R.sup.o is independently selected from the
group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy
and C.sub.1-6-haloalkyl, [0194] Ar.sup.14 and Ar.sup.15 at each
occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 4 substituents R.sup.p, wherein each R.sup.p is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and
[0195] R.sup.26 at each occurrence is independently
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl,
C.sub.1-20-alkoxy, --X.sup.9--Ar.sup.16,
--X.sup.9--Ar.sup.17--Ar.sup.16, --X.sup.9--Ar.sup.17--R.sup.29, or
--X.sup.9--Ar.sup.17--Ar.sup.18--R.sup.29, [0196] wherein [0197]
X.sup.9 at each occurrence is independently
--Z.sup.24--O--Z.sup.25--, --Z.sup.24--S--Z.sup.25, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.30, --C(O)S--, --C(O)--,
--S(O)--, --NR.sup.30C(O)--, --NR.sup.30--,
--Z.sup.24--SiR.sup.30.sub.2--Z.sup.25--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0198] wherein [0199] Z.sup.24 and Z.sup.25 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0200] R.sup.30 at
each occurrence is independently H, C.sub.1-20-alkyl or
--Z.sup.26--C.sub.6-14-aryl, wherein Z.sup.26 at each occurrence is
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, [0201] Ar.sup.16 at each
occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 5 substituents R.sup.q, wherein each R.sup.q is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0202]
Ar.sup.17 and Ar.sup.18 at each occurrence are independently
C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.r, wherein each R.sup.r is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and [0203] R.sup.29 at
each occurrence is independently C.sub.1-20-alkyl,
C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy, q
and s are the same or different and are 0, 1, 2, 3, 4 or 5, r is 0,
1 or 2, and n is an integer from 2 to 10'000.
[0204] Examples of halogen are --F, --Cl, --Br and --I.
[0205] Examples of C.sub.1-6-alkyl are methyl, ethyl, n-propyl,
isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl,
neopentyl, isopentyl and n-hexyl. Examples of C.sub.1-20-alkyl are
C.sub.1-6-alkyl, n-heptyl, n-octyl, n-(2-ethyl)hexyl, n-nonyl,
n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl,
n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,
n-nonadecyl and n-icosyl (C.sub.20). Examples of C.sub.1-30-alkyl
are C.sub.1-20-alkyl, n-docosyl (C.sub.22), n-tetracosyl
(C.sub.24), n-hexacosyl (C.sub.26), n-octacosyl (C.sub.28) and
n-triacontyl (C.sub.30).
[0206] Examples of C.sub.1-6-haloalkyl are CF.sub.3, CHF.sub.2,
CH.sub.2F, C.sub.2F.sub.5, CH.sub.2(CH.sub.2).sub.4CF.sub.3,
CF.sub.3, CCl.sub.3, CHCl.sub.2, CH.sub.2Cl, C.sub.2Cl.sub.5 and
CH.sub.2(CH.sub.2)--CCl.sub.3. Examples of C.sub.1-20-haloalkyl and
of C.sub.1-30-haloalkyl are C.sub.1-6-haloalkyl and
CH.sub.2(CH.sub.2).sub.8CF.sub.3,
CH.sub.2(CH.sub.2).sub.14CF.sub.3.
[0207] Examples of C.sub.1-6-alkoxy are methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy,
n-pentoxy, neopentoxy, isopentoxy and n-hexoxy. Examples of
C.sub.1-20-alkoxy are C.sub.1-6-alkoxy, n-heptoxy, n-octoxy,
n-nonoxy and n-decoxy, n-undecoxy, n-dodoxy, n-undecoxy,
n-dodecoxy, n-tridecoxy, n-tetradecoxy, n-pentadecoxy,
n-hexadecoxy, n-heptadecoxy, n-octadecoxy, n-nonadecoxy and
n-eicosoxy (C.sub.20).
[0208] Examples of C.sub.2-20-alkenyl are ethenyl, propenyl,
cis-2-butenyl, trans-2-butenyl, 3-butenyl, cis-2-pentenyl,
trans-2-pentenyl, cis-3-pentenyl, trans-3-pentenyl, 4-pentenyl,
2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl, docenyl,
undocenyl and oleyl (C.sub.18). Examples of C.sub.2-20-alkenyl are
also butadienyl, pentadienyl, hexadienyl, linoleyl (C.sub.18),
linolenyl (C.sub.18) and arachidonyl (C.sub.20). Examples of
C.sub.2-30-alkenyl are C.sub.2-20-alkenyl and erucyl
(C.sub.22).
[0209] Examples of C.sub.2-20-alkynyl are ethynyl, 2-propynyl,
2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl,
nonynyl, decynyl, undecynyl, dodecynyl, undecynyl, dodecynyl,
tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl,
octadecynyl, nonadecynyl and icosynyl (C.sub.20). Examples of
C.sub.2-30-alkynyl are C.sub.2-20-alkynyl.
[0210] Examples of C.sub.3-10-cycloalkyl are preferably monocyclic
C.sub.3-10-cycloalkyls such as cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, but include
also polycyclic C.sub.3-10-cycloalkyls such as decalinyl, norbornyl
and adamantyl.
[0211] Examples of C.sub.5-10-cycloalkenyl are preferably
monocyclic C.sub.5-10-cycloalkenyls such as cyclopentenyl,
cyclohexenyl, cyclohexadienyl and cycloheptatrienyl, but include
also polycyclic C.sub.5-10-cycloalkenyls.
[0212] An example of C.sub.8-10-cycloalkynyl is cyclooctynyl.
[0213] The monovalent 3 to 12 membered aliphatic heterocyclic
residues can be monocyclic monovalent 3 to 8 membered aliphatic
heterocyclic residues or polycyclic, for example bicyclic,
monovalent 7 to 12 membered aliphatic heterocyclic residues.
[0214] Examples of monocyclic monovalent 3 to 8 membered aliphatic
heterocyclic residues are monocyclic monovalent 5 membered
aliphatic heterocyclic residues containing one heteroatom such as
pyrrolidinyl, 1-pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl,
tetrahydrofuryl, 2,3-dihydrofuryl, tetrahydrothiophenyl and
2,3-dihydrothiophenyl, monocyclic monovalent 5 membered aliphatic
heterocyclic residues containing two heteroatoms such as
imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl,
oxazolidinyl, oxazolinyl, isoxazolidinyl, isoxazolinyl,
thiazolidinyl, thiazolinyl, isothiazolidinyl and isothiazolinyl,
monocyclic monovalent 5 membered aliphatic heterocyclic residues
containing three heteroatoms such as 1,2,3-triazolyl,
1,2,4-triazolyl and 1,4,2-dithiazolyl, monocyclic monovalent 6
membered aliphatic heterocyclic residues containing one heteroatom
such as piperidyl, piperidino, tetrahydropyranyl, pyranyl, thianyl
and thiopyranyl, monocyclic monovalent 6 membered aliphatic
heterocyclic residues containing two heteroatoms such as
piperazinyl, morpholinyl and morpholino and thiazinyl, monocyclic
monovalent 7 membered aliphatic heterocyclic residues containing
one hereoatom such as azepanyl, azepinyl, oxepanyl, thiepanyl,
thiapanyl, thiepinyl, and monocyclic monovalent 7 membered
aliphatic heterocyclic residues containing two hereoatom such as
1,2-diazepinyl and 1,3-thiazepinyl.
[0215] The monovalent 3 to 12 membered aliphatic heterocyclic
residues can contain one or more heteroatoms, which can
independently be selected from the group consisting of nitrogen,
oxygen, sulfur, phosphor, silicon and arsenic, preferably from the
group consisting of nitrogen, oxygen and sulfur.
[0216] Examples of monocyclic monovalent 3 to 12 membered aliphatic
heterocyclic residue substituted with *.dbd.O are 2-oxazolidonyl,
4-piperidonyl, 4-piperidono, pyrimidine-2,4(1H,3H)-dionyl and
2-pyridonyl.
[0217] An example of a bicyclic monovalent 7 to 12 membered
aliphatic heterocyclic residue is decahydronaphthyl.
[0218] C.sub.6-14-aryl can be monocyclic or polycyclic. Examples of
C.sub.6-14-aryl are monocyclic C.sub.6-aryl such as phenyl,
bicyclic C.sub.9-10-aryl such as 1-naphthyl, 2-naphthyl, indenyl,
indanyl and tetrahydronaphthyl, and tricyclic C.sub.12-14-aryl such
as anthryl, phenanthryl, fluorenyl and s-indacenyl.
[0219] C.sub.6-14-haloaryl can be monocyclic or polycyclic.
Examples of C.sub.6-14-haloaryl are 6-chlorophenyl and
2-chlorophenyl.
[0220] The monovalent 5 to 14 membered aromatic heterocyclic
residues can be monocyclic monovalent 5 to 8 membered aromatic
heterocyclic residues, or polycyclic monovalent 7 to 12 membered
aromatic heterocyclic residues, for example bicyclic or tricyclic
monovalent 9 to 14 membered aromatic heterocyclic residues.
[0221] Examples of monocyclic monovalent 5 to 8 membered aromatic
heterocyclic residues are monocyclic monovalent 5 membered aromatic
heterocyclic residues containing one heteroatom such as pyrrolyl,
furyl and thiophenyl, monocyclic monovalent 5 membered aromatic
heterocyclic residues containing two heteroatoms such as
imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl,
isothiazolyl, monocyclic monovalent 5 membered aromatic
heterocyclic residues containing three heteroatoms such as
1,2,3-triazolyl, 1,2,4-triazolyl and oxadiazolyl, monocyclic
monovalent 5 membered aromatic heterocyclic residues containing
four heteroatoms such as tetrazolyl, monocyclic monovalent 6
membered aromatic heterocyclic residues containing one heteroatom
such as pyridyl, monocyclic monovalent 6 membered aromatic
heterocyclic residues containing two heteroatoms such as pyrazinyl,
pyrimidinyl and pyridazinyl, monocyclic monovalent 6 membered
aromatic heterocyclic residues containing three heteroatoms such as
1,2,3-triazinyl, 1,2,4-triazinyl and 1,3,5-triazinyl, monocyclic
monovalent 7 membered aromatic heterocyclic residues containing one
heteroatom such as azepinyl, and monocyclic monovalent 7 membered
aromatic heterocyclic residues containing two heteroatoms such as
1,2-diazepinyl,
[0222] Examples of bicyclic monovalent 7 to 12 membered aromatic
heterocyclic residues are bicyclic 9 membered aromatic heterocyclic
residues containing one heteroatom such as indolyl, isoindolyl,
indolizinyl, indolinyl, benzofuryl, isobenzofuryl, benzothiophenyl
and isobenzothiophenyl, bicyclic monovalent 9 membered aromatic
heterocyclic residues containing two heteroatoms such as indazolyl,
benzimidazolyl, benzimidazolinyl, benzoxazolyl, benzisooxazolyl,
benzthiazolyl, benzisothiazolyl, furopyridyl and thienopyridyl,
bicyclic monovalent 9 membered aromatic heterocyclic residues
containing three heteroatoms such as benzotriazolyl,
benzoxadiazolyl, oxazolopyridyl, isooxazolopyridyl,
thiazolopyridyl, isothiazolopyridyl and imidazopyridyl, bicyclic
monovalent 9 membered aromatic heterocyclic residues containing
four heteroatoms such as purinyl, bicyclic monovalent 10 membered
aromatic heterocyclic residues containing one heteroatom such as
quinolyl, isoquinolyl, chromenyl and chromanyl, bicyclic monovalent
10 membered aromatic heterocyclic residues containing two
heteroatoms such as quinoxalinyl, quinazolinyl, cinnolinyl,
phthalazinyl, 1,5-naphthyridinyl and 1,8-naphthyridinyl, bicyclic
monovalent 10 membered aromatic heterocyclic residues containing
three heteroatoms such as pyridopyrazinyl, pyridopyrimidinyl and
pyridopyridazinyl, and bicyclic monovalent 10 membered aromatic
heterocyclic residues containing four heteroatoms such as
pteridinyl.
[0223] Examples of tricyclic monovalent 9 to 14 membered aromatic
heterocyclic residues are dibenzofuryl, acridinyl, phenoxazinyl,
7H-cyclopenta[1,2-b:3,4-b]dithiophenyl and
4H-cyclopenta[2,1-b:3,4-b]dithiophenyl.
[0224] The monovalent 5 to 14 membered aromatic heterocyclic
residue can contain one or more heteroatoms which can independently
be selected from the group consisting of nitrogen, oxygen, sulfur,
phosphor, silicon and arsenic, preferably from the group consisting
of nitrogen, oxygen and sulfur.
[0225] Examples of C.sub.1-6-alkylene are methylene, ethylene,
butylene, pentylene, hexylene and 2-methylpentylene. Examples of
C.sub.1-30-alkylene are C.sub.1-6-alkylene,
CH.sub.2(CH.sub.2).sub.10CH.sub.2 and
CH.sub.2(CH.sub.2).sub.20)CH.sub.2.
[0226] Examples of C.sub.2-6-alkenylene are ethenylene,
cis-2-butenylene, trans-butenylene, cis-2-pentenylene,
trans-2-pentenylene, trans-2-hexenylene, trans-3-hexenylene and
2-methyl-trans-3-pentenylene. Examples of C.sub.2-30-alkenylene are
C.sub.2-6-alkenylene,
CH.sub.2(CH.sub.2).sub.4--CH.dbd.CH--(CH.sub.2).sub.4CH.sub.2 and
CH.sub.2(CH.sub.2).sub.9--CH.dbd.CH--(CH.sub.2).sub.9CH.sub.2.
[0227] Examples of C.sub.1-6-haloalkylene are CF.sub.2, CCl.sub.2,
CF.sub.2CF.sub.2, CCl.sub.2CCl.sub.2, CHFCH.sub.2,
CHFCH.sub.2CH.sub.2CHF and CHF(CH.sub.2).sub.4CHF. Examples of
C.sub.1-30-haloalkylene are C.sub.1-6-haloalkylene,
CHF(CH.sub.2).sub.10CHF and CHF(CH.sub.2).sub.20CHF.
[0228] Examples of C.sub.6-14-arylene are monocyclic
C.sub.6-arylene such as phenylene, bicyclic C.sub.9-10-arylene such
as 1-naphthylene, 2-naphthyl, indenylene, indanylene and
tetrahydronaphthylene, and tricyclic C.sub.12-14-arylene such as
anthrylene, phenanthrylene, fluorenylene and s-indacenylene.
Examples of C.sub.6-24-arylene are C.sub.6-14-arylene and
pyrenylene, tetracenylene, perylenylene, indenofluorenylene,
pentacenylene, coronenylene and tetraphenylenylene.
[0229] The bivalent 5 to 14 membered aromatic heterocyclic residues
can be monocyclic bivalent 5 to 8 membered aromatic heterocyclic
residues, or polycyclic bivalent 7 to 12 membered aromatic
heterocyclic residues, for example bicyclic or tricyclic bivalent 9
to 14 membered aromatic heterocyclic residues.
[0230] Examples of monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residues are monocyclic bivalent 5 membered aromatic
heterocyclic residues containing one heteroatom such as
pyrrolylene, furylene and thiophenylene, monocyclic bivalent 5
membered aromatic heterocyclic residues containing two heteroatoms
such as imidazolylene, pyrazolylene, oxazolylene, isoxazolylene,
thiazolylene, isothiazolylene, monocyclic bivalent 5 membered
aromatic heterocyclic residues containing three heteroatoms such as
1,2,3-triazolylene, 1,2,4-triazolylene and oxadiazolylene,
monocyclic bivalent 5 membered aromatic heterocyclic residues
containing four heteroatoms such as tetrazolylene, monocyclic
bivalent 6 membered aromatic heterocyclic residues containing one
heteroatom such as pyridylene, monocyclic bivalent 6 membered
aromatic heterocyclic residues containing two heteroatoms such as
pyrazinylene, pyrimidinylene and pyridazinylene, monocyclic
bivalent 6 membered aromatic heterocyclic residues containing three
heteroatoms such as 1,2,3-triazinylene, 1,2,4-triazinylene and
1,3,5-triazinylene, monocyclic bivalent 7 membered aromatic
heterocyclic residues containing one heteroatom such as
azepinylene, and monocyclic bivalent 7 membered aromatic
heterocyclic residues containing two heteroatoms such as
1,2-diazepinylene.
[0231] Examples of bicyclic bivalent 7 to 12 membered aromatic
heterocyclic residues are bicyclic bivalent 9 membered aromatic
heterocyclic residues containing one heteroatom such as indolylene,
isoindolylene, indolizinylene, indolinylene, benzofurylene,
isobenzofurylene, benzothiophenylene and isobenzothiophenylene,
bicyclic bivalent 9 membered aromatic heterocyclic residues
containing two heteroatoms such as indazolylene, benzimidazolylene,
benzimidazolinylene, benzoxazolylene, benzisooxazolylene,
benzthiazolylene, benzisothiazolylene, furopyridylene and
thienopyridylene, bicyclic bivalent 9 membered aromatic
heterocyclic residues containing three heteroatoms such as
benzotriazolylene, benzoxadiazolylene, oxazolopyridylene,
isooxazolopyridylene, thiazolopyridylene, isothiazolopyridylene and
imidazopyridylene, bicyclic bivalent 9 membered aromatic
heterocyclic residues containing four heteroatoms such as
purinylene, bicyclic bivalent 10 membered aromatic heterocyclic
residues containing one heteroatom such as quinolylene,
isoquinolylene, chromenylene and chromanylene, bicyclic bivalent 10
membered aromatic heterocyclic residues containing two heteroatoms
such as quinoxalinylene, quinazolinylene, cinnolinylene,
phthalazinylene, 1,5-naphthyridinylene and 1,8-naphthyridinylene,
bicyclic bivalent 10 membered aromatic heterocyclic residues
containing three heteroatoms such as pyridopyrazinylene,
pyridopyrimidinylene and pyridopyridazinylene, and bicyclic
bivalent 10 membered aromatic heterocyclic residues containing four
heteroatoms such as pteridinylene.
[0232] Examples of tricyclic bivalent 9 to 14 membered aromatic
heterocyclic residues containing one heteroatom are dibenzofurylene
and acridinylene. Examples of a tricyclic bivalent 9 to 14 membered
aromatic heterocyclic residues containing two heteroatoms are
phenoxazinylene, 7H-cyclopenta[1,2-b:3,4-b']dithiophenylene and
4H-cyclopenta[2,1-b:3,4-b']dithiophenylene.
[0233] Examples of bivalent 5 to 18 membered aromatic heterocyclic
residues are bivalent 5 to 14 membered aromatic heterocyclic
residues.
[0234] The bivalent 5 to 14 membered, respectively, 5 to 18
membered aromatic heterocyclic residue can contain one or more
heteroatoms which can independently be selected from the group
consisting of nitrogen, oxygen, sulfur, phosphor, silicon and
arsenic, preferably from the group consisting of nitrogen, silicon
and sulfur.
[0235] Preferably, A.sup.1 and A.sup.2 are S.
[0236] Preferably, E is selected from the group consisting of
##STR00017##
[0237] More preferably, E is selected from the group consisting
of
##STR00018##
[0238] Most preferably, E is
##STR00019##
[0239] Preferably, R.sup.1 and R.sup.2 are the same or different
and are H, halogen, --CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.1-30-haloalkyl, --X.sup.1--R.sup.6--, --X.sup.2--Ar.sup.1--,
--X.sup.2--Ar.sup.2--Ar.sup.1, --X.sup.2--Ar.sup.2--R.sup.7 or
--X.sup.2--Ar.sup.2--Ar.sup.2--R.sup.7, [0240] wherein [0241]
X.sup.1 at each occurrence is independently --O--,
--[Z.sup.1--O].sub.a--, [O--Z.sup.1].sub.a--O, --S--,
--[Z.sup.1--S--].sub.a--, --[S--Z.sup.1].sub.a--S--, --S(O),
--C(O)--, --C(O)O--, --C(O)NR.sup.8--, C(O)S--, --C(O)--, --S(O)--,
--NR.sup.8C(O)-- or --NR.sup.8--, [0242] wherein [0243] Z.sup.1 at
each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, [0244] a at each
occurrence is independently an integer from 1 to 10 and [0245]
R.sup.8 at each occurrence is independently H, C.sub.1-20-alkyl, or
--Z.sup.2--C.sub.6-14-aryl, [0246] wherein [0247] Z.sup.2 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0248] R.sup.6 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0249] X.sup.2 at each occurrence is independently
--Z.sup.3--O--Z.sup.4--, --Z.sup.3--S--Z.sup.4--, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.9, --C(O)S--, --C(O)--, --S(O)--,
--NR.sup.9C(O)--, --Z.sup.3--SiR.sup.9.sub.2--Z.sup.4--,
C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene
or a covalent bond, [0250] wherein [0251] Z.sup.3 and Z.sup.4 at
each occurrence are independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
and [0252] R.sup.9 at each occurrence is independently H,
C.sub.1-20-alkyl, or --Z.sup.5--C.sub.6-14-aryl, [0253] wherein
[0254] Z.sup.5 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, [0255] Ar.sup.1 at each occurrence is
independently C.sub.6-14-aryl or monovalent 5 to 14 membered
aromatic hetrocyclic residue, each optionally substituted with 1 to
5 substituents R.sup.a, wherein each R.sup.a is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0256] Ar.sup.2 and
Ar.sup.3 at each occurrence are independently C.sub.6-14-arylene or
bivalent 5 to 14 membered aromatic heterocyclic residue, each
optionally substituted with 1 to 4 substituents R.sup.b, wherein
each R.sup.b is independently selected from the group consisting of
halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and
C.sub.1-6-haloalkyl, and [0257] R.sup.7 at each occurrence is
independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.1-20-haloalkyl and C.sub.1-20-alkoxy. More preferably,
R.sup.1 and R.sup.2 are the same or different and are H, halogen,
--CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.1-30-haloalkyl,
--X.sup.1--R.sup.6, --X.sup.2--Ar.sup.1,
--X.sup.2--Ar.sup.2--Ar.sup.1, --X.sup.2--Ar.sup.2--R.sup.7 or
--X.sup.2--Ar.sup.2--Ar.sup.3--R.sup.7, [0258] wherein [0259]
X.sup.1 at each occurrence is independently --O--,
--[Z.sup.1--O].sub.a--, --[O--Z.sup.1].sub.a--O, --S--,
--[Z.sup.1--S].sub.a--, or --[S--Z.sup.1].sub.a--S--, [0260]
wherein [0261] Z.sup.1 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene,
[0262] a at each occurrence is independently an integer from 1 to
10 and [0263] R.sup.6 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0264] X.sup.2 at each occurrence is independently
--Z.sup.3--O--Z.sup.4--, --Z.sup.3--S--Z.sup.4--,
C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene
or a covalent bond, [0265] wherein [0266] Z.sup.3 and Z.sup.4 at
each occurrence are independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
and [0267] Ar.sup.1 at each occurrence is independently
C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic
residue, each optionally substituted with 1 to 5 substituents
R.sup.a, wherein each R.sup.a is independently selected from the
group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy
and C.sub.1-6-haloalkyl, [0268] Ar.sup.2 and Ara at each occurrence
are independently C.sub.6-14-arylene or bivalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 4 substituents R.sup.b, wherein each R.sup.b is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and [0269] R.sup.7 at
each occurrence is independently C.sub.1-20-alkyl,
C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy.
[0270] Even more preferably, R.sup.1 and R.sup.2 are the same or
different and are H, C.sub.1-30-alkyl, C.sub.1-30-haloalkyl,
--X.sup.1--R.sup.6 or --X.sup.2--Ar.sup.1, [0271] wherein [0272]
X.sup.1 at each occurrence is independently --[Z.sup.1--O].sub.a--,
--[Z.sup.1--S].sub.a--, or --[S--Z.sup.1].sub.a--S--, [0273]
wherein [0274] Z.sup.1 at each occurrence is independently
C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, [0275] a at each
occurrence is independently an integer from 1 to 10 and [0276]
R.sup.6 at each occurrence is independently C.sub.1-30-alkyl or
C.sub.1-30-haloalkyl, [0277] X.sup.2 at each occurrence is
independently --Z.sup.3--O--Z.sup.4--, --Z.sup.3--S--Z.sup.4--,
C.sub.1-30-alkylene or C.sub.1-30-haloalkylene, [0278] wherein
[0279] Z.sup.3 and Z.sup.4 at each occurrence are independently
C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, and [0280] Ar.sup.1
at each occurrence is independently C.sub.6-14-aryl, optionally
substituted with 1 to 5 substituents R.sup.a, wherein each R.sup.a
is independently selected from the group consisting of halogen
C.sub.1-6-alkyl and C.sub.1-6-alkoxy.
[0281] Most preferably, R.sup.1 and R.sup.2 are the same or
different and are C.sub.1-30-alkyl, C.sub.1-30-haloalkyl or
--X.sup.2--Ar.sup.1, [0282] wherein [0283] X.sup.2 at each
occurrence is independently C.sub.1-30-alkylene or
C.sub.1-30-haloalkylene, and [0284] Ar.sup.1 at each occurrence is
independently C.sub.6-14-aryl, optionally substituted with 1 to 5
substituents R.sup.a, wherein each R.sup.a is independently
selected from the group consisting of halogen C.sub.1-6-alkyl and
C.sub.1-6-alkoxy.
[0285] In particular, R.sup.1 and R.sup.2 are the same or different
and are C.sub.1-30-alkyl, for example C.sub.1-20-alkyl or
C.sub.1-6-alkyl, for example methyl or n-hexyl.
[0286] Preferably, R.sup.3 is H, halogen, CN, C.sub.1-30-alkyl,
C.sub.2-30-alkenyl, C.sub.1-30-haloalkyl, --X.sup.4--R.sup.12,
--X.sup.5--Ar.sup.7, --X.sup.5--Ar.sup.9--Ar.sup.7,
--X.sup.5--Ar.sup.8--R.sup.13 or
--X.sup.5--Ar.sup.8--Ar.sup.9--R.sup.13, [0287] wherein [0288]
X.sup.4 at each occurrence is independently --[Z.sup.9--O].sub.b--,
--[Z.sup.9--S--].sub.b--, --S(O)--, --C(O)--, --C(O)O--,
--C(O)NR.sup.14-- or C(O)S--, [0289] wherein [0290] Z.sup.9 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, [0291] b at each
occurrence is independently an integer from 1 to 10 and [0292]
R.sup.14 at each occurrence is independently H, C.sub.1-20-alkyl,
or --Z.sup.10--C.sub.6-14-aryl, [0293] wherein [0294] Z.sup.10 at
each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0295] R.sup.12 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0296] X.sup.5 at each occurrence is independently
--Z.sup.11--O--Z.sup.12, --Z.sup.11--S--Z.sup.12--, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.15, --C(O)S--,
--Z.sup.11--SiR.sup.15.sub.2--Z.sup.12--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0297] wherein [0298] Z.sup.11 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene,
[0299] Z.sup.12 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, and [0300] R.sup.15 at each occurrence is
independently H, C.sub.1-20-alkyl, or --Z.sup.13--C.sub.6-14-aryl,
[0301] wherein [0302] Z.sup.13 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, [0303] Ar.sup.1 at each occurrence is
independently C.sub.6-14-aryl or monovalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 5 substituents R.sup.e, wherein each R.sup.e is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0304] Ar.sup.8 and
Ar.sup.9 at each occurrence are independently C.sub.6-14-arylene or
bivalent 5 to 14 membered aromatic heterocyclic residue, each
optionally substituted with 1 to 4 substituents R.sup.f, wherein
each R.sup.f is independently selected from the group consisting of
halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and
C.sub.1-6-haloalkyl and [0305] R.sup.13 at each occurrence is
independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy.
[0306] More preferably, R.sup.3 is H, C.sub.1-30-alkyl,
C.sub.2-30-alkenyl, C.sub.1-30-haloalkyl, --X.sup.4--R.sup.12,
--X.sup.5--Ar.sup.7, --X.sup.5--Ar.sup.8--Ar.sup.7,
--X.sup.5--Ar.sup.8--R.sup.13 or
--X.sup.5--Ar.sup.8--Ar.sup.9--R.sup.13, [0307] wherein [0308]
X.sup.4 at each occurrence is independently --[Z.sup.9--O].sub.b--
or --[Z.sup.9--S--].sub.b--, [0309] wherein [0310] Z.sup.9 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, and [0311] b at
each occurrence is independently an integer from 1 to 10 and [0312]
R.sup.12 at each occurrence is independently C.sub.1-30-alkyl,
C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl, [0313] X.sup.5 at each
occurrence is independently --Z.sup.11--O--Z.sup.12,
--Z.sup.11--S--Z.sup.12--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0314] wherein [0315] Z.sup.11 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene,
and [0316] Z.sup.12 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, and [0317] Ar.sup.7 at each occurrence is
independently C.sub.6-14-aryl or monovalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 5 substituents R.sup.e, wherein each R.sup.e is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0318] Ar.sup.8 and
Ar.sup.9 at each occurrence are independently C.sub.6-14-arylene or
bivalent 5 to 14 membered aromatic heterocyclic residue, each
optionally substituted with 1 to 4 substituents R.sup.f, wherein
each R.sup.f is independently selected from the group consisting of
halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and
C.sub.1-6-haloalkyl, and [0319] R.sup.13 at each occurrence is
independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy.
[0320] Most preferably, R.sup.3 is --X.sup.5--Ar.sup.7,
--X.sup.5--Ar.sup.8--Ar.sup.7, --X.sup.5--Ar.sup.8--R.sup.13 or
--X.sup.5--Ar.sup.8--Ar.sup.9--R.sup.13, [0321] wherein [0322]
X.sup.5 at each occurrence is a covalent bond, [0323] Ar.sup.7 at
each occurrence is independently C.sub.6-14-aryl or monovalent 5 to
14 membered aromatic heterocyclic residue, each optionally
substituted with 1 to 5 substituents R.sup.e, wherein each R.sup.e
is independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0324]
Ar.sup.8 and Ar.sup.9 at each occurrence are independently
C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.f, wherein each R.sup.f is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and [0325] R.sup.13 at
each occurrence is independently C.sub.1-20-alkyl,
C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy.
[0326] In particular, R.sup.3 is --X.sup.5--Ar.sup.8--R.sup.13,
[0327] wherein [0328] X.sup.5 is a covalent bond, [0329] Ar.sup.8
is C.sub.6-14-arylene, for example phenylene, and [0330] R.sup.13
is C.sub.1-20-alkyl.
[0331] For example R.sup.3 is
##STR00020##
[0332] Preferably, G.sup.1 and G.sup.2 are the same or different
and are phenylene, such as
##STR00021##
or, preferably, a monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue selected from the group consisting of
##STR00022## [0333] wherein [0334] M.sup.1 is S, O, NH or
SiR.sup.sR.sup.s, preferably M.sup.1 is S or NH, more preferably
M.sup.1 is S, wherein R.sup.s is hydrogen or C.sub.1-30-alkyl,
which phenylene or monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue are optionally substituted with 1 to 2
substituents R.sup.i, wherein each R.sup.i is independently
selected from the group consisting of --CN, C.sub.1-30-alkyl,
--Z.sup.17--O--C.sub.1-30-alkyl, --Z.sup.17--S--C.sub.1-30-alkyl,
--Z.sup.17--C.sub.3-10-cycloalkyl, --Z.sup.17--C.sub.6-14-aryl,
--Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.17-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue is optionally substituted with 1 to 4
substituents R, wherein each R is independently selected from the
group consisting of halogen, --CN, *.dbd.O, --NH(C.sub.1-20-alkyl),
--N(C.sub.1-20-alkyl).sub.2, --N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--N(C.sub.6-14-aryl).sub.2, --S(O).sub.m--C.sub.1-20-alkyl,
--S(O).sub.m--OC.sub.1-20-alkyl, --S(O).sub.m--OC.sub.1-14-aryl,
--CHO, --C(O)--C.sub.1-20-alkyl, --C(O)--C.sub.6-14-aryl,
--C(O)--OC.sub.1-20-alkyl, --C(O)--OC.sub.6-14-aryl,
--C(O)NH.sub.2, --C(O)NH--C.sub.1-20-alkyl,
--C(O)N(C.sub.1-20-alkyl).sub.2, --C(O)NH--C.sub.6-14-aryl,
--C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(O)N(C.sub.6-14-aryl).sub.2, --C(S)NH.sub.2,
--C(S)NH--C.sub.1-20-alkyl, --C(S)N(C.sub.1-20-alkyl).sub.2,
--C(S)N(C.sub.6-14-aryl).sub.2,
--C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(S)NH--C.sub.6-14-aryl, --S(O).sub.mNH.sub.2,
--S(O).sub.mNH(C.sub.1-20-alkyl),
--S(O).sub.mN(C.sub.1-20-alkyl).sub.2,
--S(O).sub.mNH(C.sub.6-14-aryl),
--S(O).sub.mN(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--S(O).sub.mN(C.sub.6-14-aryl).sub.2 and
Si(C.sub.1-20-alkyl).sub.3, and wherein C.sub.3-10-cycloalkyl,
C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic
residue and monovalent 5 to 14 membered aromatic heterocyclic
residue is optionally substituted with 1 to 4 substituents R.sup.k,
wherein each R.sup.k is independently selected from the group
consisting of C.sub.1-20-alkyl, C.sub.1-20-alkoxy,
--S--C.sub.1-20-alkyl, C.sub.1-20-haloalkyl, [0335] wherein [0336]
Z.sup.17 at each occurrence is independently C.sub.1-6-alkylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0337] m at each
occurrence is independently 0, 1 or 2.
[0338] Preferably, each R is independently selected from the group
consisting of C.sub.1-30-alkyl, --Z.sup.17--O--C.sub.3-10-alkyl,
--Z.sup.17--S--C.sub.3-10-cycloalkyl,
--Z.sup.17--C.sub.3-10-cycloalkyl, --Z.sup.17--C.sub.6-14-aryl,
--Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.17-monovalent 5 to 14 membered aromatic
heterocyclic residue,
wherein C.sub.1-30-alkyl, C.sub.3-10-cycloalkyl, C.sub.6-14-aryl,
monovalent 3 to 12 membered aliphatic heterocyclic residue and
monovalent 5 to 14 membered aromatic heterocyclic residue is
optionally substituted with 1 to 4 substituents R.sup.j, wherein
each R.sup.j is independently selected from the group consisting of
halogen, --CN and *.dbd.O, and wherein C.sub.3-10-cycloalkyl,
C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic
residue and monovalent 5 to 14 membered aromatic heterocyclic
residue is optionally substituted with 1 to 4 substituents R.sup.k,
wherein each R.sup.k is independently selected from the group
consisting of C.sub.1-20-alkyl, C.sub.1-20-alkoxy,
C.sub.1-20-haloalkyl, [0339] wherein [0340] Z.sup.17 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.1-6-haloalkylene or a covalent bond.
[0341] More preferably, each R is independently selected from the
group consisting of C.sub.1-30-alkyl and
--Z.sup.17--C.sub.6-14-aryl,
wherein C.sub.1-30-alkyl and C.sub.6-14-aryl are optionally
substituted with 1 to 4 substituents R.sup.j, wherein each R.sup.j
is independently selected from the group consisting of halogen,
--CN and *.dbd.O, [0342] wherein [0343] Z.sup.17 at each occurrence
is a covalent bond and C.sub.6-14-aryl is optionally substituted
with 1 to 4 substituents R.sup.k, wherein each R.sup.k is
independently selected from the group consisting of
C.sub.1-20-alkyl and C.sub.1-20-alkoxy.
[0344] Most preferably, each R.sup.i is independently
C.sub.1-30-alkyl, preferably n-octyl, n-(2-ethyl)-hexyl, n-nonyl,
n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl,
n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,
n-nonadecyl and n-icosyl (C.sub.20), more preferably,
n-dodecyl.
[0345] More preferably, G.sup.1 and G.sup.2 are the same or
different and are phenylene, such as
##STR00023##
or, preferably, a monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue selected from the group consisting of
##STR00024##
which phenylene or monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue are optionally substituted with 1 to 2
substituents R.sup.i, wherein each R.sup.i is independently
selected from the group consisting of C.sub.1-30-alkyl,
--Z.sup.17--O--C.sub.1-30-alkyl, --Z.sup.17--S--C.sub.3-10-alkyl,
--Z.sup.17--C.sub.3-10-cycloalkyl, --Z.sup.17--C.sub.6-14-aryl,
--Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.17-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue is optionally substituted with 1 to 4
substituents R.sup.j, wherein each R.sup.j is independently
selected from the group consisting of halogen, --CN and *.dbd.O,
and wherein C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to
12 membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue is optionally substituted
with 1 to 4 substituents R.sup.k, wherein each R.sup.k is
independently selected from the group consisting of
C.sub.1-20-alkyl, C.sub.1-20-alkoxy, C.sub.1-20-haloalkyl, [0346]
wherein [0347] Z.sup.17 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.1-6-haloalkylene or a covalent bond.
[0348] Most preferably, G.sup.1 and G.sup.2 are the same or
different and are a monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue which monocyclic bivalent 5 to 8 membered
aromatic heterocyclic residue is
##STR00025##
which monocyclic bivalent 5 to 8 membered aromatic heterocyclic
residue is substituted with 1 to 2 substituents R, wherein each R
is independently selected from the group consisting of
C.sub.1-30-alkyl and --Z.sup.17--C.sub.6-14-aryl, wherein
C.sub.1-30-alkyl and C.sub.6-14-aryl are optionally substituted
with 1 to 4 substituents R.sup.j, wherein each R.sup.j is
independently selected from the group consisting of halogen, --CN
and *.dbd.O, and wherein C.sub.6-14-aryl is optionally substituted
with 1 to 4 substituents R.sup.k, wherein each R.sup.k is
independently selected from the group consisting of
C.sub.1-20-alkyl and C.sub.1-20-alkoxy, [0349] wherein [0350]
Z.sup.17 at each occurrence is a covalent bond.
[0351] In particular, G.sup.1 and G.sup.2 are the same or different
and are a monocyclic bivalent 5 to 8 membered aromatic heterocyclic
residue which monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue is
##STR00026##
which monocyclic bivalent 5 to 8 membered aromatic heterocyclic
residue is substituted with 1 substituent R.sup.i, wherein R.sup.i
is C.sub.1-30-alkyl, preferably n-octyl, n-(2-ethyl)hexyl, n-nonyl,
n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl,
n-tetradecyl, n pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,
n-nonadecyl and n-icosyl (C.sub.20), more preferably,
n-dodecyl.
[0352] Preferably, L is C.sub.6-24-arylene or a bivalent 5 to 18
membered aromatic heterocyclic residue, wherein C.sub.6-24-arylene
and bivalent 5 to 18 membered aromatic heterocyclic residue are
optionally substituted with 1 to 4 substituents R.sup.l, wherein
each R.sup.l is independently selected from the group consisting of
--CN, C.sub.1-30-alkyl, --Z.sup.18--O--C.sub.1-30-alkyl,
--Z.sup.18--S--C.sub.1-30-alkyl, --Z.sup.18--C.sub.3-10-cycloalkyl,
--Z.sup.18--C.sub.6-14-aryl, --Z.sup.18-monovalent 3 to 12 membered
aliphatic heterocyclic residue and --Z.sup.18-monovalent 5 to 14
membered aromatic heterocyclic residue,
wherein C.sub.1-30-alkyl, C.sub.3-10-cycloalkyl, C.sub.6-14-aryl,
monovalent 3 to 12 membered aliphatic heterocyclic residue and
monovalent 5 to 14 membered aromatic heterocyclic residue is
optionally substituted with 1 to 4 substituents R.sup.m, wherein
each R.sup.m is independently selected from the group consisting of
halogen, --CN, *.dbd.O, --NH(C.sub.1-20-alkyl),
--N(C.sub.1-20-alkyl).sub.2, --N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--N(C.sub.6-14-aryl).sub.2, --S(O).sub.o--C.sub.1-20-alkyl,
--S(O)O--OC.sub.1-20-alkyl, --S(O).sub.o--OC.sub.6-14-aryl, --CHO,
--C(O)--C.sub.1-20-alkyl, --C(O)--C.sub.6-14-aryl,
--C(O)--OC.sub.1-20-alkyl, --C(O)--OC.sub.6-14-aryl,
--C(O)NH.sub.2, --C(O)NH--C.sub.1-20-alkyl,
--C(O)N(C.sub.1-20-alkyl).sub.2, --C(O)NH--C.sub.6-14-aryl,
--C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(O)N(C.sub.6-14-aryl).sub.2, --C(S)NH.sub.2,
--C(S)NH--C.sub.1-20-alkyl, --C(S)N(C.sub.1-20-alkyl).sub.2,
--C(S)N(C.sub.6-14-aryl).sub.2,
--C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(S)NH--C.sub.6-14-aryl, --S(O).sub.oNH.sub.2,
--S(O).sub.oNH(C.sub.1-20-alkyl),
--S(O).sub.oN(C.sub.1-20-alkyl).sub.2,
--S(O).sub.oNH(C.sub.6-14-aryl),
--S(O)ON(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--S(O).sub.oN(C.sub.6-14-aryl).sub.2 and
Si(C.sub.1-20-alkyl).sub.3, and wherein C.sub.3-10-cycloalkyl,
C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic
residue and monovalent 5 to 14 membered aromatic heterocyclic
residue is optionally substituted with 1 to 4 substituents R.sup.k,
wherein each R.sup.k is independently selected from the group
consisting of C.sub.1-20-alkyl, C.sub.1-20-alkoxy,
--S--C.sub.1-20-alkyl, C.sub.1-20-haloalkyl, [0353] wherein [0354]
Z.sup.18 at each occurrence is independently C.sub.1-6-alkylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0355] o at each
occurrence is independently 0, 1 or 2, or
L is
[0356] ##STR00027## [0357] wherein [0358] R.sup.23 and R.sup.24 are
the same or different and are H, halogen, --CN, C.sub.1-30-alkyl,
C.sub.2-30-alkenyl, C.sub.1-30-haloalkyl, --X.sup.7--R.sup.25,
--X.sup.8--Ar.sup.13, --X.sup.8--Ar.sup.14--Ar.sup.13,
--X.sup.8--Ar.sup.14--R.sup.26 or
--X.sup.8--Ar.sup.14--Ar.sup.15--R.sup.26, [0359] wherein [0360]
X.sup.7 at each occurrence is independently --O--,
--[Z.sup.19--O].sub.o--, --[O--Z.sup.19].sub.o--O--, --S--,
--[Z.sup.19--S].sub.o--, --[S--Z.sup.19].sub.o--S--, --S(O),
--C(O)--, --C(O)O--, --C(O)NR.sup.27--, C(O)S--, --C(O)--,
--S(O)--, --NR.sup.27C(O)-- or --NR.sup.27--, [0361] wherein [0362]
Z.sup.19 at each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, [0363] c at each
occurrence is independently an integer from 1 to 10 and [0364]
R.sup.27 at each occurrence is independently H, C.sub.1-20-alkyl,
or --Z.sup.20--C.sub.6-14-aryl, [0365] wherein [0366] Z.sup.20 at
each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0367] R.sup.25 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0368] X.sup.8 at each occurrence is independently
--Z.sup.21--O--Z.sup.22--, --Z.sup.21--S--Z.sup.22--, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.28, --C(O)S--, --C(O)--,
--S(O)--, --NR.sup.28C(O)--, --NR.sup.28--,
--Z.sup.21--SiR.sup.28.sub.2--Z.sup.22--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0369] wherein [0370] Z.sup.21 and Z.sup.22 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0371] R.sup.28 at
each occurrence is independently H, C.sub.1-20-alkyl, or
--Z.sup.23--C.sub.6-14-aryl, [0372] wherein [0373] Z.sup.23 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0374] Ar.sup.14 at each occurrence is independently
C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic
residue, each optionally substituted with 1 to 5 substituents
R.sup.o, wherein each R.sup.o is independently selected from the
group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy
and C.sub.1-6-haloalkyl, [0375] Ar.sup.14 and Ar.sup.15 at each
occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 4 substituents R.sup.p, wherein each R.sup.p is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and
[0376] R.sup.26 at each occurrence is independently
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl and
C.sub.1-20-alkoxy.
[0377] Preferably, each R.sup.l, is independently selected from the
group consisting of C.sub.1-30-alkyl,
--Z.sup.18--O--C.sub.1-30-alkyl, --Z.sup.18--S--C.sub.1-30-alkyl,
--Z.sup.18--C.sub.3-10-cycloalkyl, --Z.sup.18--C.sub.6-14-aryl,
--Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.18-monovalent 5 to 14 membered aromatic
heterocyclic residue,
wherein C.sub.1-30-alkyl, C.sub.3-10-cycloalkyl, C.sub.6-14-aryl,
monovalent 3 to 12 membered aliphatic heterocyclic residue and
monovalent 5 to 14 membered aromatic heterocyclic residue is
optionally substituted with 1 to 4 substituents R.sup.m, wherein
each R.sup.m is independently selected from the group consisting of
halogen, --CN and *.dbd.O, and wherein C.sub.3-10-cycloalkyl,
C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic
residue and monovalent 5 to 14 membered aromatic heterocyclic
residue is optionally substituted with 1 to 4 substituents R.sup.n,
wherein each R.sup.n is independently selected from the group
consisting of C.sub.1-20-alkyl, C.sub.1-20-alkoxy,
C.sub.1-20-haloalkyl, [0378] wherein [0379] Z.sup.18 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.1-6-haloalkylene or a covalent bond.
[0380] More preferably, each R.sup.l is independently selected from
the group consisting of C.sub.1-30-alkyl and
--Z.sup.18--C.sub.6-14-aryl,
wherein C.sub.1-30-alkyl and C.sub.6-14-aryl are optionally
substituted with 1 to 4 substituents R.sup.m, wherein each R.sup.m
is independently selected from the group consisting of halogen,
--CN and *.dbd.O, and wherein C.sub.6-14-aryl is optionally
substituted with 1 to 4 substituents R.sup.n, wherein each R.sup.n
is independently selected from the group consisting of
C.sub.1-20-alkyl and C.sub.1-20-alkoxy, [0381] wherein [0382]
Z.sup.18 at each occurrence is a covalent bond.
[0383] Most preferably, each R.sup.l is independently
C.sub.1-30-alkyl, preferably n-octyl, n-(2-ethyl)-hexyl, n-nonyl,
n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl,
n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,
n-nonadecyl and n-icosyl (C.sub.20), more preferably,
n-hexadecyl.
[0384] Preferably, R.sup.23 and R.sup.24 are the same or different
and are H, halogen, --CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.1-30-haloalkyl, --X.sup.7--R.sup.25, --X.sup.8--Ar.sup.13,
--X.sup.8--Ar.sup.14--Ar.sup.13, --X.sup.8--Ar.sup.14--R.sup.26 or
--X.sup.8--Ar.sup.14--Ar.sup.15--R.sup.26, [0385] wherein [0386]
X.sup.7 at each occurrence is independently --O--,
--[Z.sup.19--O].sub.c--, --[O--Z.sup.19].sub.c, --O--, --S--,
[Z.sup.19--S--].sub.c--, or --[S--Z.sup.19].sub.c--S--, [0387]
wherein [0388] Z.sup.19 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene,
[0389] c at each occurrence is independently an integer from 1 to
10 and [0390] R.sup.25 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0391] X.sup.8 at each occurrence is independently
--Z.sup.21--O--Z.sup.22--, --Z.sup.21--S--Z.sup.22--,
C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene
or a covalent bond, [0392] wherein [0393] Z.sup.21 and Z.sup.22 at
each occurrence are independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
and [0394] Ar.sup.13 at each occurrence is independently
C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic
residue, each optionally substituted with 1 to 5 substituents
R.sup.o, wherein each R.sup.o is independently selected from the
group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy
and C.sub.1-6-haloalkyl, [0395] Ar.sup.14 and Ar.sup.15 at each
occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 4 substituents R.sup.p, wherein each R.sup.p is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and
[0396] R.sup.26 at each occurrence is independently
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or
C.sub.1-20-alkoxy.
[0397] More preferably, R.sup.23 and R.sup.24 are the same or
different and are H, C.sub.1-30-alkyl, C.sub.1-30-haloalkyl,
--X.sup.7--R.sup.25 or --X.sup.8--Ar.sup.13, [0398] wherein [0399]
X.sup.7 at each occurrence is independently
--[Z.sup.19--O].sub.c--, --[Z.sup.19--S--].sub.c--, or
--[S--Z.sup.19].sub.c--S--, [0400] wherein [0401] Z.sup.19 at each
occurrence is independently C.sub.1-6-alkylene or
C.sub.1-6-haloalkylene, [0402] c at each occurrence is
independently an integer from 1 to 10 and [0403] R.sup.25 at each
occurrence is independently C.sub.1-30-alkyl or
C.sub.1-30-haloalkyl, [0404] X.sup.8 at each occurrence is
independently --Z.sup.21--O--Z.sup.22--, --Z.sup.21--S--Z.sup.22--,
C.sub.1-30-alkylene or C.sub.1-30-haloalkylene, [0405] wherein
[0406] Z.sup.21 and Z.sup.22 at each occurrence are independently
C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, and [0407] Ar.sup.13
at each occurrence is independently C.sub.6-14-aryl, optionally
substituted with 1 to 5 substituents R.sup.o, wherein each R.sup.o
is independently selected from the group consisting of halogen
C.sub.1-6-alkyl and C.sub.1-6-alkoxy.
[0408] Most preferably, R.sup.23 and R.sup.24 are the same or
different and are H, C.sub.1-30-alkyl or C.sub.1-30-haloalkyl, in
particular H.
[0409] More preferably, L is a bivalent 5 to 18 membered aromatic
heterocyclic residue, wherein the bivalent 5 to 18 membered
aromatic heterocyclic residue is optionally substituted with 1 to 4
substituents R.sup.l, wherein each R.sup.l is independently
selected from the group consisting of C.sub.1-30-alkyl,
--Z.sup.18--O--C.sub.1-30-alkyl, --Z.sup.18--S--C.sub.1-30-alkyl,
--Z.sup.18--C.sub.3-10-cycloalkyl, --Z.sup.18--C.sub.6-14-aryl,
--Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.18-monovalent 5 to 14 membered aromatic
heterocyclic residue,
wherein C.sub.1-30-alkyl, C.sub.3-10-cycloalkyl, C.sub.6-14-aryl,
monovalent 3 to 12 membered aliphatic heterocyclic residue and
monovalent 5 to 14 membered aromatic heterocyclic residue is
optionally substituted with 1 to 4 substituents R.sup.m, wherein
each R.sup.m is independently selected from the group consisting of
halogen, --CN and *.dbd.O, and wherein C.sub.3-10-cycloalkyl,
C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic
residue and monovalent 5 to 14 membered aromatic heterocyclic
residue is optionally substituted with 1 to 4 substituents R.sup.n,
wherein each R.sup.n is independently selected from the group
consisting of C.sub.1-20-alkyl, C.sub.1-20-alkoxy,
C.sub.1-20-haloalkyl, [0410] wherein [0411] Z.sup.18 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.1-6-haloalkylene or a covalent bond, or
L is
##STR00028##
[0412] wherein R.sup.23 and R.sup.24 are the same or different and
are H, halogen, --CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.1-30-haloalkyl, --X.sup.7--R.sup.25, --X.sup.8--Ar.sup.13,
--X.sup.8--Ar.sup.14--Ar.sup.13, --X.sup.8--Ar.sup.14--R.sup.26 or
--X.sup.8--Ar.sup.14--Ar.sup.15--R.sup.26, [0413] wherein [0414]
X.sup.7 at each occurrence is independently --O--,
--[Z.sup.19--O].sub.c--, --[O--Z.sup.19].sub.c--, --O--, --S--,
--[Z.sup.19--S].sub.c--, or --[S--Z.sup.19].sub.c--S--, [0415]
wherein [0416] Z.sup.19 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene,
[0417] c at each occurrence is independently an integer from 1 to
10 and [0418] R.sup.25 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0419] X.sup.8 at each occurrence is independently
--Z.sup.21--O--Z.sup.22--, --Z.sup.21--S--Z.sup.22--,
C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene
or a covalent bond, [0420] wherein [0421] Z.sup.21 and Z.sup.22 at
each occurrence are independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
and [0422] Ar.sup.13 at each occurrence is independently
C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic
residue, each optionally substituted with 1 to 5 substituents
R.sup.o, wherein each R.sup.o is independently selected from the
group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy
and C.sub.1-6-haloalkyl, [0423] Ar.sup.14 and Ar.sup.15 at each
occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 4 substituents R.sup.p, wherein each R.sup.p is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and
[0424] R.sup.26 at each occurrence is independently
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or
C.sub.1-20-alkoxy.
[0425] Even more preferably, L is a bivalent 5 to 18 membered
aromatic heterocyclic residue selected from the group consisting
of
##STR00029## ##STR00030## ##STR00031## ##STR00032##
wherein the bivalent 5 to 18 membered aromatic heterocyclic residue
is optionally substituted with 1 to 4 substituents R.sup.l, wherein
each R.sup.l R.sup.l is independently selected from the group
consisting of C.sub.1-30-alkyl and --Z.sup.18--C.sub.6-14-aryl,
wherein C.sub.1-30-alkyl and C.sub.6-14-aryl are optionally
substituted with 1 to 4 substituents R.sup.m, wherein each R.sup.m
is independently selected from the group consisting of halogen,
--CN and *.dbd.O, and wherein C.sub.6-14-aryl is optionally
substituted with 1 to 4 substituents R.sup.n, wherein each R.sup.n
is independently selected from the group consisting of
C.sub.1-20-alkyl and C.sub.1-20-alkoxy, [0426] wherein [0427]
Z.sup.18 at each occurrence is a covalent bond, [0428] wherein,
[0429] M.sup.1, M.sup.2 and M.sup.3 can be the same or different
and are S, O, NH or SiR.sup.tR.sup.t, preferably M.sup.1, M.sup.2
are S or NH, and M.sup.3 is S, O, NH or SiR.sup.tR.sup.t, more
preferably M.sup.1 and M.sup.2 are S, and M.sup.3 is NH or
SiR.sup.tR.sup.t, [0430] wherein R' is H or C.sub.1-30-alkyl,
or
L is
[0431] ##STR00033## [0432] wherein [0433] R.sup.23 and R.sup.24 are
the same or different and are H, C.sub.1-30-alkyl,
C.sub.1-30-haloalkyl, --X.sup.7--R.sup.25 or --X.sup.8--Ar.sup.13,
[0434] wherein [0435] X.sup.7 at each occurrence is independently
--[Z.sup.19--O].sub.c--, --[Z.sup.19--S--].sub.c--, or
--[S--Z.sup.19].sub.c--S--, [0436] wherein [0437] Z.sup.19 at each
occurrence is independently C.sub.1-6-alkylene or
C.sub.1-6-haloalkylene, [0438] c at each occurrence is
independently an integer from 1 to 10 and [0439] R.sup.25 at each
occurrence is independently C.sub.1-30-alkyl or
C.sub.1-30-haloalkyl, [0440] X.sup.8 at each occurrence is
independently --Z.sup.21--O--Z.sup.22--, --Z.sup.21--S--Z.sup.22--,
C.sub.1-30-alkylene or C.sub.1-30-haloalkylene, [0441] wherein
[0442] Z.sup.21 and Z.sup.22 at each occurrence are independently
C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, and [0443] Ar.sup.13
at each occurrence is independently C.sub.6-14-aryl, optionally
substituted with 1 to 5 substituents R.sup.o, wherein each R.sup.o
is independently selected from the group consisting of halogen
C.sub.1-6-alkyl and C.sub.1-6-alkoxy.
[0444] Even more preferably,
L is a bivalent 5 to 18 membered aromatic heterocyclic residue
selected from the group consisting of
##STR00034## ##STR00035## ##STR00036## ##STR00037##
wherein the bivalent 5 to 18 membered aromatic heterocyclic residue
is optionally substituted with 1 to 4 substituents R', wherein each
wherein each R.sup.l R.sup.l is independently selected from the
group consisting of C.sub.1-30-alkyl and
--Z.sup.18--C.sub.6-14-aryl, wherein C.sub.1-30-alkyl and
C.sub.6-14-aryl are optionally substituted with 1 to 4 substituents
R.sup.m, wherein each R.sup.m is independently selected from the
group consisting of halogen, --CN and *.dbd.O, and wherein
C.sub.6-14-aryl is optionally substituted with 1 to 4 substituents
R.sup.n, wherein each R.sup.n is independently selected from the
group consisting of C.sub.1-20-alkyl and C.sub.1-20-alkoxy, [0445]
wherein [0446] Z.sup.18 at each occurrence is a covalent bond,
[0447] wherein R.sup.t is hydrogen or C.sub.1-30-alkyl, or
L is
[0448] ##STR00038## [0449] wherein [0450] R.sup.23 and R.sup.24 are
the same or different and are H, C.sub.1-30-alkyl,
C.sub.1-30-haloalkyl, --X.sup.7--R.sup.25 or --X.sup.8--Ar.sup.13,
[0451] wherein [0452] X.sup.7 at each occurrence is independently
--[Z.sup.19--O].sub.c--, --[Z.sup.19--S--].sub.c--, or
--[S--Z.sup.19].sub.c--S--, [0453] wherein [0454] Z.sup.19 at each
occurrence is independently C.sub.1-6-alkylene or
C.sub.1-6-haloalkylene, [0455] c at each occurrence is
independently an integer from 1 to 10 and [0456] R.sup.25 at each
occurrence is independently C.sub.1-30-alkyl or
C.sub.1-30-haloalkyl, [0457] X.sup.8 at each occurrence is
independently --Z.sup.21--O--Z.sup.22--, --Z.sup.21--S--Z.sup.22--,
C.sub.1-30-alkylene or C.sub.1-30-haloalkylene, [0458] wherein
[0459] Z.sup.21 and Z.sup.22 at each occurrence are independently
C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, and [0460] Ar.sup.13
at each occurrence is independently C.sub.6-14-aryl, optionally
substituted with 1 to 5 substituents R.sup.o, wherein each R.sup.o
is independently selected from the group consisting of halogen
C.sub.1-6-alkyl and C.sub.1-6-alkoxy.
[0461] Even more preferably,
L is a bivalent 5 to 18 membered aromatic heterocyclic residue
selected from the group consisting of
##STR00039## ##STR00040##
wherein the bivalent 5 to 18 membered aromatic heterocyclic residue
is optionally substituted with 1 to 4 substituents R.sup.l, wherein
each R.sup.l R.sup.l is independently selected from the group
consisting of C.sub.1-30-alkyl and --Z.sup.18--C.sub.6-14-aryl,
wherein C.sub.1-30-alkyl and C.sub.6-14-aryl are optionally
substituted with 1 to 4 substituents R.sup.m, wherein each R.sup.m
is independently selected from the group consisting of halogen,
--CN and *.dbd.O, and wherein C.sub.6-14-aryl is optionally
substituted with 1 to 4 substituents R.sup.n, wherein each R.sup.n
is independently selected from the group consisting of
C.sub.1-20-alkyl and C.sub.1-20-alkoxy, [0462] wherein [0463]
Z.sup.18 at each occurrence is a covalent bond, [0464] wherein
R.sup.t is hydrogen or C.sub.1-30-alkyl, or
L is
[0465] ##STR00041## [0466] wherein [0467] R.sup.23 and R.sup.24 are
the same or different and are H, C.sub.1-30-alkyl,
C.sub.1-30-haloalkyl, --X.sup.7--R.sup.25 or --X.sup.8--Ar.sup.13,
[0468] wherein [0469] X.sup.7 at each occurrence is independently
--[Z.sup.19--O].sub.c--, --[Z.sup.19--S--].sub.c--, or
--[S--Z.sup.19].sub.c--S--, wherein [0470] Z.sup.19 at each
occurrence is independently C.sub.1-6-alkylene or
C.sub.1-6-haloalkylene, [0471] c at each occurrence is
independently an integer from 1 to 10 and [0472] R.sup.25 at each
occurrence is independently C.sub.1-30-alkyl or
C.sub.1-30-haloalkyl, [0473] X.sup.8 at each occurrence is
independently --Z.sup.21--O--Z.sup.22--, --Z.sup.21--S--Z.sup.22--,
C.sub.1-30-alkylene or C.sub.1-30-haloalkylene, [0474] wherein
[0475] Z.sup.21 and Z.sup.22 at each occurrence are independently
C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, and [0476] Ar.sup.13
at each occurrence is independently C.sub.6-14-aryl, optionally
substituted with 1 to 5 substituents R.sup.o, wherein each R.sup.o
is independently selected from the group consisting of halogen
C.sub.1-6-alkyl and C.sub.1-6-alkoxy.
[0477] Most preferably,
L is
##STR00042##
[0478] wherein each R.sup.l is independently C.sub.1-30-alkyl,
preferably n-octyl, n-(2-ethyl)hexyl, n-nonyl, n-decyl, n-undecyl,
n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,
n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl
and n-icosyl (C.sub.20), more preferably, n-hexadecyl, or
L is
##STR00043##
[0479] wherein R.sup.23 and R.sup.24 are the same or different and
are H, C.sub.1-30-alkyl or C.sub.1-30-haloalkyl, in particular
H.
[0480] Preferably, q, r and s are 0 or 1, with the proviso that q,
r and s are not all 0 at the same time.
[0481] Preferably, n is an integer from 1 to 5000, 1 to 1000, 1 to
100, 1 to 50 or from 1 to 30, for example n can be an integer from
2 to 5000, 2 to 1000, 2 to 50, 2 to 30. In some embodiments, n can
be an integer from 4 to 1000, 4 to 100, 8 to 1000 or 8 to 100.
[0482] In one embodiment,
A.sup.1 and A.sup.2 are S,
E is
[0483] ##STR00044## [0484] wherein [0485] R.sup.1 and R.sup.2 are
the same or different and are H, C.sub.1-30-alkyl,
C.sub.1-30-haloalkyl, --X.sup.1--R.sup.6 or --X.sup.2--Ar.sup.1,
[0486] wherein [0487] X.sup.1 at each occurrence is independently
--[Z.sup.1--O].sub.a--, --[Z.sup.1--S--].sub.a--, or
--[S--Z.sup.1].sub.a--S--, [0488] wherein [0489] Z.sup.1 at each
occurrence is independently C.sub.1-6-alkylene or
C.sub.1-6-haloalkylene, [0490] a at each occurrence is
independently an integer from 1 to 10 and [0491] R.sup.6 at each
occurrence is independently C.sub.1-30-alkyl or
C.sub.1-30-haloalkyl, [0492] X.sup.2 at each occurrence is
independently --Z.sup.3--O--Z.sup.4--, --Z.sup.3--S--Z.sup.4--,
C.sub.1-30-alkylene or C.sub.1-30-haloalkylene, [0493] wherein
[0494] Z.sup.3 and Z.sup.4 at each occurrence are independently
C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, and [0495] Ar.sup.1
at each occurrence is independently C.sub.6-14-aryl, optionally
substituted with 1 to 5 substituents R.sup.a, wherein each R.sup.a
is independently selected from the group consisting of halogen
C.sub.1-6-alkyl and C.sub.1-6-alkoxy.
[0496] L is a bivalent 5 to 18 membered aromatic heterocyclic
residue, wherein the bivalent 5 to 18 membered aromatic
heterocyclic residue is optionally substituted with 1 to 4
substituents R.sup.l, wherein each R.sup.l is independently
selected from the group consisting of C.sub.1-30-alkyl,
--Z.sup.18--O--C.sub.1-30-alkyl, --Z.sup.18--S--C.sub.1-30-alkyl,
--Z.sup.18--C.sub.3-10-cycloalkyl, --Z.sup.18--C.sub.6-14-aryl,
--Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.18-monovalent 5 to 14 membered aromatic
heterocyclic residue,
wherein C.sub.1-30-alkyl, C.sub.3-10-cycloalkyl, C.sub.6-14-aryl,
monovalent 3 to 12 membered aliphatic heterocyclic residue and
monovalent 5 to 14 membered aromatic heterocyclic residue is
optionally substituted with 1 to 4 substituents R.sup.m, wherein
each R.sup.m is independently selected from the group consisting of
halogen, --CN and *.dbd.O, and wherein C.sub.3-10-cycloalkyl,
C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic
residue and monovalent 5 to 14 membered aromatic heterocyclic
residue is optionally substituted with 1 to 4 substituents R.sup.n,
wherein each R.sup.n is independently selected from the group
consisting of C.sub.1-20-alkyl, C.sub.1-20-alkoxy,
C.sub.1-20-haloalkyl, [0497] wherein [0498] Z.sup.18 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.1-6-haloalkylene or a covalent bond, q and s are 0, r is 1,
and n is an integer from 1 to 1000, preferably 4 to 100.
[0499] In a second embodiment,
A.sup.1 and A.sup.2 are S,
E is
[0500] ##STR00045## [0501] wherein [0502] R.sup.1 and R.sup.2 are
the same or different and are H, C.sub.1-30-alkyl,
C.sub.1-30-haloalkyl, --X.sup.1--R.sup.6 or --X.sup.2--Ar.sup.1,
[0503] wherein [0504] X.sup.1 at each occurrence is independently
--[Z.sup.1--O].sub.a--, --[Z.sup.1--S].sub.a--, or
--[S--Z.sup.1].sub.a--S--, [0505] wherein [0506] Z.sup.1 at each
occurrence is independently C.sub.1-6-alkylene or
C.sub.1-6-haloalkylene, [0507] a at each occurrence is
independently an integer from 1 to 10 and [0508] R.sup.6 at each
occurrence is independently C.sub.1-30-alkyl or
C.sub.1-30-haloalkyl, [0509] X.sup.2 at each occurrence is
independently --Z.sup.3--O--Z.sup.4--, --Z.sup.3--S--Z.sup.4--,
C.sub.1-30-alkylene or C.sub.1-30-haloalkylene, [0510] wherein
[0511] Z.sup.3 and Z.sup.4 at each occurrence are independently
C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, and [0512] Ar.sup.1
at each occurrence is independently C.sub.6-14-aryl, optionally
substituted with 1 to 5 substituents R.sup.a, wherein each R.sup.a
is independently selected from the group consisting of halogen
C.sub.1-6-alkyl and C.sub.1-6-alkoxy,
[0513] G.sup.1 and G.sup.2 are the same or different and are
phenylene such as
##STR00046##
or, preferably, a monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue selected from the group consisting of
##STR00047##
which phenylene or monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue are optionally substituted with 1 to 2
substituents R.sup.i, wherein each R.sup.i is independently
selected from the group consisting of C.sub.1-30-alkyl,
--Z.sup.17--O--C.sub.1-30-alkyl, --Z.sup.17--S--C.sub.1-30-alkyl,
--Z.sup.17--C.sub.3-10-cycloalkyl, --Z.sup.17--C.sub.6-14-aryl,
--Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.17-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue is optionally substituted with 1 to 4
substituents R.sup.j, wherein each R.sup.j is independently
selected from the group consisting of halogen, --CN and *.dbd.O,
and wherein C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to
12 membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue is optionally substituted
with 1 to 4 substituents R.sup.k, wherein each R.sup.k is
independently selected from the group consisting of
C.sub.1-20-alkyl, C.sub.1-20-alkoxy, C.sub.1-20-haloalkyl, [0514]
wherein [0515] Z.sup.17 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.1-6-haloalkylene or a covalent bond.
L is
[0516] ##STR00048## [0517] wherein [0518] R.sup.23 and R.sup.24 are
the same or different and are H, C.sub.1-30-alkyl,
C.sub.1-30-haloalkyl, --X.sup.7--R.sup.25 or --X.sup.8--Ar.sup.13,
[0519] wherein [0520] X.sup.7 at each occurrence is independently
--[Z.sup.19--O].sub.c--, --[Z.sup.19--S--].sub.c--, or
--[S--Z.sup.19].sub.c--S--, [0521] wherein [0522] Z.sup.19 at each
occurrence is independently C.sub.1-6-alkylene or
C.sub.1-6-haloalkylene, [0523] c at each occurrence is
independently an integer from 1 to 10 and [0524] R.sup.25 at each
occurrence is independently C.sub.1-30-alkyl or
C.sub.1-30-haloalkyl, [0525] X.sup.8 at each occurrence is
independently C.sub.1-30-alkylene or C.sub.1-30-haloalkylene,
[0526] wherein [0527] Z.sup.21 and Z.sup.22 at each occurrence are
independently C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, and
[0528] Ar.sup.13 at each occurrence is independently
C.sub.6-14-aryl, optionally substituted with 1 to 5 substituents
R.sup.o, wherein each R.sup.o is independently selected from the
group consisting of halogen C.sub.1-6-alkyl and C.sub.1-6-alkoxy, q
and s are 1, r is 1, and n is an integer from 1 to 1000, preferably
from 2 to 50.
[0529] In a third embodiment,
A.sup.1 and A.sup.2 are S,
E is
[0530] ##STR00049## [0531] wherein [0532] R.sup.1 and R.sup.2 are
the same or different and are H, C.sub.1-30-alkyl,
C.sub.1-30-haloalkyl, --X.sup.1--R.sup.6 or --X.sup.2--Ar.sup.1,
[0533] wherein [0534] X.sup.1 at each occurrence is independently
--[Z.sup.1--O].sub.a--, --[Z.sup.1--S].sub.a--, or
--[S--Z.sup.1].sub.a--S--, [0535] wherein [0536] Z.sup.1 at each
occurrence is independently C.sub.1-6-alkylene or
C.sub.1-6-haloalkylene, [0537] a at each occurrence is
independently an integer from 1 to 10 and [0538] R.sup.6 at each
occurrence is independently C.sub.1-30-alkyl or
C.sub.1-30-haloalkyl, [0539] X.sup.2 at each occurrence is
independently --Z.sup.3--O--Z.sup.4--, --Z.sup.3--S--Z.sup.4--,
C.sub.1-30-alkylene or C.sub.1-30-haloalkylene, [0540] wherein
[0541] Z.sup.3 and Z.sup.4 at each occurrence are independently
C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, and [0542] Ar.sup.1
at each occurrence is independently C.sub.6-14-aryl, optionally
substituted with 1 to 5 substituents R.sup.a, wherein each R.sup.a
is independently selected from the group consisting of halogen
C.sub.1-6-alkyl and C.sub.1-6-alkoxy,
[0543] G.sup.1 and G.sup.2 are the same or different and are
phenylene such as
##STR00050##
or, preferably, a monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue selected from the group consisting of
##STR00051##
which phenylene or monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue are optionally substituted with 1 to 2
substituents R.sup.i, wherein each R.sup.i is independently
selected from the group consisting of C.sub.1-30-alkyl,
--Z.sup.17--O--C.sub.1-30-alkyl, --Z.sup.17--S--C.sub.1-30-alkyl,
--Z.sup.17C.sub.3-10-cycloalkyl, --Z.sup.17--C.sub.6-14-aryl,
--Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.17-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue is optionally substituted with 1 to 4
substituents R.sup.j, wherein each R.sup.j is independently
selected from the group consisting of halogen, --CN and *.dbd.O,
and wherein C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to
12 membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue is optionally substituted
with 1 to 4 substituents R.sup.k, wherein each R.sup.k is
independently selected from the group consisting of
C.sub.1-20-alkyl, C.sub.1-20-alkoxy, C.sub.1-20-haloalkyl, [0544]
wherein [0545] Z.sup.17 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.1-6-haloalkylene or a covalent bond, q
and s are 1, r is 0, and n is an integer from 1 to 1000, preferably
from 1 to 30.
[0546] In a fourth embodiment,
A.sup.1 and A.sup.2 are S,
E is
[0547] ##STR00052## [0548] wherein [0549] R.sup.3 is
--X.sup.5--Ar.sup.7, --X.sup.5--Ar.sup.8--Ar.sup.7,
--X.sup.5--Ar.sup.8--R.sup.13 or
--X.sup.5--Ar.sup.8--Ar.sup.9--R.sup.13, [0550] wherein [0551]
X.sup.5 at each occurrence is a covalent bond, [0552] Ar.sup.7 at
each occurrence is independently C.sub.6-14-aryl or monovalent 5 to
14 membered aromatic heterocyclic residue, each optionally
substituted with 1 to 5 substituents R.sup.e, wherein each R.sup.e
is independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0553]
Ar.sup.8 and Ar.sup.9 at each occurrence are independently
C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.f, wherein each R.sup.f is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and [0554] R.sup.13 at
each occurrence is independently C.sub.1-20-alkyl,
C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy,
G.sup.1 and G.sup.2 are the same or different and are phenylene
such as
##STR00053##
[0554] or, preferably, a monocyclic bivalent 5 to 8 membered
aromatic heterocyclic residue selected from the group consisting
of
##STR00054##
which phenylene or monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue are optionally substituted with 1 to 2
substituents R, wherein each R is independently selected from the
group consisting of C.sub.1-30-alkyl,
--Z.sup.17--O--C.sub.1-30-alkyl, --Z.sup.17--S--C.sub.1-30-alkyl,
--Z.sup.17--C.sub.3-10-cycloalkyl, --Z.sup.17--C.sub.6-14-aryl,
--Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.17-monovalent 5 to 14 membered aromatic
heterocyclic residue, wherein C.sub.1-30-alkyl,
C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered
aliphatic heterocyclic residue and monovalent 5 to 14 membered
aromatic heterocyclic residue is optionally substituted with 1 to 4
substituents R.sup.j, wherein each R.sup.j is independently
selected from the group consisting of halogen, --CN and *.dbd.O,
and wherein C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to
12 membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue is optionally substituted
with 1 to 4 substituents R.sup.k, wherein each R.sup.k is
independently selected from the group consisting of
C.sub.1-20-alkyl, C.sub.1-20-alkoxy, C.sub.1-20-haloalkyl, [0555]
wherein [0556] Z.sup.17 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.1-6-haloalkylene or a covalent bond,
L is
[0557] ##STR00055## [0558] wherein [0559] R.sup.23 and R.sup.24 are
the same or different and are H, C.sub.1-30-alkyl,
C.sub.1-30-haloalkyl, --X.sup.7--R.sup.25 or --X.sup.8--Ar.sup.13,
[0560] wherein [0561] X.sup.7 at each occurrence is independently
--[Z.sup.19--O].sub.c--, --[Z.sup.19--S--].sub.c--, or
--[S--Z.sup.19].sub.c--S--, [0562] wherein [0563] Z.sup.19 at each
occurrence is independently C.sub.1-6-alkylene or
C.sub.1-6-haloalkylene, [0564] c at each occurrence is
independently an integer from 1 to 10 and [0565] R.sup.25 at each
occurrence is independently C.sub.1-30-alkyl or
C.sub.1-30-haloalkyl, [0566] X.sup.8 at each occurrence is
independently C.sub.1-30-alkylene or C.sub.1-30-haloalkylene,
[0567] wherein [0568] Z.sup.21 and Z.sup.22 at each occurrence are
independently C.sub.1-6-alkylene or C.sub.1-6-haloalkylene, and
[0569] Ar.sup.13 at each occurrence is independently
C.sub.6-14-aryl, optionally substituted with 1 to 5 substituents
R.sup.o, wherein each R.sup.o is independently selected from the
group consisting of halogen C.sub.1-6-alkyl and C.sub.1-6-alkoxy, q
and s are 1, r is 1, and n is an integer from 1 to 1000, preferably
from 2 to 50.
[0570] Examples of compounds, oligomers or polymers of formula 1
are
##STR00056##
wherein n is an integer from 1 to 1000, preferably 1 to 100, 1 to
50 or from 1 to 30, for example n can be an integer from 2 to 1000,
2 to 100, 2 to 50, 2 to 30, or an integer from 4 to 100 or 8 to
100.
[0571] Also part of the present invention is a process for the
preparation of the compound, oligomer or polymer of formula
##STR00057## [0572] wherein [0573] A.sup.1 and A.sup.2 can be the
same or different and are S or Se, [0574] E is selected from the
group consisting of
[0574] ##STR00058## [0575] wherein [0576] R.sup.1 and R.sup.2 can
be the same or different and are H, halogen, --CN,
C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-20-alkynyl,
C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12
membered aliphatic heterocyclic residue, --X.sup.1--R.sup.6,
--X.sup.2--Ar.sup.1, --X.sup.2--Ar.sup.2--Ar.sup.1,
--X.sup.2--Ar.sup.2--R.sup.7 or
--X.sup.2--Ar.sup.2--Ar.sup.3--R.sup.7, [0577] wherein [0578]
X.sup.1 at each occurrence is independently --O--,
--[Z.sup.1--O].sub.a--, [O--Z.sup.1].sub.a--, --O--, --S--,
--[Z.sup.1--S--].sub.a--, --[S--Z.sup.1].sub.a--S--, --S(O),
--C(O)--, --C(O)O--, --C(O)NR.sup.8, C(O)S--, --C(O)--, --S(O)--,
--NR.sup.8C(O)-- or --NR.sup.8--, [0579] wherein [0580] Z.sup.1 at
each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, [0581] a at each
occurrence is independently an integer from 1 to 10 and [0582]
R.sup.8 at each occurrence is independently H, C.sub.1-20-alkyl, or
--Z.sup.2--C.sub.6-14-aryl, [0583] wherein [0584] Z.sup.2 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0585] R.sup.6 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0586] X.sup.2 at each occurrence is independently
--Z.sup.3--O--Z.sup.4--, --S(O)--, --C(O)--, --C(O)O--,
--C(O)NR.sup.9, --C(O)S--, --O(CO)--, --S(CO)--, --NR.sup.9C(O)--,
--NR.sup.9--, --Z.sup.3--SiR.sup.9.sub.2--Z.sup.4--,
C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene
or a covalent bond, [0587] wherein [0588] Z.sup.3 and Z.sup.4 at
each occurrence are independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
and [0589] R.sup.9 at each occurrence is independently H,
C.sub.1-20-alkyl, or --Z.sup.5--C.sub.6-14-aryl, [0590] wherein
[0591] Z.sup.5 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, [0592] Ar.sup.1 at each occurrence is
independently C.sub.6-14-aryl or monovalent 5 to 14 membered
aromatic hetrocyclic residue, each optionally substituted with 1 to
5 substituents R.sup.a, wherein each R.sup.a is independently
selected from the group consisting of halogen, CN, 016 alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0593] Ar.sup.2 and
Ar.sup.3 at each occurrence are independently C.sub.6-14-arylene or
bivalent 5 to 14 membered aromatic heterocyclic residue, each
optionally substituted with 1 to 4 substituents R.sup.b, wherein
each R.sup.b is independently selected from the group consisting of
halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and
C.sub.1-6-haloalkyl, and [0594] R.sup.7 at each occurrence is
independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.1-20-haloalkyl, C.sub.1-20-alkoxy, --X.sup.3--Ar.sup.4,
--X.sup.3--Ar.sup.5--Ar.sup.4, --X.sup.3--Ar.sup.5--R.sup.10, or
--X.sup.3--Ar.sup.5--Ar.sup.6--R.sup.10, [0595] wherein [0596]
X.sup.3 at each occurrence is independently
--Z.sup.6--O--Z.sup.7--, --Z.sup.6--S--Z.sup.7, --S(O)--, --C(O)--,
--C(O)O--, --(O)NR.sup.11, --C(O)S--, --O(CO)--, --S(CO)--,
--NR.sup.11C(O)--, --NR.sup.11--,
--Z.sup.6--SiR.sup.11.sub.2--Z.sup.7--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0597] wherein [0598] Z.sup.6 and Z.sup.7 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0599] R.sup.11 at
each occurrence is independently H, C.sub.1-20-alkyl or
--Z.sup.8--C.sub.6-14-aryl, wherein Z.sup.8 at each occurrence is
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, [0600] Ar.sup.4 at each
occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 5 substituents R.sup.c, wherein each R.sup.c is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0601]
Ar.sup.5 and Ar.sup.6 at each occurrence are independently
C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.d, wherein each R.sup.d is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and [0602] R.sup.10 at
each occurrence is independently C.sub.1-20-alkyl,
C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy,
[0603] R.sup.3, R.sup.4 and R.sup.5 can be the same or different
and are H, halogen, --CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12
membered aliphatic heterocyclic residue, --X.sup.4--R.sup.12,
--X.sup.5--Ar.sup.7, --X.sup.5--Ar.sup.8--Ar.sup.7,
--X.sup.5--Ar.sup.8--R.sup.13 or
--X.sup.5--Ar.sup.8--Ar.sup.9--R.sup.13, [0604] wherein [0605]
X.sup.4 at each occurrence is independently --[Z.sup.9--O].sub.b--,
--[Z.sup.9--S--].sub.b--, --S(O)--, --C(O)--, --C(O)O--,
--C(O)NR.sup.14-- or C(O)S--, [0606] wherein [0607] Z.sup.9 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, [0608] b at each
occurrence is independently an integer from 1 to 10 and [0609]
R.sup.14 at each occurrence is independently H, C.sub.1-20-alkyl,
or --Z.sup.10--C.sub.6-14-aryl, wherein Z.sup.10 at each occurrence
is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, [0610] R.sup.12 at each
occurrence is independently C.sub.1-30-alkyl, C.sub.2-30-alkenyl or
C.sub.1-30-haloalkyl, [0611] X.sup.5 at each occurrence is
independently --Z.sup.11--O--Z.sup.12, --Z.sup.11--S--Z.sup.12--,
--S(O)--, --C(O)--, --C(O)O--, --C(O)NR.sup.15, --C(O)S--,
--Z.sup.11--SiR.sup.15.sub.2--Z.sup.12--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0612] wherein [0613] Z.sup.11 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene,
[0614] Z.sup.12 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, and [0615] R.sup.15 at each occurrence is
independently H, C.sub.1-20-alkyl, or --Z.sup.13--C.sub.6-14-aryl,
[0616] wherein [0617] Z.sup.13 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, [0618] Ar.sup.7 at each occurrence is
independently C.sub.6-14-aryl or monovalent 5 to 14 membered
aromatic heterocyclic residue, each optionally substituted with 1
to 5 substituents R.sup.e, wherein each R.sup.e is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0619] Ar.sup.8 and
Ar.sup.9 at each occurrence are independently C.sub.6-14-arylene or
bivalent 5 to 14 membered aromatic heterocyclic residue, each
optionally substituted with 1 to 4 substituents R.sup.f, wherein
each R.sup.f is independently selected from the group consisting of
halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and
C.sub.1-6-haloalkyl and [0620] R.sup.13 at each occurrence is
independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.1-20-haloalkyl, C.sub.1-20-alkoxy, --X.sup.6--Ar.sup.10,
--X.sup.6--Ar.sup.11--Ar.sup.10, --X.sup.6--Ar.sup.11--R.sup.16, or
--X.sup.6--Ar.sup.11--Ar.sup.12--R.sup.17, [0621] wherein [0622]
X.sup.6 at each occurrence is independently
--Z.sup.14--O--Z.sup.15, --Z.sup.14--S--Z.sup.15, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.18, --C(O)S--, --O(CO)--,
--S(CO)--, --NR.sup.18C(O)--, --NR.sup.18--,
--Z.sup.14--SiR.sup.18.sub.2--Z.sup.15--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0623] wherein [0624] Z.sup.14 and Z.sup.15 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0625] R.sup.18 at
each occurrence is independently H, C.sub.1-20-alkyl or
--Z.sup.16--C.sub.6-14-aryl, wherein Z.sup.16 at each occurrence is
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, [0626] Ar.sup.10 at each
occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 5 substituents R.sup.g, wherein each R.sup.g is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0627]
Ar.sup.11 and Ar.sup.12 at each occurrence are independently
C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.h, wherein each R.sup.h is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkoxy
and C.sub.1-6-haloalkyl and [0628] R.sup.17 at each occurrence is
independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy, [0629] R.sup.19 is O or
C(CN).sub.2, and [0630] R.sup.20 and R.sup.21 are the same or
different and are R.sup.22 or CN, [0631] wherein R.sup.22 has the
same meaning as R.sup.1,
[0632] G.sup.1 and G.sup.2 are the same or different and are
phenylene or a monocyclic bivalent 5 to 8 membered aromatic
heterocyclic residue, which phenylene and monocyclic bivalent 5 to
8 membered aromatic heterocyclic residue are optionally substituted
with 1 to 4 substituents R.sup.i, wherein each R.sup.i is
independently selected from the group consisting of halogen, --CN,
--NO.sub.2, OH, C.sub.1-30-alkyl, C.sub.2-30-alkenyl,
C.sub.2-30-alkynyl, --Z.sup.17--O--C.sub.1-30-alkyl,
--Z.sup.17--S--C.sub.1-30-alkyl, --Z.sup.17--C.sub.3-10-cycloalkyl,
--Z.sup.17--C.sub.5-10-cycloalkenyl,
--Z.sup.17--C.sub.8-10-cycloalkynyl, --Z.sup.17--C.sub.6-14-aryl,
--Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.17-monovalent 5 to 14 membered aromatic
heterocyclic residue,
wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl,
C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12
membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue is optionally substituted
with 1 to 4 substituents R.sup.j, wherein each R.sup.j is
independently selected from the group consisting of halogen, --CN,
--NO.sub.2, *.dbd.O, --OH, --NH.sub.2, --NH(C.sub.1-20-alkyl),
--N(C.sub.1-20-alkyl).sub.2, --N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--N(C.sub.6-14-aryl).sub.2, --S(O).sub.mH, --S(O).sub.2OH,
--S(O).sub.m--OC.sub.1-20-alkyl, --S(O).sub.m--OC.sub.6-14-aryl,
--CHO, --C(O)--C.sub.1-20-alkyl, --C(O)--C.sub.6-14-aryl, --C(O)OH,
--C(O)--OC.sub.1-20-alkyl, --C(O)--OC.sub.6-14-aryl,
--C(O)NH.sub.2, --C(O)NH--C.sub.1-20-alkyl,
--C(O)N(C.sub.1-20-alkyl).sub.2, --C(O)NH--C.sub.6-14-aryl,
--C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(O)N(C.sub.6-14-aryl).sub.2, --C(S)NH.sub.2,
--C(S)NH--C.sub.1-20-alkyl, --C(S)N(C.sub.1-20-alkyl).sub.2,
--C(S)N(C.sub.6-14-aryl).sub.2,
--C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(S)NH--C.sub.6-14-aryl, --S(O).sub.mNH.sub.2,
--S(O).sub.mNH(C.sub.1-20-alkyl),
--S(O).sub.mN(C.sub.1-20-alkyl).sub.2,
--S(O).sub.mNH(C.sub.6-14-aryl),
--S(O).sub.mN(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--S(O).sub.mN(C.sub.6-14-aryl).sub.2, SiH.sub.3,
SiH(C.sub.1-20-alkyl).sub.2, SiH.sub.2(C.sub.1-20-alkyl) and
Si(C.sub.1-20-alkyl).sub.3, and wherein C.sub.3-10-cycloalkyl,
C.sub.5-10-cycloalkenyl, --C.sub.8-10-cycloalkynyl,
C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic
residue and monovalent 5 to 14 membered aromatic heterocyclic
residue is optionally substituted with 1 to 4 substituents R.sup.k,
wherein each R.sup.k is independently selected from the group
consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.2-20-alkynyl, C.sub.1-20-alkoxy, C.sub.1-20-haloalkyl, [0633]
wherein [0634] Z.sup.17 at each occurrence is independently
C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or
a covalent bond, and [0635] m at each occurrence is independently
0, 1 or 2,
[0636] L is C.sub.6-24-arylene or a bivalent 5 to 18 membered
aromatic heterocyclic residue, wherein C.sub.6-24-arylene and
bivalent 5 to 18 membered aromatic heterocyclic residue are
optionally substituted with 1 to 4 substituents R.sup.l, wherein
each R.sup.l is independently selected from the group consisting of
halogen, --CN, --NO.sub.2, *.dbd.O, OH,
*.dbd.O(C.sub.1-30-alkyl).sub.2, C.sub.1-30-alkyl,
C.sub.2-30-alkenyl, C.sub.2-30-alkynyl,
--Z.sup.18--O--C.sub.1-30-alkyl, --Z.sup.18--S--C.sub.1-30-alkyl,
--Z.sup.18--C.sub.3-10-cycloalkyl,
--Z.sup.18--C.sub.5-10-cycloalkenyl,
--Z.sup.18--C.sub.8-10-cycloalkynyl, --Z.sup.18--C.sub.6-14-aryl,
--Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic
residue and --Z.sup.18-monovalent 5 to 14 membered aromatic
heterocyclic residue,
wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl,
C.sub.3-10-cycloalkyl, C.sub.6-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12
membered aliphatic heterocyclic residue and monovalent 5 to 14
membered aromatic heterocyclic residue is optionally substituted
with 1 to 4 substituents R.sup.m, wherein each R.sup.m is
independently selected from the group consisting of halogen, --CN,
--NO.sub.2, *.dbd.O, --OH, --NH.sub.2, --NH(C.sub.1-20-alkyl),
--N(C.sub.1-20-alkyl).sub.2, --N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--N(C.sub.6-14-aryl).sub.2, --S(O).sub.oH,
--S(O).sub.o--C.sub.1-20-alkyl, --S(O).sub.2OH,
--S(O).sub.o--OC.sub.1-20-alkyl, --S(O).sub.o--OC.sub.6-14-aryl,
--CHO, --C(O)--C.sub.1-20-alkyl, --C(O)--C.sub.6-14-aryl, --C(O)OH,
--C(O)--OC.sub.1-20-alkyl, --C(O)--OC.sub.6-14-aryl,
--C(O)NH.sub.2, --C(O)NH--C.sub.1-20-alkyl,
--C(O)N(C.sub.1-20-alkyl).sub.2, --C(O)NH--C.sub.6-14-aryl,
--C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(O)N(C.sub.6-14-aryl).sub.2, --C(S)NH.sub.2,
--C(S)NH--C.sub.1-20-alkyl, --C(S)N(C.sub.1-20-alkyl).sub.2,
--C(S)N(C.sub.6-14-aryl).sub.2,
--C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--C(S)NH--C.sub.6-14-aryl, --S(O).sub.oNH.sub.2,
--S(O)ONH(C.sub.1-20-alkyl), --S(O).sub.oN(C.sub.1-20-alkyl).sub.2,
--S(O)ONH(C.sub.6-14-aryl),
--S(O).sub.oN(C.sub.1-20-alkyl)-C.sub.6-14-aryl,
--S(O).sub.oN(C.sub.6-14-aryl).sub.2, SiH.sub.3,
SiH(C.sub.1-20-alkyl).sub.2, SiH.sub.2(C.sub.1-20-alkyl) and
Si(C.sub.1-20-alkyl).sub.3, and wherein C.sub.3-10-cycloalkyl,
C.sub.6-10-cycloalkenyl, --C.sub.8-10-cycloalkynyl,
C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic
residue and monovalent 5 to 14 membered aromatic heterocyclic
residue is optionally substituted with 1 to 4 substituents R.sup.n,
wherein each R.sup.n is independently selected from the group
consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl,
C.sub.2-20-alkynyl, C.sub.1-20-alkoxy, --S--C.sub.1-20-alkyl,
C.sub.1-20-haloalkyl, [0637] wherein [0638] Z.sup.18 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
and [0639] o at each occurrence is independently 0, 1 or 2, or
L is
[0640] ##STR00059## [0641] wherein [0642] R.sup.23 and R.sup.24 can
be the same or different and are H, halogen, --CN,
C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-20-alkynyl,
C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl,
C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12
membered aliphatic heterocyclic residue, --X.sup.7--R.sup.25,
--X.sup.8--Ar.sup.13, --X.sup.8--Ar.sup.14--Ar.sup.13,
--X.sup.8--Ar.sup.14--R.sup.26 or
--X.sup.8--Ar.sup.14--Ar.sup.15--R.sup.26, [0643] wherein [0644]
X.sup.7 at each occurrence is independently --O--,
--[Z.sup.19--O].sub.c--, --[O--Z.sup.19].sub.c--, --O--, --S--,
--[Z.sup.19--S--].sub.c--, --[S--Z.sup.19].sub.c--S--, --S(O),
--C(O)--, --C(O)O--, --C(O)NR.sup.27--, C(O)S--, --C(O)--,
--S(O)--, --NR.sup.27C(O)-- or --NR.sup.27--, [0645] wherein [0646]
Z.sup.19 at each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, [0647] c at each
occurrence is independently an integer from 1 to 10 and [0648]
R.sup.27 at each occurrence is independently H, C.sub.1-20-alkyl,
or --Z.sup.20--C.sub.6-14-aryl, [0649] wherein [0650] Z.sup.20 at
each occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0651] R.sup.25 at each occurrence is independently
C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl,
[0652] X.sup.8 at each occurrence is independently
--Z.sup.21--O--Z.sup.22--, --Z.sup.21--S--Z.sup.22--, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.28, --C(O)S--, --O(CO)--,
--S(CO)--, --NR.sup.28C(O)--, --NR.sup.28--,
--Z.sup.21--SiR.sup.28.sub.2--Z.sup.22--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0653] wherein [0654] Z.sup.21 and Z.sup.22 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0655] R.sup.28 at
each occurrence is independently H, C.sub.1-20-alkyl, or
--Z.sup.23--C.sub.6-14-aryl, [0656] wherein [0657] Z.sup.23 at each
occurrence is independently C.sub.1-6-alkylene,
C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond,
[0658] Ar.sup.12 at each occurrence is independently
C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic
residue, each optionally substituted with 1 to 5 substituents
R.sup.o, wherein each R.sup.o is independently selected from the
group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy
and C.sub.1-6-haloalkyl, [0659] Ar.sup.14 and Ar.sup.15 at each
occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 4 substituents R.sup.p, wherein each R.sup.p is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and
[0660] R.sup.26 at each occurrence is independently
C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl,
C.sub.1-20-alkoxy, --X.sup.9--Ar.sup.16,
--X.sup.9--Ar.sup.17--Ar.sup.16, --X.sup.9--Ar.sup.17--R.sup.29, or
--X.sup.9--Ar.sup.17--Ar.sup.18--R.sup.29, [0661] wherein [0662]
X.sup.9 at each occurrence is independently
--Z.sup.24--O--Z.sup.25--, --Z.sup.24--S--Z.sup.25, --S(O)--,
--C(O)--, --C(O)O--, --C(O)NR.sup.30, --C(O)S--, --O(CO)--,
--S(CO)--, --NR.sup.30C(O)--, --NR.sup.30--,
--Z.sup.24--SiR.sup.30.sub.2--Z.sup.25--, C.sub.1-30-alkylene,
C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond,
[0663] wherein [0664] Z.sup.24 and Z.sup.25 at each occurrence are
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, and [0665] R.sup.30 at
each occurrence is independently H, C.sub.1-20-alkyl or
--Z.sup.26--C.sub.6-14-aryl, wherein Z.sup.26 at each occurrence is
independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene,
C.sub.1-6-haloalkylene or a covalent bond, [0666] Ar.sup.16 at each
occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14
membered aromatic heterocyclic residue, each optionally substituted
with 1 to 5 substituents R.sup.q, wherein each R.sup.q is
independently selected from the group consisting of halogen, CN,
C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, [0667]
Ar.sup.17 and Ar.sup.18 at each occurrence are independently
C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic
heterocyclic residue, each optionally substituted with 1 to 4
substituents R.sup.r, wherein each R.sup.r is independently
selected from the group consisting of halogen, CN, C.sub.1-6-alkyl,
C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and [0668] R.sup.26 at
each occurrence is independently C.sub.1-20-alkyl,
C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy, q
and s are the same or different and are 0, 1, 2, 3, 4 or 5, r is 0,
1 or 2, and n is an integer from 1 to 10'000, which process
comprises, preferably, (i) the step of reacting a compound of
formula
##STR00060##
[0668] wherein A.sup.1, A.sup.2 and E are as defined above, and Hal
is halogen, preferably --Br, with a compound of formula
##STR00061##
wherein G.sup.1, G.sup.2, L, q, r, and s are as defined above, and
R.sup.31, R.sup.32, R.sup.33, R.sup.34, R.sup.35 and R.sup.36 are
the same and are C.sub.1-30-alkyl, preferably C.sub.1-6-alkyl, most
preferably n-butyl or methyl, in the presence of a metal catalyst,
or (ii) the step of reacting a compound of formula
##STR00062##
wherein A.sup.1, A.sup.2 and E, G.sup.1, G.sup.2, r and s are as
defined above, and Hal is halogen, preferably --Br, with a compound
of formula
##STR00063##
wherein L and r are as defined above, and R.sup.31, R.sup.32,
R.sup.33, R.sup.34, R.sup.35 and R.sup.36 are the same and are
C.sub.1-30-alkyl, preferably C.sub.1-6-alkyl, most preferably
n-butyl or methyl, in the presence of a metal catalyst, or (iii)
the step of reacting a compound of formula
##STR00064##
wherein A.sup.1, A.sup.2 and E are as defined above, and R.sup.31,
R.sup.32, R.sup.33, R.sup.34, R.sup.35 and R.sup.36 are the same
and are C.sub.1-30-alkyl, preferably C.sub.1-6-alkyl, most
preferably n-butyl or methyl, with a compound of formula
##STR00065##
wherein G.sup.1, G.sup.2, L, q, r, and s are as defined above, and
Hal is halogen, preferably --Br, in the presence of a metal
catalyst, or (iv) the step of reacting a compound of formula
##STR00066##
wherein A.sup.1, A.sup.2, E, G.sup.1, G.sup.2, r and s are as
defined above, and R.sup.31, R.sup.32, R.sup.33, R.sup.34, R.sup.35
and R.sup.36 are the same and are C.sub.1-30-alkyl, preferably
C.sub.1-6-alkyl, most preferably n-butyl or methyl, with a compound
of formula
##STR00067##
wherein L and r are as defined above, and Hal is halogen,
preferably --Br, in the presence of a metal catalyst.
[0669] Preferably R.sup.31, R.sup.32, R.sup.33, R.sup.34, R.sup.35
and R.sup.36 are methyl or n-butyl.
[0670] The metal catalyst is preferably a palladium catalyst such
tris(dibenzylideneacetone)-dipalladium(0), preferably in
combination with a phosphine such as tri-o-tolylphosphine. The
reaction is preferably performed at elevated temperatures such 80
to 200.degree. C., preferably 90 to 150.degree. C. The reaction can
be performed in an inert organic solvent such as chlorobenzene. The
reaction can be stopped by the addition of end cappers such as
2-bromothiophene and 2-tributylstannylthiophene. The crude product
may be worked up by conventional methods, for example by extracting
the crude product with an appropriate solvent, for example with
acetone.
[0671] Alternatively, the compound, oligomer or polymer of
formula
##STR00068##
wherein A.sup.1, A.sup.2, E, G.sup.1, L, G.sup.2, q, r, s and n are
as defined above, can be prepared by the process as outlined above
but using
##STR00069##
wherein G.sup.1, G.sup.2, L, q, r, and s are as defined above, and
R.sup.37, R.sup.38, R.sup.39 and R.sup.40 are the same and are H or
C.sub.1-30-alkyl, or R.sup.37 and R.sup.38, respectively, R.sup.39
and R.sup.40 form together with --O--B--O-- a 5 to 8-membered
cyclic ring, for example a pinacol type ring of formula
##STR00070##
instead of the compound of formula 3,
##STR00071##
wherein L and r are as defined above, and R.sup.37, R.sup.38,
R.sup.39 and R.sup.40 are the same and are H or C.sub.1-30-alkyl,
or R.sup.37 and R.sup.38, respectively, R.sup.39 and R.sup.40 form
together with --O--B--O-- a 5 to 8-membered cyclic ring, for
example a pinacol type ring of formula
##STR00072##
instead of the compound of formula 9,
##STR00073##
wherein A.sup.1, A.sup.2 and E are as defined above, and R.sup.37,
R.sup.38, R.sup.39 and R.sup.40 are the same and are H or
C.sub.1-30-alkyl, or R.sup.37 and R.sup.38, respectively, R.sup.39
and R.sup.40 form together with --O--B--O-- a 5 to 8-membered
cyclic ring, for example a pinacol type ring of formula
##STR00074##
instead of the compound of formula 10, or
##STR00075##
wherein A.sup.1, A.sup.2, E, G.sup.1, G.sup.2, r and s are as
defined above, and R.sup.37, R.sup.38, R.sup.39 and R.sup.40 are
the same and are H or C.sub.1-30-alkyl, or R.sup.37 and R.sup.38,
respectively, R.sup.39 and R.sup.40 form together with --O--B--O--
a 5 to 8-membered cyclic ring, for example a pinacol type ring of
formula
##STR00076##
instead of the compound of formula 12.
[0672] The compound of formula
##STR00077##
wherein A.sup.1 and A.sup.2 are as defined above, and Hal is
halogen, preferably --Br,
and E is
##STR00078##
[0673] wherein R.sup.1, R.sup.2 and R.sup.3 are as defined above,
can be prepared by a process, which comprises the step of reacting
a compound of formula
##STR00079##
wherein A.sup.1, A.sup.2 and E are as defined above, and R.sup.41,
R.sup.42, R.sup.43, R.sup.44, R.sup.45 and R.sup.46 are
C.sub.1-30-alkyl, preferably C.sub.1-6-alkyl, more preferably
isopropyl, with a halogenating agent in the presence of an acidic
catalyst.
[0674] The halogenating agent is preferably Br.sub.2. The acidic
catalyst is preferably trichloroacetic acid. The reaction is
preferably carried out in an inert organic solvent such as
chloroform. The reaction is preferably carried out at ambient
temperature, for example at a temperature from 15 to 30.degree. C.,
more preferably at a temperature from 18 to 26.degree. C. The
reaction mixture can be worked up by conventional methods.
[0675] The compound of formula
##STR00080##
wherein A.sup.1, A.sup.2 and E are as defined above, and R.sup.41,
R.sup.42, R.sup.43, R.sup.44, R.sup.45 and R.sup.46 are
C.sub.1-30-alkyl, preferably C.sub.1-6-alkyl, more preferably
isopropyl, can be prepared by a process, which comprises the step
of coupling a compound of formula
##STR00081##
wherein A.sup.1, A.sup.2, R.sup.41, R.sup.42, R.sup.43, R.sup.44,
R.sup.45 and R.sup.46 are as defined above, and Hal is halogen,
preferably --Br, with H-E-H or
##STR00082##
wherein R.sup.47, R.sup.48, R.sup.49 and R.sup.50 are the same and
are H or C.sub.1-30-alkyl, or R.sup.47 and R.sup.48, respectively,
R.sup.49 and R.sup.50 form together with --O--B--O-- a 5 to
8-membered cyclic ring, for example a pinacol type ring of
formula.
##STR00083##
in the presence of a metal catalyst.
[0676] The metal catalyst can be a palladium catalyst such as
tetrakis(triphenylphosphine)palladium(0), or
tris(dibenzylideneacetone)dipalladium(0) in combination with a
phosphine such as rac-BI NAP or tri-tert-butylphosphine.
Preferably, the reaction is carried out in the presence of a base
such as potassium carbonate or sodium tertbutoxide. The reaction
can be carried out in an inert organic solvent such as toluene, or
in mixtures of inert organic solvents and water, for example in
mixtures of toluene and water. The reaction can be carried out at
elevated temperatures, for example at a temperature from 70 to
200.degree. C., preferably at a temperature from 80 to 150.degree.
C. The reaction mixture can be worked up by conventional
methods.
[0677] If E is
##STR00084##
the vic-bis(pinacolatoboryl) complex
##STR00085##
is preferably used in the reaction.
[0678] This vic-bis(pinacolatoboryl) complex can be synthesized via
platinum catalyzed boronation of
##STR00086##
[0679] The compound of formula
##STR00087##
wherein A.sup.1 and A.sup.2 are as defined above, R.sup.41,
R.sup.42, R.sup.43, R.sup.44, R.sup.45 and R.sup.46 are
C.sub.1-30-alkyl, preferably, C.sub.1-20-alkyl, preferably
C.sub.1-6-alkyl, more preferably isopropyl, and Hal is halogen,
preferably --Br, can be prepared by a process which comprises the
step of reacting
##STR00088##
wherein A.sup.1 and A.sup.2 are as defined above, and Hal is
halogen, preferably --Br, with R.sup.41R.sup.42R.sup.43Si--Hal and
R.sup.44R.sup.45R.sup.46Si--Hal and a base, wherein R.sup.41,
R.sup.42, R.sup.43, R.sup.44, R.sup.45 and R.sup.46 are as defined
above, and Hal is halogen, preferably --Br.
[0680] An example of a base is lithium diisopropylamide. The
reaction can be performed in an inert organic solvent, for example
THF. The reaction can be performed at a temperature of 0 to
-100.degree. C., preferably at -40 to -90.degree. C., preferably at
around -78.degree. C. The reaction mixture obtained can be
worked-up by conventional methods.
[0681] The compound of formula
##STR00089##
wherein A.sup.1 and A.sup.2 are as defined above, and Hal is
halogen, preferably --Br, can be prepared by a process comprising
the step of reacting
##STR00090##
wherein A.sup.1 and A.sup.2 are as defined above, with a
halogenating agent.
[0682] An example of a halogenating agent is N-bromosuccinimide.
The reaction can be performed in an inert organic solvent, for
example DMF. The reaction can be performed at elevated temperature,
for example at a temperature from 20 to 100.degree. C., preferably
at 40 to 80.degree. C. The reaction mixture obtained can be
worked-up by conventional methods.
[0683] A compound of formula 2d can also be prepared via
thiocyanation of 2,6-diamino-benzothiazole 18 as reported by
Landquist, J. K. J. Chem. Soc. C 1967, 2212 to 2220, followed by
Sandmeyer reaction as depicted below
##STR00091##
[0684] A compound of formula 2e can also be prepared via
condensation of 3,6-diamino-1,2-phenylene dihydrogen thiosulphate
19 with thiophene-2-carboxylic acid in analogy to the processes
described by Green, A. G. J. Chem. Soc., Trans. 1903, 83, 1201 to
1212, and by Cox, R. J.; Clecak, N. J. J. Org. Chem. 1968, 33, 2132
to 2133, followed by halogenation as depicted below
##STR00092##
[0685] The compound of formula
##STR00093##
wherein A.sup.1 and A.sup.2 are as defined above, and Hal is
halogen, preferably --Br, and E is selected from the group
consisting of
##STR00094##
wherein R.sup.4, R.sup.5, R.sup.19, R.sup.20 and R.sup.21 are as
defined above, can be prepared by a process, which comprises the
step of reacting a compound of formula
##STR00095##
wherein A.sup.1 and A.sup.2 are as defined above, R.sup.41,
R.sup.42, R.sup.43, R.sup.44, R.sup.45 and R.sup.46 are
C.sub.1-30-alkyl, preferably C.sub.1-6-alkyl, more preferably
isopropyl, and Hal is halogen, preferably --Br, with a suitable
compound to incorporate E, in the presence of a base such as butyl
lithium.
[0686] For example, the compounds of formulae 2f, 2g, 2h and 2i can
be prepared as follows:
##STR00096## ##STR00097##
[0687] The compound of formula
##STR00098##
wherein A.sup.1 and A.sup.2 are as defined above, and Hal is
halogen, preferably --Br, and E is selected from the group
consisting of
##STR00099##
wherein R.sup.4, R.sup.5, R.sup.19, R.sup.20 and R.sup.21 are as
defined above, can also be prepared by a process, which comprises
the step of reacting a compound of formula
##STR00100##
wherein A.sup.1 and A.sup.2 are as defined above, R.sup.41,
R.sup.42, R.sup.43, R.sup.44, R.sup.45 and R.sup.46 are
C.sub.1-30-alkyl, preferably C.sub.1-6-alkyl, more preferably
isopropyl, with a suitable compound to incorporate E, in the
presence of a base such as lithium diisopropylamide, for example as
described for similar compounds in WO 2009/069687.
[0688] The compound of formula
##STR00101##
wherein A.sup.1 and A.sup.2 are as defined above, R.sup.41,
R.sup.42, R.sup.43, R.sup.44, R.sup.45 and R.sup.46 are
C.sub.1-30-alkyl, preferably C.sub.1-6-alkyl, more preferably
isopropyl, can be prepared via oxidative coupling of
##STR00102##
[0689] For example the compound of formula 20a can be prepared as
follows:
##STR00103##
[0690] The compound of formula
##STR00104##
wherein A.sup.1 and A.sup.2 can be the same or different and are S
or Se, E is selected from the group consisting of
##STR00105##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.19,
R.sup.20 and R.sup.21 are as defined above, G.sup.1 and G.sup.2 are
are as defined above, q and s are as defined above, and Hal is
halogen, can be prepared by reacting the compound of formula
##STR00106##
wherein A.sup.1 and A.sup.2 are as defined above, and Hal is
halogen, with suitable compounds to incorporate G.sup.1 and
G.sup.2, such as stannyl functionalized G.sup.1 and G.sup.2 or
borate functionalized G.sup.1 or G.sup.2 or Grignard functionalized
G.sup.1 and G.sup.2, in the presence of a metal catalyst, followed
by halogenation.
[0691] For example, the compound of formula 8a can be prepared as
follows:
##STR00107##
[0692] Also part of the invention is the compound of formula
##STR00108##
wherein A.sup.1 and A.sup.2 can be the same or different and are S
or Se, E is selected from the group consisting of
##STR00109##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.19,
R.sup.20 and R.sup.21 are as defined above and Hal is halogen.
[0693] Also part of the invention is the compound of formula
##STR00110##
wherein A.sup.1 and A.sup.2 can be the same or different and are S
or Se,
E is
##STR00111##
[0694] and R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45 and
R.sup.46 are C.sub.1-30-alkyl, preferably C.sub.1-6-alkyl, more
preferably isopropyl.
[0695] Also part of the invention is a compound of formula
##STR00112##
wherein A.sup.1 and A.sup.2 can be the same or different and are S
or Se, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45 and
R.sup.46 are C.sub.1-30-alkyl, preferably C.sub.1-6-alkyl, more
preferably isopropyl, and Hal is halogen, preferably --Br.
[0696] Also part of the present invention is an electronic device
comprising the compounds, oligomers and polymers of the present
invention.
[0697] The electronic device can be any electronic device, for
example an organic photovoltaic (OPV) cell, an organic field-effect
transistor (OFET) or an organic light emitting diode (OLED).
Preferably, it is an organic field-effect transistor.
[0698] The organc field effect transistor comprising the compounds,
oligomers and polymers of the present invention can be prepared by
solution deposition of a solution of the compounds, oligomers and
polymers of the present invention in a suitable solvent. The
solvent can be an organic solvent, for example 1,2-dichlorobenzene.
Solution deposition can be performed by methods known in the art,
for example by spin coating, for example at 2000 rpm, 255 acc (acc:
spin acceleration), 1 minute.
[0699] The organic field effect transistor can have any
architecture known in the art, for example a bottom gate bottom
contact (BGBC) architecture as depicted in FIG. 1. When the organic
field effect transistor has a bottom gate bottom contact (BGBC)
architecture, the substrate (or gate electrode), the gate
dielectric, and the source and drain electrodes can be any
substrate, gate dielectric, source and drain electrode known in the
art. For example, the substrate (or gate electrode) can be heavily
doped silicon wafer, the gate dielectric can be thermally grown
silica, and the source and drain electrode can be made of gold
which is lithographically patterned. Before deposition of the
compounds, oligomers and polymers of the present invention as
semiconductors, the device can be vapor treated with
hexamethyldisilazane (HMDS).
[0700] Also part of the invention is the use of the compound,
oligomer or polymer of the present invention as organic
semiconducting material.
[0701] The compounds, oligomers and polymers of the present
invention show a surprising high ioniziation potential, which may
contribute to better ambient oxidative stability. The compounds,
oligomers and polymers of the present invention are compatible with
liquid processing techniques and are suitable for use as
semiconductors in organic field effect transistors. The organic
field effect transistor using the compounds, oligomers and polymers
of the present invention as semiconductors show good field-effect
mobilities and on/off ratios.
[0702] FIG. 1 shows an organic field effect transistor having a
bottom gate bottom contact (BGBC) architecture.
EXAMPLES
Example 1
Preparation of
2,2'-dibromo-(5,6-dihexylbenzo[2,1-d;3,4-d']bisthiazole) (2a)
##STR00113##
[0703] Preparation of 4,4'-dibromo-5,5'-bithiazole (6a)
[0704] N-bromosuccinimide (6.35 g, 35.66 mmol, 4 eq.) is added to a
stirred homogeneous solution of 5,5'-bithiazole (7a) (1.5 g, 8.9
mmol) in anhydrous DMF (125 mL). The reaction mixture is heated at
60.degree. C. for 3 hours. The reaction mixture is washed
subsequently with an aqueous solution of 10% sodium bicarbonate
(200 mL), extracted with dichloromethane (200 mL), washed with
water (3.times.100 mL) and sodium chloride saturated water (100
mL), and dried over anhydrous sodium sulfate. The crude product is
re-crystallized from dichloromethane/n-hexane (1:10). Yellowish
crystals are obtained. .sup.1H-NMR (d-chloroform) (400 MHz):
.delta. 8.87 (s, 2H). .sup.13C-NMR (d-chloroform) (400 MHz):
.delta. 154.8, 129.3, 122.5.
Preparation of
2,2'-bis(triisopropylsilyl)-4,4'-dibromo-5,5'-bithiazole (5a)
[0705] 1.84 mL of a 2M solution of lithium diisopropylamide (0.39
g, 3.68 mmol, 2.4 eq.) in THF is added dropwise to a solution of
4,4'-dibromo-5,5'-bithiazoles (6a) (0.5 g, 1.53 mmol) in anhydrous
THF (20 mL) at -78.degree. C. over 10 minutes. The reaction mixture
is allowed to stir for 3 hours, and then triisopropylsilyl chloride
(0.709 g, 0.79 mL, 3.68 mmol, 2.4 eq.) is added slowly. The
reaction mixture is warmed up to room temperature overnight. The
reaction mixture is diluted with ethyl acetate (140 mL), and the
organic layer is washed with sodium bicarbonate saturated water (70
mL) and sodium chloride saturated water (70 mL), dried over
magnesium sulfate and concentrated in vacuo. Column chromatography
using gradient solvent from n-hexane to ethyl acetate/n-hexane
(5/95) provides a yellow solid. .sup.1H-NMR (d-chloroform) (400
MHz): .delta. 2.43-1.5 (m, J=8 Hz, 6H), .delta. 1.16-1.18 (d, J=7.6
Hz, 36H). .sup.13C-NMR (d-chloroform) (400 MHz): .delta. 172.7,
130.5, 125.1, 18.7, 11.8.
Preparation of
2,2'-bis(triisopropylsilyl)-(5,6-dihexylbenzo[2,1-d;3,4-d']bisthiazole)
(4a)
[0706] A mixture of 5a (0.5 g, 0.783 mmol) and
tetrakis(triphenylphosphine)palladium(0) (0.090 g, 0.078 mmol, 0.1
eq.) is degassed 3 times. A solution of
vic-bis(pinacolatoboryl)-7-tetradecene (0.456 g, 1.018 mmol, 1.3
eq.), in anhydrous toluene (5 mL) is added, followed by 12 mL of
toluene (total 17 mL anhydrous toluene). Subsequently 2.8 mL of
degassed aqueous solution of potassium carbonate (0.64 g, 4.70
mmol, 6 eq.) is added. The reaction mixture is stirred and heated
at 100.degree. C. overnight. The reaction mixture is allowed to
cool to room temperature, and is diluted with ethyl acetate (50
mL). The resulting reaction mixture is washed with ammonium
chloride saturated water (50 mL) and the aqueous layer is extracted
with ethyl acetate (3.times.50 mL). The combined organic layers are
washed with sodium chloride saturated water (25 mL), dried over
magnesium sulfate, and concentrated in vacuo. Column chromatography
using a gradient solvent from n-hexane to ethyl acetate/n-hexane
(10/90) provides an off-white solid. .sup.1H-NMR (d-chloroform)
(400 MHz): .delta. 3.37 (dd, J=8 Hz, 4H), .delta. 1.74-1.76 (m, J=8
Hz, 4H), .delta. 1.47-1.55 (m, J=8 Hz, 6H), .delta. 1.33-1.37 (m,
J=8 Hz, 12H), .delta. 1.2-1.22 (d, J=8 Hz, 36H), .delta. 0.87-0.92
(t, J=7.6 Hz, 6H). LC-MS: 95% purity with m/z 673.4.
Preparation of
2,2'-dibromo-(5,6-dihexylbenzo[2,1-d;3,4-d']bisthiazole) (2a)
[0707] A solution of bromine (0.34 g, 0.11 mL, 2.11 mmol, 4 eq.) in
chloroform (5 mL) containing trichloroacetic acid (7 mg) is added
dropwise and slowly to a solution of 4a (0.355 g, 0.527 mmol) in
chloroform (8 mL) at 0.degree. C. The reaction mixture is stirred
at room temperature for 3 days. The reaction mixture is diluted
with dichloromethane (50 mL), washed with an aqueous solution of 20
weight % sodium thiosulfate (50 mL) and with an aqueous solution of
10 weight % sodium bicarbonate (50 mL). Subsequently the organic
layer is dried over magnesium sulfate and concentrated in vacuo.
Purification by column chromatography (ethyl acetate/n-hexane
(10/90)) followed by re-crystallisation from ethanol affords light
brown crystals. .sup.1H-NMR (d-chloroform) (400 MHz): .delta. 3.17
(dd, J=8 Hz, 4H), .delta. 1.66 (m, J=8 Hz, 4H), .delta. 1.47 (m,
J=8 Hz, 4H), .delta. 1.35 (m, J=8 Hz, 8H), .delta. 0.92 (t, J=7.6
Hz, 6H). LC-MS: 98% purity with m/z 519. Elemental analysis
(calcd): C, 46.34 (46.36); H, 5.06 (5.09).
Example 2
Preparation of poly(benzobisthiazole-cyclopentadithiophene)
(1a)
##STR00114##
[0709] Dibromo-benzobisthiazole (2a) (60 mg, 0.116 mmol, 1 eq.),
bis(trimethylstannyl)-cyclopentadithiophene (3a) (110 mg, 0.116
mmol, 1 eq.), tris(dibenzylidene-acetone)dipalladium(0) (3.2 mg,
0.003 mmol, 3% eq.) and tri-o-tolylphosphine (2.1 mg, 0.007 mmol,
6% eq.) are added into a Schlenk flask and degassed 3 times.
Chlorobenzene (4 mL) is added and the reaction mixture is stirred
at 100.degree. C. overnight then at 130.degree. C. for 2 days.
2-Bromothiophene (0.01 mL) and 2-tributylstannylthiophene (0.01 mL)
are added as end cappers, with 2-bromothiophene added first
followed by 2-tributylstannylthiophene 2 hours later. After another
2 hours stirring, the reaction mixture is cooled to room
temperature. The reaction mixture is then added dropwise to
methanol (200 mL), filtered, and then subjected to Soxhlet
extraction with acetone. The polymer is recovered as solid mass and
showed Mn=8360 g/mol (Mw=24264 g/mol & PDI=2.92). Elemental
analysis (calcd): C, 70.77 (74.48); H, 8.93 (9.63).
Example 3
Preparation of poly(benzobisthiazole-bisthienylethylene) (1b)
##STR00115##
[0711] Dibromo-benzobisthiazole (2a) (55 mg, 0.106 mmol, 1 eq.)
prepared as described in example 1,
bis(2-trimethylstannyl-4-dodecylthienyl)ethylene (3b) (90.7 mg,
0.106 mmol, 1 eq.), tris(dibenzylideneacetone)dipalladium(0) (2.9
mg, 0.003 mmol, 3% eq.) and tri-o-tolylphosphine (1.9 mg, 0.006
mmol, 6% eq.) are added into a Schlenk flask and degassed 3 times.
Chlorobenzene (2 mL) is added and the reaction mixture is stirred
at 130.degree. C. for 2 days. 2-Bromothiophene (0.01 mL) and
2-tributylstannylthiophene (0.01 mL) are added as end cappers, with
2-bromothiophene added first followed by 2-tributylstannylthiophene
2 hours later. After another 2 hours stirring, the reaction mixture
is cooled to room temperature. The mixture is filtered and the
filtrate is concentrated and added dropwise to methanol (200 mL),
filtered, and then subjected to Soxhlet extraction with acetone.
The polymer is recovered as solid mass and showed Mn=3368 g/mol
(Mw=4749 g/mol & D=1.41).
Example 4
Preparation of poly(benzobisthiazole-bithiophene) (1c)
##STR00116##
[0712] Preparation of
2,2'-dibromo-(5,6-dimethylbenzo[2,1-d;3,4-d']bisthiazole) (2b)
[0713] Dibromo-benzobisthiazole (2b) is prepared in analogy to
2,2'-dibromo-(5,6-dihexyl-benzo[2,1-d;3,4-d']bisthiazole) (2a) in
example 1, except that vic-bis(pinacolatoboryl)-2-butene (with the
equivalent of 1.3 eq to the substrate 5a) is used instead of
vic-bis-(pinacolatoboryl)-7-tetradecene (with the equivalent of 1.3
eq to the substrate 5a).
Preparation of poly(benzobisthiazole-bithiophene) (1c)
[0714] Dibromo-benzobisthiazole (2b) (79 mg, 0.209 mmol, 1 eq.) is
added as a 4.2 mL chlorobenzene solution into a pre-degassed
mixture of bis(2-trimethylstannyl-2-do-decylthiophene) (3c) (173.1
mg, 0.209 mmol, 1 eq.), tris(dibenzylideneacetone)dipalladium(0)
(5.7 mg, 0.003 mmol, 3% eq.) and tri-o-tolylphosphine (3.8 mg,
0.006 mmol, 6% eq.). The reaction mixture is stirred at 130.degree.
C. for 2 days. After two days of reaction,
tris(dibenzylideneacetone)-dipalladium(0) (5.7 mg, 0.003 mmol, 3%
eq.) and tri-o-tolylphosphine (3.8 mg, 0.006 mmol, 6% eq.) is
added. After four days of reaction, another portion of
tris(dibenzylidene-acetone)dipalladium(0) (5.7 mg, 0.003 mmol, 3%
eq.) and tri-o-tolylphosphine (3.8 mg, 0.006 mmol, 6% eq.) is
added. After total 6 days, the polymerization is stopped by the
addition of 2-bromothiophene (0.01 mL) and
2-tributylstannylthiophene (0.01 mL). 2-Bromothiophene is added
first followed by 2-tributylstannylthiophene 4 hours later. After
another 24 hours stirring, the reaction mixture is cooled to room
temperature. The mixture is filtered and the filtrate is
concentrated and added dropwise to a methanolic solution of 5
weight % HCl (200 mL). The polymer is filtered and before soxhlet
extraction in acetone showed Mn=959 g/mol (Mw=1410 g/mol &
D=1.47).
Example 5
Preparation of N-4-decylaniline-2,6-dibromo
dithiazolo[2,3-d;3',2'-b]pyrrole (2c)
##STR00117##
[0715] Preparation of N-4-decylaniline-2,6-bis(triisoproylsilyl)
dithiazolo[2,3-d;3',2'-b]pyrrole) (4b)
[0716] A mixture of bis(triisopropylsilyl)-dibromobithiazole (5a)
(790 mg, 1.237 mmol), tris(dibenzylideneacetone)dipalladium(0) (113
mg, 0.123 mmol, 0.1 eq.), sodium tert-but-oxide (200 mg, 2.968
mmol, 2.4 eq.) and rac-BINAP (153 mg, 0.347 mmol, 0.2 eq.) is
degassed 3 times. 4-n-Decylaniline (360 mg, 1.546 mmol, 1.25 eq.)
in anhydrous toluene (18 mL) is added. The reaction mixture is
stirred and heated at 100.degree. C. for 2 days under nitrogen.
After the mono-aminated intermediate is formed
tris(dibenzylidene-acetone)dipalladium(0) (56 mg, 0.061 mmol, 0.05
eq.) and 0.36 mL of a 10 weight % solution of
tri-tert-butylphosphine (24 mg, 0.173 mmol, 0.1 eq.) in n-hexane is
added. The reaction mixture is stirred at 100.degree. C. for 2 days
under nitrogen. Afterwards the reaction mixture is diluted with
ethyl acetate (100 mL). The resulting reaction mixture is washed
with ammonium chloride saturated water (100 mL) and the aqueous
layer is extracted with ethyl acetate (3.times.70 mL). The combined
organic layers are washed with sodium chloride saturated water (50
mL), dried over magnesium sulfate, and concentrated in vacuo.
Column chromatography using ethyl acetate/n-hexane (2/98) provided
off-white solid. .sup.1H-NMR (d-chloroform) (400 MHz): .delta. 8.58
(d, J=9.6 Hz, 2H), .delta. 7.34 (d, J=8.4 Hz, 2H), .delta. 2.28
(dd, J=8 Hz, 2H), .delta. 1.65 (m, J=8 Hz, 2H), .delta. 1.52-1.46
(m, J=8 Hz, 6H), .delta. 1.27 (s, 14H), .delta. 1.19-1.21 (d, J=8
Hz, 36H), .delta. 0.88 (t, J=7.6 Hz, 3H).
Preparation of N-4-decylaniline-2,6-dibromo
dithiazolo[2,3-d;3',2'-b]pyrrole (2c)
[0717] A solution of bromine (0.16 g, 0.05 mL, 1.01 mmol, 4 eq.) in
chloroform (3 mL) containing trichloroacetic acid (4 mg) is slowly
and dropwise added to a solution of 4b (0.180 g, 0.253 mmol) in
chloroform (4 mL) at 0.degree. C. The reaction mixture is stirred
at room temperature for 2 days. The reaction mixture is diluted
with dichloromethane (50 mL), washed with an aqueous solution of 20
weight % sodium thiosulfate (50 mL) and an aqueous solution of 10
weight % sodium bicarbonate (50 mL). Subsequently the organic layer
is dried over magnesium sulfate and concentrated in vacuo.
Purification by column chromatography using n-hexane followed by
re-crystallisation from n-hexane affords white flakes. .sup.1H-NMR
(d-chloroform) (400 MHz): .delta. 7.88 (d, J=8.4 Hz, 2H), .delta.
7.35 (d, J=8 Hz, 2H), .delta. 2.66 (dd, J=7.6 Hz, 2H), .delta. 1.63
(m, J=7.6 Hz, 2H), .delta. 1.28 (s, 14H), .delta. 0.88 (t, J=7.6
Hz, 3H). LC-MS: 97.2% purity with m/z 556. Elemental analysis
(calcd): C, 47.54 (47.58); H, 4.46 (4.54).
Example 6
Preparation of poly(dithiazolopyrrole-bisthienylethylene) (1d)
##STR00118##
[0719] Dibromo-dithiazolopyrrole (2c) (36 mg, 0.065 mmol, 1 eq.)
prepared as described in example 5,
bis(2-trimethylstannyl-4-dodecylthienyl)ethylene (3d) (55.4 mg,
0.065 mmol, 1 eq.), tris(dibenzylideneacetone)dipalladium(0) (3.6
mg, 0.004 mmol, 6% eq.) and tri-o-tolylphosphine (2.4 mg, 0.008
mmol, 12% eq.) are added into a Schlenk flask and degassed 3 times.
Chlorobenzene (1.5 mL) is added and the reaction mixture is stirred
at 130.degree. C. for 2 days. After two days of reaction,
tris(dibenzylideneacetone)dipalladium(0) (3.6 mg, 0.004 mmol, 6%
eq.) and tri-o-tolylphosphine (2.4 mg, 0.008 mmol, 12% eq.) was
added. After total reaction of 3 days, the polymerization is
stopped by the addition of 2-bromothiophene (0.01 mL) followed by
2-tributylstannylthiophene (0.01 mL) 3 hours later. After another 3
hours stirring, the reaction mixture is cooled to room temperature
and added dropwise to methanol (100 mL), filtered, and then
subjected to Soxhlet extraction with acetone. The polymer is
recovered as solid mass and showed Mn=4305 g/mol (Mw=7571 g/mol
& D=1.76).
Measurement of the Ionization Potential of Polymer 1a
[0720] The oxidative stability of .pi.-conjugated polymers may be
contributed by their ionization potential (IP), that is, on the
energy of the highest occupied molecular orbital (HOMO) with
respect to vacuum. The ionization potential (IP) is also reflected
as negative value of the HOMO energy level (E.sub.HOMO) of a
molecule, oligomer or polymer,
IP=-E.sub.HOMO
and can be measured by cyclic voltammetry (CV).
[0721] The HOMO energy levels (E.sub.HOMO) of
poly(benzobisthiazole-cyclopentadithiophene) (1a), prepared as
described in example 2, and comparative polymer 22a, which is
described by Xiao, S; Zhou H.; You, W. in Macromolecules 2008, 41,
5688-5696, are determined by cyclic voltammetry (CV).
##STR00119##
[0722] Cyclic voltamogramms are recorded from thin films of polymer
1a, respectively comparative polymer 22a, drop-casted from 0.5
mg/mL chloroform solutions. A Pt disk is used as a working
electrode and Ag/AgCl reference electrode is employed. The
measurement is done in tetrabutylammonium tetrafluoroborate as
electrolyte and ferrocene/ferrocenium redox couple (Fc/Fc.sup.+) is
used as an internal reference, which has a known reduction
potential of 4.8 eV. The electrochemical (oxidation and reduction)
onset is determined at the position where the current starts to
differ from the baseline and the HOMO energy level (E.sub.HOMO) is
calculated from the onset oxidation potential (E.sub.Ox), as shown
in the equation below:
E.sub.HOMO=-(E.sub.Ox+4.8)[eV]
[0723] The results are outlined in table 1.
TABLE-US-00001 TABLE 1 polymer E.sub.HOMO [eV] 1a -5.44 22a
(comparative) -5.04
[0724] As can be derived from table 1, the HOMO energy level
(E.sub.HOMO) value of polymer 1a is decreased by 0.4 eV compared to
the HOMO energy level (E.sub.HOMO) value of comparative polymer
22a, and thus the ionization potential (IP) and consequently the
oxidative stability of polymer 1a is higher than the one of
comparative polymer 22a.
Fabrication of an Organic Field-Effect Transistor using Polymer 1a
as Semiconductor
[0725] An organic field effect transistor is made in bottom gate
bottom contact (BGBC) architecture, as depicted in FIG. 1. Heavily
doped Si wafer are used as substrate and gate electrode with 200 nm
thermally grown SiO.sub.2 serving as gate dielectric. Source and
drain electrode are made of gold which is lithographically
patterned. Before semiconductor deposition, the substrate is vapor
treated with hexamethyldisilazane (HMDS). The polymer 1a solution
is prepared by solubilizing the polymer 1a in 1,2-dichloro-benzene
and heating it inside oven until soluble. Subsequently,
semiconductor solution deposition of the polymer 1a is done by spin
coating (deposition condition: 2000 rpm, 255 acc, 1 minute). The
organic field effect transistor is made in ambient environment.
Testing of the Organic Field-Effect Transistor using Polymer 1a as
Semiconductor
[0726] The hole mobility (.mu..sub.o), onset voltage (V.sub.on,
voltage when the drain current increases abruptly and can be
measured), and the on/off ratio of the organic field effect
transistor using polymer 1a as semiconductor are determined at room
temperature and after annealing at 200.degree. C. for 30 minutes,
in order to observe the effect of annealing on the semiconductor
performance. The organic field effect transistor is tested in
ambient environment. Channel length (L)=5 .mu.m, Channel width
(W)=350 .mu.m, W/L=70. Measurement is performed at: gate voltage
(Vg)=sweep from 20 to -90 V, drain voltage (Vd)=-90 V,
[0727] The results are outlined in table 2.
TABLE-US-00002 TABLE 2 hole mobility .mu..sub.p [cm.sup.2/Vs]
V.sub.on[V] On/Off ratio at RT 0.2 .times. 10.sup.-3 -5 2.66
.times. 10.sup.4 after annealing 1.06 .times. 10.sup.-3 5 6.01
.times. 10.sup.4 at 200.degree. C.
* * * * *