U.S. patent application number 11/047972 was filed with the patent office on 2005-06-30 for method of doping organic semiconductors with quinone derivatives and 1, 3, 2 - dioxaborine derivatives.
Invention is credited to Hartmann, Horst, Kuehl, Olaf, Pfeiffer, Martin, Youxuan, Zheng, Zeika, Olaf.
Application Number | 20050139810 11/047972 |
Document ID | / |
Family ID | 34442480 |
Filed Date | 2005-06-30 |
United States Patent
Application |
20050139810 |
Kind Code |
A1 |
Kuehl, Olaf ; et
al. |
June 30, 2005 |
Method of doping organic semiconductors with quinone derivatives
and 1, 3, 2 - dioxaborine derivatives
Abstract
The invention relates to the use of an organic mesomeric
compound as organic dopant for doping an organic semiconducting
matrix material for varying the electrical properties thereof. In
order to be able to handle organic semiconductors more easily in
the production process and to be able to produce electronic
components with doped organic semiconductors more reproducibly, a
quinone or quinone derivative or a 1,3,2-dioxaborine or a
1,3,2-dioxaborine derivative may be used as a mesomeric compound,
which under like evaporation conditions has a lower volatility than
tetrafluorotetracyanoquinonedimethane (F4TCNQ).
Inventors: |
Kuehl, Olaf; (Markkleeberg,
DE) ; Hartmann, Horst; (Dresden, DE) ; Zeika,
Olaf; (Theiben, DE) ; Pfeiffer, Martin;
(Dresden, DE) ; Youxuan, Zheng; (Dresden,
DE) |
Correspondence
Address: |
BAKER & BOTTS
30 ROCKEFELLER PLAZA
NEW YORK
NY
10112
|
Family ID: |
34442480 |
Appl. No.: |
11/047972 |
Filed: |
January 31, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11047972 |
Jan 31, 2005 |
|
|
|
10792133 |
Mar 3, 2004 |
|
|
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Current U.S.
Class: |
252/500 |
Current CPC
Class: |
C09B 69/105 20130101;
H01L 51/0051 20130101; H01L 51/0052 20130101; H01L 51/007 20130101;
H01L 51/0074 20130101; Y02P 70/50 20151101; H01L 51/0071 20130101;
C09B 69/109 20130101; H01L 51/001 20130101; Y02B 10/10 20130101;
H01L 51/0078 20130101; C09K 11/06 20130101; C09K 2211/1011
20130101; Y02E 10/549 20130101; C09K 2211/1092 20130101; H01L
51/002 20130101; H01L 51/0072 20130101; H01L 51/0059 20130101; H01L
51/506 20130101; C09B 69/102 20130101; H01L 51/0092 20130101; H01L
51/008 20130101; H01L 51/0054 20130101; H01L 51/0067 20130101; H01L
51/0079 20130101; C09K 2211/1007 20130101 |
Class at
Publication: |
252/500 |
International
Class: |
H01B 001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 4, 2003 |
DE |
103 57 044.6 |
Claims
1-54. (canceled)
55. Dopand for doping an organic semiconducting matrix material,
wherein the dopand is an organic, mesomeric quinon or quinon
derivative compound selected from the group consisting of compounds
having one of the following structures: 4243wherein in structure
(40) R.sub.1-R.sub.4 is independently Cl, CN, aryl or heteroary,
wherein aryl and heteroaryl have one or more substituents selected
from the group consisting of CN, NO.sub.2, CF.sub.3,
perfluoroalkyl, SO.sub.3R and halogen, wherein A and B are selected
from 44wherein in structure (41) R.sub.1-R.sub.8 is independently
Cl, F, CN, NO.sub.2, perfluoroalkyl, aryl or heteroaryl, wherein
aryl and heteroaryl have one or more substituents selected from the
group consisting of CN, NO.sub.2, NO, perfluoroalkyl, S0.sub.3R,
and halogen; wherein in structure (42) R.sub.1-R.sub.6 is
independently Cl, F, CN, NO.sub.2, NO, perfluoroalkyl, aryl or
heteroaryl, wherein aryl and heteroaryl have one or more
substituents selected from the group consisting of CN, NO.sub.2,
perfluoroalkyl, SO.sub.3R and halogen, wherein A and B are selected
from the group consisting of 45wherein in structure (43)
R.sub.1-R.sub.8 is independently Cl, F, perfluoroalkyl, CN,
NO.sub.2, NO, aryl or heteroaryl, wherein aryl and heteroaryl have
one or more substituents selected from the group consisting of CN,
NO.sub.2, perfluoroalkyl, SO.sub.3R and halogen; wherein in
structure (44) R.sub.1-R.sub.6 is independently Cl, F, CN,
NO.sub.2, NO, perfluoroalkyl, aryl or heteroaryl, wherein aryl and
heteroaryl have one or more substituents selected from the group
consisting of CN, NO.sub.2, perfluoroalkyl, SO.sub.3R and halogen;
wherein in structure (45) R.sub.1-R.sub.4 is independently Cl, F,
NO.sub.2, NO, perfluoroalkyl, aryl, or heteroaryl, wherein aryl and
heteroaryl have one or more substituents selected from the group
consisting of CN, NO.sub.2, perfluoroalkyl, SO.sub.3R and halogen;
wherein in structure (46) R.sub.1-R.sub.6 is independently Cl, F,
CN, NO.sub.2, NO, perfluoroalkyl, aryl or heteroaryl, wherein aryl
and heteroaryl have one or more substituents selected from the
group consisting of CN, NO.sub.2, perfluoroalkyl, S0.sub.3R and
halogen; wherein in structure (47) R.sub.1-R.sub.12 is
independently Cl, F, CN, NO.sub.2, NO, perfluoroalkyl, aryl or
heteroaryl, wherein aryl and heteroaryl have one or more
substituents selected from the group consisting of CN, NO.sub.2,
perfluoroalkyl, SO.sub.3R and halogen, or wherein R.sub.1, R.sub.3,
R.sub.9 and R.sub.12 are hydrogen and R.sub.2, R.sub.4-R.sub.8,
R.sub.10 and R.sub.11 is independently Cl, F, CN, NO.sub.2, NO,
perfluoroalkyl, aryl or heteroaryl, wherein aryl and heteroaryl
have one or more substituents selected from the group consisting of
CN, NO.sub.2, perfluoroalkyl, SO.sub.3R and halogen; wherein in
structure (48) R.sub.1-R.sub.12 is independently Cl, F, CN,
NO.sub.2, NO, perfluoroalkyl, aryl or heteroaryl, wherein aryl and
heteroaryl have one or more substituents selected from the group
consisting of CN, NO.sub.2, perfluoroalkyl, SO.sub.3R and halogen;
and wherein the dopand, under like evaporation conditions, has a
lower volatility than tetrafluorotetracyano-quinonedimethane
(F.sub.4TCQ).
56. Dopand according to claim 55, wherein the substituents A, B, C
and D in structures (41), and (43) to (48) are the same or
different and are selected from the group consisting of: 46
57. Dopand according to claim 55 or 56, wherein perfluoroalkyl is
CF.sub.3, and halogen is fluorine or chlorine.
58. Dopand according to claim 55, wherein the dopand is a quinoid
system having a quinoid ring and one, two or three annulated
aromatic rings.
59. Dopand according to claim 58, wherein the aromatic rings have
one or more hetero atoms.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation application of
U.S. patent application Ser. No. 10/792,133, filed Mar. 3, 2004,
which claimed priority to German Patent Application No. 103 57
044.6, filed Dec. 4, 2003, both of which are incorporated herein by
reference in their entirety.
BACKGROUND OF THE INVENTION
[0002] The invention relates to the use of an organic mesomeric
compound as an organic dopant for doping an organic semiconducting
matrix material for varying the electrical properties thereof, a
doped semiconducting matrix material, and an electronic component
made of the latter.
[0003] The doping of silicon semiconductors has already been state
of art for several decades. By this method, an increase in
conductivity, initially quite low, is obtained by generation of
charge carriers in the material as well as, depending upon the type
of dopant used, a variation in the Fermi level of the
semiconductor.
[0004] However, several years ago it was also disclosed that
organic semiconductors may likewise be strongly influenced with
regard to their electrical conductivity by doping. Such organic
semiconducting matrix materials may be made up either of compounds
with good electron-donor properties or of compounds with good
electron-acceptor properties. For doping electron-donor materials,
strong electron acceptors such as tetracyanoquinonedimethane (TCNQ)
or 2,3,5,6-tetrafluorotetracyano- 1,4-benzoquinonedimethane
(F4TCNQ) have become well known. M. Pfeiffer, A. Beyer, T. Fritz,
K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 (1998) and J.
Blochwitz, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73
(6), 729-731 (1998). By electron transfer processes, these produce
so-called holes in electron donor-like base materials
(hole-transport materials), owing to the number and mobility of
which the conductivity of the base material is relatively
significantly varied. For example, N,N'-perarylated benzidines TPD
or N,N',N" perarylated starburst compounds, such as the substance
TDATA, but also certain metal phthalocyanines, such as in
particular zinc phthalocyanine ZnPc, are known as matrix materials
with hole-transport properties.
[0005] However, the compounds previously investigated have
disadvantages for technical use in the production of doped
semiconducting organic layers or of suitable electronic components
with doped layers of this kind. The manufacturing processes in
large technical production plants or those on a technical scale
cannot always be precisely controlled, requiring high control and
regulation expenses during processing in order to obtain the
desired product quality, or to undesirable tolerances of the
products. In addition, there are disadvantages associated with the
use of previously known organic donors with regard to electronic
component structures, such as light-emitting diodes (OLEDs),
field-effect transistors (FETs) or solar cells themselves due to
production difficulties related to handling of dopants. The
electronic components may exhibit undesirable heterogeneities or
the electronic components may exhibit undesirable aging effects. In
addition, care has to be taken to see that the dopants used have
appropriate electron affinities and other properties suitable for
the particular application, since under certain conditions the
dopants also help to determine the conductivity or other electrical
properties of the organic semiconducting layer.
[0006] The object of the invention is to prepare organic dopants
for doping organic semiconductors which are easier to handle during
the production process and which result in electronic components
whose organic semiconducting materials are capable of being
produced reproducibly.
SUMMARY OF THE INVENTION
[0007] The invention relates to the use of an organic mesomeric
compound as organic dopant for doping an organic semiconducting
matrix material for varying the electrical properties thereof. In
order to be able to handle organic semiconductors more easily in
the production process and to be able to produce electronic
components with doped organic semiconductors more reproducibly, a
quinone or quinone derivative or a 1,3,2-dioxaborine or a
1,3,2-dioxaborine derivative may be used as a mesomeric compound,
which under like evaporation conditions has a lower volatility than
tetrafluorotetracyanoquinonedimethane (F4TCNQ).
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 shows the doping of ZnPc with
N,N'-dicyano-2,3,5,6-tetrafluo- ro-1,4-quinonediimine
(F4DCNQI).
[0009] FIG. 2 shows the doping of ZnPc with
N,N'-dicyan-2,5-dichloro-1,4-q- uinonediimine (C12DCNQI).
[0010] FIG. 3 shows the doping of ZnPc with
N,N'-dicyano-2,5-dichloro-3,6-- difluoro-1,4-quinonediimine
(C12F2DCNQI).
[0011] FIG. 4 shows the doping of ZnPc with
N,N'-dicyano-2,3,5,6,7,8-hexaf- luoro-1,4-naphtho-quinonediimine
(F6DCNNOI).
[0012] FIG. 5 shows the doping of ZnPc with
1,4,5,8-tetrahydro-1,4,5,8-tet-
rathia-2,3,6,7-tetracyano-anthraquinone (CN4TTAQ).
[0013] FIG. 6 shows the doping of ZnPc with
2,2,7,7-tetrafluoro-2,7-dihydr- o-1,3,6,8-tetraoxa-2,7-dibora
4,9,10,11,12-pentachloro-benzo[e]pyrene.
DETAILED DESCRIPTION OF THE INVENTION
[0014] The present invention relates to an organic mesomeric
compound usable as an organic dopant, which is a quinone or quinone
derivative, in particular an unsubstituted, substituted or
anellated quinone or quinone derivative, or a 1,3,2-dioxaborine or
1,3,2-dioxaborine derivative, in particular, an unsubstituted,
substituted or anellated 1,3,2-dioxaborine or 1,3,2-dioxaborine
derivative and which under like conditions of evaporation has a
lower volatility than tetrafluorotetracyanoquinonedimet- hane
(F4TCNQ). The quinone derivatives of the present invention are, in
particular, quinoid systems in which one, two or more quinoid
oxygen atoms is/are replaced by a mesomerically and/or inductively
electron-attracting, double bond-bonded substituent, in particular,
by one of the substituents indicated below. Inductively
electron-attracting is to be understood as those residues, which
with respect to carbon, have an inductive effect on unsaturated
hydrocarbons. Due to high evaporation temperature and low
volatility under similar conditions, production processes can be
controlled better and carried out with less effort and greater
reproducibly. The preparation of quinones and their derivatives or
1,3,2-dioxaborines and their derivatives as dopants permit
sufficient electrical conductivity of the organic semiconducting
matrix with favorable electron affinity of the dopants in the
respective components at low coefficients of diffusion, which
ensure component structures remaining constant over time. In
addition, charge-carrier injection of contacts into the doped layer
can be improved by the dopants. Additionally, the doped organic
semiconducting material and the resulting electronic component,
because of the compounds used according to the invention, can have
improved long-term stability. This relates, for example, to a
reduction in the dopant concentration with time. In addition, this
relates to the stability of the doped layer, which is located
adjacent to undoped layers of an electrooptical component,
resulting in electrooptical components with high long-term
stability of electrooptical properties, such as luminous yield at a
given wavelength, efficiency of a solar cell or the like.
[0015] Preferred refinements follow from the dependent claims.
[0016] Here volatility may be determined as the evaporation rate
measured under like conditions, for example, a pressure of
2.times.10.sup.-4 Pa and a specified evaporation temperature of
150.degree. C. Alternatively, the volatility may be determined as
the evaporation rate of a substrate measured as layer thickness
growth per unit of time (nm/s) under otherwise like conditions. The
volatility of the compounds according to the present invention is
.ltoreq.0.95 times or 0.9 times, preferably .ltoreq.0.8 times, more
preferably .ltoreq.0.5 times, even more preferably .ltoreq.0.1
times or .ltoreq.0.05 times or .ltoreq.0.01 times that of F4TCNQ or
less.
[0017] The evaporation rate of the substrate with the compounds
according to the present invention may be determined, for example,
by the use of a quartz thickness monitor, as is customarily used
for example in the production of OLEDs. In particular, the ratio of
the evaporation rates of matrix materials and dopants may be
measured by independent measurements thereof with the use of two
separate quartz thickness monitors to adjust the doping ratio.
[0018] The volatility relative to that of F4TCNQ may in each
instance be referred to that of the pure compound or to the
volatility in a given matrix material, for example ZnPc.
[0019] It goes without saying that the compounds used according to
the present invention preferably are procured in such a way that
they evaporate relatively or practically undecomposed. Under
certain circumstances, however, precursors may alternatively be
selectively used as dopant sources, which release the compounds
used according to the present invention, for example acid addition
salts, a volatile or non-volatile inorganic or organic acid, or
charge-transfer complexes thereof, where the acids or electron
donors preferably are not or are only slightly volatile or the
charge-transfer complex itself works as dopant.
[0020] The dopant preferably is selected in such a way that under
otherwise like conditions, such as doping concentration, molar
ratio of dopant matrix, layer thickness, and current, in a given
matrix material (for example, zinc phthalocyanine or another matrix
material mentioned further below) generates a conductivity just as
high as or preferably higher than F4TCNQ. Such a conductivity may
be a conductivity (s/cm) greater than or equal to 1.1 times, 1.2
times or greater than/equal to 1.5 times or two times that of
F4TCNQ as dopant.
[0021] The dopant used according to the present invention
preferably is selected in such a way that the semiconducting
organic matrix material doped with the dopant, after a temperature
change from 100.degree. C. to room temperature (20.degree. C.)
still has .gtoreq.20%, preferably .gtoreq.30%, more preferably
.gtoreq.50% or 60% of the conductivity (s/cm) of the value at
100.degree. C.
[0022] According to the present invention, a variety of quinone
derivatives and in addition 1,3,2-dioxaborines may be used as
dopants for the said preferred hole-transport materials HT.
[0023] Quinoid Structures
[0024] In quinonoid compounds used according to the present
invention, one, two, three or four or all quinoid .dbd.O groups of
the quinoid compound, which may represent an ortho or para-quinoid
system, where alternatively mixed ortho-para quinoid systems may
occur in multinuclear quinoid systems, may be selected from the
group, as they are defined below for the substituents S1 to S11,
S13 to S21, optionally alternatively without S1, the substituents
being defined below.
[0025] For a quinoid compound used according to the invention, one,
two, three, four or more or all substituents for a quinoid .dbd.O
group may be selected from the group consisting of S1-S11, S14-S16,
optionally alternatively without S1, or be selected from the group
consisting of S1, S5-S14 and S16, optionally alternatively without
S1, or be selected from the group consisting of S3, S4, S6-S10,
S15, S16, optionally alternatively without S1.
[0026] Alternatively, for a quinoid compound used according to the
invention one, two, three, four or more or all substituents for a
quinoid .dbd.O group may be selected from the group consisting of
S1, S5, S7-S9, S11, S14, S16-21, optionally alternatively without
S1, or from the group S1, S5, S8, S9, S11, S14, S16, S18,
optionally alternatively without S1.
[0027] In particular, one, two, three, four or more or all
substituents for a quinoid group .dbd.O may be .dbd.C(CN).sub.2 or
.dbd.N(CN) or .dbd.N(NO2).sub.2 or .dbd.C(CN) (C(O)R) or
.dbd.N(C(O)R). Preferably one, two, three or four or more or all
quinoid substituents of the quinoid system contain a mesomerically
linked --NO2 and/or --C(O)R group.
[0028] Compounds having the following basic quinoid skeletons may
be used according to the invention. 123456
[0029] where in compounds 3, 3b, 3c, m may be 0, 1, 2, 3, 4 to 6 or
greater, and where in addition, in compounds 25-27 the substituent
Z of a group M may be alike or unlike another substituent X, Y, V,
W,
[0030] where in compound 25 the two groups M or for M equals
.dbd.C=Z the two groups Z may be alike or unlike, and where in
compound 32 preferably one or both groups M are not .dbd.C=Z.
[0031] It goes without saying that the compounds indicated in each
instance may comprise all stereoisomers, in particular syn and anti
isomers, providing that these are sterically possible in each
instance.
[0032] Here the substituents T, U, V, W, X, Y and Z preferably
represent mesomeric and/or referred to carbon or a hydrocarbon, in
particular a saturated hydrocarbon, inductively attracting double
bond-bonded substituents.
[0033] In particular, for compounds 1-33 the substituents T, U, V,
W, X, Y and/or Z may in each instance be unlike or alike and be
selected from the group consisting of: 78
[0034] where R preferably is an organic residue or hydrogen. R17
may in particular alternatively be --CF.sub.3, or perfluoroalkyl,
in particular with C1-C6. If the substituent is S17, X and Y of the
substituent S17 preferably are not again S17 and/or S18 to S21.
[0035] The substituents T, U, V, W, X and/or Z in compounds 1-33
may in particular in each instance be alike or unlike and be
selected from the group consisting of 9
[0036] where R preferably is an organic residue or hydrogen, while
R17 of group S8 in particular may alternatively be --CF.sub.3 or in
general perfluoroalkyl, in particular with C1 to C6. In particular,
one, two, three, four or all of the substituents may be selected
from this group. In particular, X and Y may be alike or unlike and
X or Y or X and Y may be selected from this group. In particular, V
and W may be alike or unlike and V or W or V and W may be selected
from this group.
[0037] The substituents T, U, V, W, X, Y and/or Z in compounds 1 to
33 may in each instance be alike or unlike and be selected from the
group consisting of 10
[0038] where R preferably is an organic residue or hydrogen, while
R17 of group S8 in particular may alternatively be --CF3 or in
general perfluoroalkyl, in particular with C1 to C6. In particular,
one, two, three, four or all of the substituents may be selected
from this group. In particular, X and Y may be alike or unlike and
X or Y or X and Y may be selected from this group. In particular, V
and W may be the alike or unlike and V or W or V and W may be
selected from this group.
[0039] The substituents T, U, V, W, X, Y and/or Z in compounds 1 to
33 may in each instance be alike or unlike and may be selected from
the group consisting of 11
[0040] where R preferably is an organic residue or hydrogen, while
R17 of the group S8 in particular may alternatively be --CF.sub.3
or in general perfluoroalkyl, in particular with C1 to C6. In
particular, one, two, three, four or all of the substituents may be
selected from this group. In particular, X and Y may be alike or
unlike and X or Y or X and Y may be selected from this group. In
particular, V and W may be alike or unlike and V or W or V and W
may be selected from this group.
[0041] The substituents T, U, V, W, X, Y and/or Z in compounds 1 to
33 may alternatively in each instance be alike or unlike and be
selected from the group consisting of S1, S5, S7-S9, S11, S14,
S16-21, optionally alternatively without S1, or from the group S1,
S5, S8, S9, S11, S14, S16, S18, optionally alternatively without
S1. In particular, one, two, three, four or all of the substituents
may be selected from this group. In particular, X and Y may be
alike or unlike and X or Y or X and Y may be selected from this
group. In particular, V and W may be alike or unlike and V or W or
V and W may be selected from this group.
[0042] The following relationships between the substituents may
apply to compounds 1 to 33. The following substituent relationships
may in particular apply to the group of substituents S1 to S21. The
following substituent relationships may apply to the group of
substituents S1 to S11, S14 to S16. The following substituent
relationships may apply to the group of substituents S1, S5-S14,
S16. The following substituent relationships may apply to the group
S3, S4, S6-10, S15, S16.
[0043] X and/or Y may not or may not simultaneously be .dbd.O or
.dbd.C(CN)2. This applies in particular to a mononuclear quinoid
dopant, whose substituents preferably form or represent one or no
aromatic ring system. In particular, this may apply to the
compounds 1 and 20. V and/or W may not or may not simultaneously be
.dbd.O or .dbd.C(CN)2.
[0044] Preferably, in the compound used according to the invention,
in each instance .dbd.X and .dbd.X are alike and/or .dbd.U and =T
are alike and/or .dbd.V and .dbd.W are alike.
[0045] The substituents AA and BB preferably are in each instance
alike, and may alternatively be unlike one another.
[0046] At least one or two of the substituents in the group .dbd.X,
.dbd.Y, .dbd.U, .dbd.V, =T, .dbd.W, =Z or all substituents in the
said group may be unlike .dbd.O. .dbd.X and .dbd.Y may be unlike
.dbd.O.
[0047] Preferably, at least one or two of the substituents in the
group .dbd.X, .dbd.Y, .dbd.U, .dbd.V, =T, .dbd.W, =Z or all
substituents in the group are unlike .dbd.S.
[0048] Preferably at least one or both substituents in the group
.dbd.X and .dbd.Y are unlike .dbd.S.
[0049] At least one or two of the substituents in the group .dbd.X
and .dbd.Y, .dbd.U, .dbd.V, =T, .dbd.W, =Z or all substituents in
the group may unlike .dbd.C(CN).sub.2.
[0050] At least one or both substituents in the group .dbd.X and
.dbd.Y may be unlike .dbd.C(CN).sub.2.
[0051] Preferably at least one or both substituents in the group
.dbd.X and .dbd.Y are .dbd.N(CN). Preferably, one or both
substituents .dbd.V and .dbd.W are .dbd.N(CN) and/or one or both
substituents .dbd.U and =T are .dbd.N(CN).
[0052] Preferably at least one or both substituents in the group
.dbd.X and .dbd.Y and/or one or both substituents in the group
.dbd.V and .dbd.W equal .dbd.N(NO2).
[0053] Preferably at least one or both substituents in the group
.dbd.X and .dbd.Y and/or one or both substituents in the group
.dbd.V and .dbd.W equal .dbd.NR, where R may alternatively be
--CF.sub.3 or in general perfluoroalkyl, in particular with
C1-C6.
[0054] Preferably at least one or both substituents in the group
.dbd.X and .dbd.Y and/or one or both substituents in the group
.dbd.V and .dbd.W equal .dbd.N(C(O)R.sup.18.
[0055] Preferably at least one or both substituents in the group
.dbd.X and .dbd.Y and/or one or both substituents in the group
.dbd.V and .dbd.W equal .dbd.C(NO.sub.2).sub.2.
[0056] Preferably at least one or both substituents in the group
.dbd.X and .dbd.Y and/or one or both substituents in the group
.dbd.V and .dbd.W equal .dbd.C(C(O)R.sup.13) (C(O)R.sup.14).
[0057] Preferably at least one or both substituents in the group
.dbd.X and .dbd.Y and/or one or both substituents in the group
.dbd.V and .dbd.W equal .dbd.C(CF.sub.3).sub.2 or in general
.dbd.C(perfluoroalkyl) 2, in particular with C1-6.
[0058] Preferably at least one or two or more or all substituents
in the group .dbd.X, .dbd.Y.dbd.U.dbd.V=T.dbd.W=Z equal
.dbd.N(CN)
[0059] Preferably at least one or two or more or all substituents
in the group .dbd.X, .dbd.Y, .dbd.U, .dbd.V, =T, .dbd.W =Z equal
.dbd.C(CN.sub.2).sub.2 or contain a NO.sub.2 group conjugated with
the quinoid system.
[0060] Preferably at least one or two or more or all substituents
in the group .dbd.X, .dbd.Y, .dbd.U, .dbd.V, =T, .dbd.W, =Z equal
.dbd.N(NO.sub.2).
[0061] Preferably at least one or two or more or all substituents
in the group .dbd.X, .dbd.Y, .dbd.U, .dbd.V, =T, .dbd.W, =Z are
.dbd.NR, where R may in particular alternatively be --CF.sub.3 or
perfluoroalkyl with in particular C1-6.
[0062] Preferably at least one or two or more or all substituents
in the group .dbd.X, .dbd.Y, .dbd.U, .dbd.V, =T, .dbd.W, =Z are
.dbd.N(C(O)R.sup.18).
[0063] Preferably at least one or two or more or all substituents
in the group .dbd.X, .dbd.Y, .dbd.U, .dbd.V, =T, .dbd.W, =Z are
.dbd.C(C(O)R.sub.13) (C(O)R.sub.14) or contain a C(O)R group
conjugated with the quinoid system.
[0064] Preferably at least one or two or more or all substituents
in the group .dbd.X, .dbd.Y, .dbd.U, .dbd.V, =T, .dbd.W, =Z are
.dbd.C(CF.sub.3).sub.2 or in general .dbd.C(perfluoroalkyl).sub.2,
in particular with C1-6.
[0065] In particular, for the compounds 1-31 X may be .dbd.Y in
each instance or all substituents X, Y, U, V, T, W, Z may be alike,
without being limited thereto. Correspondingly, in a quinoid
compound generally all quinoid substituents may be alike.
[0066] Optionally, X or Y or X and Y are not O, in particular for
the compounds 1 or 20 or for compounds with only one quinoid ring.
Optionally, X or Y or X and Y are not S, in particular for the
compounds 1 or 20. Optionally, X or Y or X and Y are not
.dbd.C(CN)2, in particular, for compounds 1 or 20. This applies in
particular to a compound with only one 6-membered quinoid ring, in
particular, a ring with 6 C atoms.
[0067] If the compound has at least one or two or more quinoid =0
groups and/or .dbd.S groups, as applied to one of the compounds 1
to 33, to T, U, V, W, X, Y or Z, in particular in the case when X
or Y or X and Y is O or S, the quinoid ring, in particular when
only one quinoid ring is present, preferably with at least one or
at least two aryl residues, of which one, more or all may
alternatively have heteroatoms, is anellated or substituted.
[0068] The substituents AA and/or BB are double-bond, mesomerically
and/or inductively electron-attracting substituents, preferably
selected from the following group 1213
[0069] where optionally other suitable divalent, in particular
including double-bond, substituents may alternatively be used. R28
may in particular alternatively be --CF.sub.3 or another
perfluoroalkyl group, preferably with C1-6.
[0070] The compound according to the present invention may
represent a quinoid system with a quinoid ring and 1, 2 or 3 or
more anellated and/or in each instance aromatic rings forming a
residue R. The aromatic rings may in each instance have one or more
heteroatoms and be substituted or unsubstituted. The quinoid system
may be an ortho or para quinoid system. The quinoid system may in
particular be selected from the group of compounds 1-33, without
being limited thereto. One, two, three or more or all of the
aromatic rings may alternatively be alike or unlike by a group
-M1-C(R) .dbd.C(R).dbd.C(R)-M2- or -M1-C(=Z)-M2- with M1, M2 and be
selected from the group --O--, --S--, --NR--.
[0071] The invention also comprises compounds with a quinoid system
of two rings of 5 or 6 ring atoms in each instance, which may be
anellated with 1, 2, 3,4, 5 or 6 or more aromatic rings and/or be
substituted with formation of a residue R. The aromatic rings may
be substitute or unsubstituted.
[0072] The rings in each instance preferably have 6 atoms, which
may be 6 carbon atoms. In one or more rings or in each compound as
a whole, 1, 2, 3 or 4 or more C atoms may be replaced by
heteroatoms such as O, S, N. A variety of quinoid systems may be
anellated, mesomerically bonded by one or more double or triple
bonds, which may be C--C bonds or heteroatom-C-- bonds, or
otherwise linked. The bond may in particular be selected from the
group of compounds 1-33, without being limited thereto. One, two,
three or more or all of the aromatic rings may alternatively be
alike or unlike M1, M2 by a group -M1-C(R) .dbd.C(R)-M2 or
-M1-C(=Z)-M2- and be selected from the group --O--, --S--,
--NR--.
[0073] In addition, the present invention relates to compounds
having 3 or 4 quinoid rings of 5 or 6 atoms independent of one
another in each instance, which may have 1, 2, 3, 4, 5, 6, 7, 8, 9
or 10 anellated aromatic rings or forming a residue R with 6 atoms.
The aromatic rings may be substituted or unsubstituted. Of the
carbon atoms of a ring, a plurality of rings or the compound as a
whole 1, 2, 3 or 4 atoms may be heteroatoms such as O, N or P. The
compound may in particular be selected from the group of compounds
1-33, without being limited thereto. One, two, three or more or all
of the aromatic rings may alternatively be alike or unlike M1, M2
by a group -M1-C(R) .dbd.C(R)-M2 or -M1-C(=Z)-M2- and be selected
from the group --O--, --S--, --NR--.
[0074] Irrespective thereof, the compounds used according to the
present invention may have 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 aryl
residues, of which preferably at least one, more or especially
preferably all are anellated with one or more quinoid systems
and/or with one another, and/or form the residues R. The aromatic
rings may be substituted or unsubstituted. Here heteroaryl residues
are also to be understood as aryl residues. The aryl residues may
in each instance link two quinoid rings to one another, preferably
with mesomeric linkage of the quinoid rings. The quinoid system may
be selected from the group of compounds 1-33, without being limited
thereto. One, two, three or more or all of the aromatic rings may
alternatively be alike or unlike M1, M2 by a group
-M1-C(R).dbd.C(R)-M2 or -M1-C(=Z)-M2- and be selected from the
group --O--, --S--, --NR--. Thus, for example, in the compounds 4,
22 or 23 in each instance 2 or 3 or more (hetero)aryl rings may be
located between the quinoid rings, bridging them.
[0075] The aromatic rings of the said quinoid systems and/or the
groups -M1-C(R).dbd.C(R)-M2 or -M1-C(=Z)-M2- are preferably
perhalogenated, in particular perfluorinated or
percyano-substituted. Preferably no additional non-aromatic and/or
non-quinoid rings are contained.
[0076] Irrespective thereof, the compounds used according to the
present invention may have 2, 3, 4, 5 or 6 or more quinoid ring
systems. Preferably, one, more or all of the quinoid rings are 5 or
6-membered. Ring carbon atoms may be replaced by heteroatoms. At
least two, more or all of the quinoid rings may be anellated
together with mesomeric linkage to form a larger quinoid system or
be mesomerically linked by one or more bridges or not linked with
formation of a larger mesomeric system. The compound may in
particular be selected from the group of compounds 1-33, without
being limited thereto. The quinoid system may in particular be
selected from the group of compounds 1-33, without being limited
thereto. One, two, three or more or all of the aromatic rings may
alternatively be alike or unlike M1, M2 by a group
-M1-C(R).dbd.C(R)-M2 or -M1-C(=Z)-M2- and be selected from the
group --O--, --S--, --NR--.
[0077] The substituents A, B, K, D, E, F, G, H of the compounds 14
and 15 may be unlike or alternatively alike and assume the
following structures, imionitrogen .dbd.N--, phosphine .dbd.P-- or
the substituted methylene carbon .dbd.C.dbd.R.sup.1-8.
[0078] It is understood that in all compounds according to the
invention, a plurality or all N atoms may in each instance be
replaced by P atoms.
[0079] In particular, the following compounds with the following
substitution patterns may be used according to the invention:
[0080] The compounds 1, 2, 3(m=0), 3(m=1), 3(m=3), 3(m=4), 3b(m=1),
3b(m=2), 3b(m=3), 3b(m=4), 3c(m=1), 3c(m=2), 3c(m=3), 3c(m=4), 6,
7, 10, 11, 11a, 14, 15, 16, 17, 18, 19, 20, 21 (for M unlike
.dbd.C=Z), 26 (for M unlike .dbd.C=Z), 27 (for M like --O--, --S--,
--NR-- or .dbd.C=Z with Z=S1, S2, S3, S4, S5, S6, S7, S8, S9, S10,
S11, S12, S13, S14, S15, S16, S17, S18, S19, S20 or S21), 28 (for
U.dbd.S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13, S14,
S15, S16, S17, S18, S19, S20 or S21), 30 (with M equal to --O--,
--S--, --NR-- or .dbd.C=T with T.dbd.S1, S2, S3, S4, S5, S6, S7,
S8, S8, S10, S11, S12, S13, S14, S15, S16, S17, S18, S19, S20 or
S21), 32, 33 have the following concrete substitution patterns in
each instance, where to each one of the compounds in succession is
assigned the substituent X of a first line and the substituent Y
below it of the following line
[0081] with X and Y in each instance as follows:
[0082] X: S1, S1, S1, S1, S1, S1, S1, S1, S1, S1, S1, S1, S1, S
[0083] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0084] X: S1, S1, S1, S1, S1, S1, S1
[0085] Y: S15, S16, S17, S18, S19, S20, S21
[0086] or with X and Y in each instance as follows:
[0087] X: S2, S2, S2, S2, S2, S2, S2, S2, S2, S2, S2, S2, S2,
S2
[0088] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0089] X: S2, S2, S2, S2, S2, S2, S2
[0090] Y: S15, S16, S17, S18, S19, S20, S21
[0091] or with X and Y in each instance as follows:
[0092] X: S3, S3, S3, S3, S3, S3, S3, S3, S3, S3, S3, S3, S3,
S3
[0093] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12,S13,
S14
[0094] X: S3, S3, S3, S3, S3, S3, S3
[0095] Y: S15, S16, S17, S18, S19, S20, S21
[0096] or with X and Y in each instance as follows:
[0097] X: S4, S4, S4, S4, S4, S4, S4, S4, S4, S4, S4, S4, S4,
S4
[0098] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0099] X: S4, S4, S4, S4, S4, S4, S4
[0100] Y: S15, S16, S17, S18, S19, S20, S21
[0101] Or with X and Y in each instance as follows:
[0102] X: S5, S5, S5, S5, S5, S5, S5, S5, S5, S5, S5, S5, S5,
S5
[0103] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0104] X: S5, S5, S5, S5, S5, S5, S5
[0105] Y: S15, S16, S17, S18, S19, S20, S21
[0106] Or with X and Y in each instance as follows:
[0107] X: S6, S6, S6, S6, S6, S6, S6, S6, S6, S6, S6, S6, S6,
S6
[0108] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0109] X: S6, S6, S6, S6, S6, S6, S6
[0110] Y: S15, S16, S17, S18, S19, S20, S21
[0111] Or with X and Y in each instance as follows:
[0112] X: S7, S7, S7, S7, S7, S7, S7, S7, S7, S7, S7, S7, S7,
S7
[0113] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0114] X: S7, S7, S7, S7, S7, S7, S7
[0115] Y: S15, S16, S17, S18, S19, S20, S21
[0116] Or with X and Y in each instance as follows:
[0117] X: S8, S8, S8, S8, S8, S8, S8, S8, S8, S8, S8, S8, S8,
S8
[0118] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0119] X: S8, S8, S8, S8, S8, S8, S8
[0120] Y: S15, S16, S17, S18, S19, S20, S21
[0121] Or with X and Y in each instance as follows:
[0122] X: S9, S9, S9, S9, S9, S9, S9, S9, S9, S9, S9, S9, S9,
S9
[0123] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0124] X: S9, S9, S9, S9, S9, S9, S9
[0125] Y: S15, S16, S17, S18, S19, S20, S21
[0126] Or with X and Y in each instance as follows:
[0127] X: S10, S10, S10, S10, S10, S10, S10, S10, S10, S10, S10,
S10
[0128] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0129] X: S10, S10, S10, S10, S10, S10, S10, S10, S10
[0130] Y: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0131] or with X and Y in each instance as follows:
[0132] X: S11, S11, S11, S11, S11, S11, S11, S11, S11, S11, S11,
S11
[0133] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0134] X: S11, S11, S11, S11, S11, S11, S11, S11
[0135] Y: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0136] or with X and Y in each instance as follows:
[0137] X: S12, S12, S12, S12, S12, S12, S12, S12, S12, S12, S12,
S12
[0138] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0139] X: S12, S12, S12, S12, S12, S12, S12, S12
[0140] Y: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0141] or with X and Y in each instance as follows:
[0142] X: S13, S13, S13, S13, S13, S13, S13, S13, S13, S13, S13,
S13
[0143] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0144] X: S13, S13, S13, S13, S13, S13, S13, S13
[0145] Y: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0146] or with X and Y in each instance as follows:
[0147] X: S14, S14, S14, S14, S14, S14, S14, S14, S14, S14, S14,
S14
[0148] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0149] X: S14, S14, S14, S14, S14, S14, S14, S14
[0150] Y: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0151] or with X and Y in each instance as follows:
[0152] X: S15, S15, S15, S15, S15, S15, S15, S15, S15, S15, S15,
S15
[0153] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0154] X: S15, S15, S15, S15, S15, S15, S15, S15
[0155] Y: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0156] or with X and Y in each instance as follows:
[0157] X: S16, S16, S16, S16, S16, S16, S16, S16, S16, S16, S16,
S16
[0158] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0159] X: S16, S16, S16, S16, S16, S16, S16, S16
[0160] Y: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0161] or with X and Y in each instance as follows:
[0162] X: S17, S17, S17, S17, S17, S17, S17, S17, S17, S17, S17,
S17
[0163] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0164] X: S17, S17, S17, S17, S17, S17, S17, S17
[0165] Y: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0166] or with X and Y in each instance as follows:
[0167] X: S18, S18, S18, S18, S18, S18, S18, S18, S18, S18, S18,
S18
[0168] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0169] X: S18, S18, S18, S18, S18, S18, S18, S18
[0170] Y: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0171] or with X and Y in each instance as follows:
[0172] X: S19, S19, S19, S19, S19, S19, S19, S19, S19, S19, S19,
S19
[0173] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0174] X: S19, S19, S19, S19, S19, S19, S19, S19
[0175] Y: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0176] or with X and Y in each instance as follows:
[0177] X: S20, S20, S20, S20, S20, S20, S20, S20, S20, S20, S20,
S20
[0178] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0179] X: S20, S20, S20, S20, S20, S20, S20, S20
[0180] Y: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0181] or with X and Y in each instance as follows:
[0182] X: S21, S21, S21, S21, S21, S21, S21, S21, S21, S21, S21,
S21
[0183] Y: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0184] X: S21, S21, S21, S21, S21, S21, S21, S21
[0185] Y: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0186] The compounds 4, 5, 5b, 5c, 8, 9, 12, 21 (where 2 residues M
are equal to V and W), 22, 23, 24, 24a, 24b, 25 and 26 (for M
unlike .dbd.C=Z), 27 (for M unlike .dbd.C=Z), 29, 31 have the
following concrete substitution patterns in each instance, where to
each one of the compounds in succession is assigned the substituent
X of a first line and the substituent V below it of the following
line, as indicated at the beginning of the line in each
instance.
[0187] with X .dbd.Y and V .dbd.W
[0188] and with X and V as follows:
[0189] X: S1, S1, S1, S1, S1, S1, S1, S1, S1, S1, S1, S1, S1,
S1
[0190] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0191] X: S1, S1, S1, S1, S1, S1, S1
[0192] V: S15, S16, S17, S18, S19, S20, S21
[0193] or with X and V as follows:
[0194] X: S2, S2, S2, S2, S2, S2, S2, S2, S2, S2, S2, S2, S2,
S2
[0195] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0196] X: S2, S2, S2, S2, S2, S2, S2
[0197] V: S15, S16, S17, S18, S19, S20, S21
[0198] or with X and V as follows:
[0199] X: S3, S3, S3, S3, S3, S3, S3, S3, S3, S3, S3, S3, S3,
S3
[0200] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0201] X: S3, S3, S3, S3, S3, S3, S3
[0202] V: S15, S16, S17, S18, S19, S20, S21
[0203] or with X and V as follows:
[0204] X: S4, S4, S4, S4, S4, S4, S4, S4, S4, S4, S4, S4, S4,
S4
[0205] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0206] X: S4, S4, S4, S4, S4, S4, S4
[0207] V: S15, S16, S17, S18, S19, S20, S21
[0208] or with X and V as follows:
[0209] X: S5, S5, S5, S5, S5, S5, S5, S5, S5, S5, S5, S5, S5,
S5
[0210] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0211] X: S5, S5, S5, S5, S5, S5, S5
[0212] V: S15, S16, S17, S18, S19, S20, S21
[0213] or with X and V as follows:
[0214] X: S6, S6, S6, S6, S6, S6, S6, S6, S6, S6, S6, S6, S6,
S6
[0215] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0216] X: S6, S6, S6, S6, S6, S6, S6
[0217] V: S15, S16, S17, S18, S19, S20, S21
[0218] or with X and V as follows:
[0219] X: S7, S7, S7, S7, S7, S7, S7, S7, S7, S7, S7, S7, S7,
S7
[0220] V: S1,S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0221] X: S7, S7, S7, S7, S7, S7, S7
[0222] V: S15, S16, S17, S18, S19, S20, S21
[0223] or with X and V as follows:
[0224] X: S8, S8, S8, S8, S8, S8, S8, S8, S8, S8, S8, S8, S8,
S8
[0225] V: S1,S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0226] X: S8, S8, S8, S8, S8, 8, S8
[0227] V: S15, S16, S17, S18, S19, S20, S21
[0228] or with X and V as follows:
[0229] X: S9, S9, S9, S9, S9, S9, S9, S9, S9, S9, S9, S9, S9,
S9
[0230] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12, S13,
S14
[0231] X: S9, S9, S9, S9, S9, S9, S9
[0232] V: S15, S16, S17, S18, S19, S20, S21
[0233] or with X and V as follows:
[0234] X: S10, S10, S10, S10, S10, S10, S10, S10, S10, S10, S10,
S10
[0235] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0236] X: S10, S10, S10, S10, S10, S10, S10, S10, S10
[0237] V: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0238] or with X and V as follows:
[0239] X: S11, S11, S11, S11, S11, S11, S11, S11, S11, S11, S11,
S11
[0240] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0241] X: S11, S11, S11, S11, S11, S11, S11, S11
[0242] V: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0243] or with X and V as follows:
[0244] X: S12, S12, S12, S12, S12, S12, S12, S12, S12, S12, S12,
S12
[0245] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0246] X: S12, S12, S12, S12, S12, S12, S12, S12
[0247] V: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0248] or with X and V as follows:
[0249] X: S13, S13, S13, S13, S13, S13, S13, S13, S13, S13, S13,
S13
[0250] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0251] X: S13, S13, S13, S13, S13, S13, S13, S13
[0252] V: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0253] or with X and V as follows:
[0254] X: S14, S14, S14, S14, S14, S14, S14, S14, S14, S14, S14,
S14
[0255] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0256] X: S14, S14, S14, S14, S14, S14, S14, S14
[0257] V: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0258] or with X and V as follows:
[0259] X: S15, S15, S15, S15, S15, S15, S15, S15, S15, S15, S15,
S15
[0260] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0261] X: S15, S15, S15, S15, S15, S15, S15, S15
[0262] V: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0263] or with X and V as follows:
[0264] X: S16, S16, S16, S16, S16, S16, S16, S16, S16, S16, S16,
S16
[0265] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0266] X: S16, S16, S16, S16, S16, S16, S16, S16
[0267] V: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0268] or with X and V as follows:
[0269] X: S17, S17, S17, S17, S17, S17, S17, S17, S17, S17, S17,
S17
[0270] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0271] X: S17, S17, S17, S17, S17, S17, S17, S17
[0272] V: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0273] or with X and V as follows:
[0274] X: S18, S18, S18, S18, S18, S18, S18, S18, S18, S18, S18,
S18
[0275] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0276] X: S18, S18, S18, S18, S18, S18, S18, S18,
[0277] V: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0278] or with X and V as follows:
[0279] X: S19, S19, S19, S19, S19, S19, S19, S19, S19, S19, S19,
S19
[0280] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0281] X: S19, S19, S19, S19, S19, S19, S19, S19, S19
[0282] V: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0283] or with X and V as follows:
[0284] X: S20, S20, S20, S20, S20, S20, S20, S20, S20, S20, S20,
S20
[0285] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0286] X: S20, S20, S20, S20, S20, S20, S20, S20, S21
[0287] V: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0288] or with X and V as follows:
[0289] X: S21, S21, S21, S21, S21, S21, S21, S21, S21, S21, S21,
S21
[0290] V: S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11, S12
[0291] X: S21, S21, S21, S21, S21, S21, S21, S21, S21
[0292] V: S13, S14, S15, S16, S17, S18, S19, S20, S21
[0293] The invention in addition comprises the said compounds 4, 5,
5b, 5c, 8, 9, 12, 21 (where 2 residues M are equal to V and W), 22,
23, 24, 24a, 24b, 25 and 26 (for M unlike .dbd.C =Z), 27 (for M
unlike .dbd.C =Z), 29, 31 when for the substituents X.dbd.V and
Y.dbd.W with the concrete substitution patterns when in the tables
mentioned above V is replaced by Y for these compounds and when to
each one of the compounds in succession is assigned the substituent
X of a first line and the substituent Y below it of the following
line.
[0294] The invention in addition comprises the said compounds 4, 5,
5b, 5c, 8, 9, 12, 21 (where 2 residues M are equal to V and W), 22,
23, 24, 24a, 24b, 25, and 26 (for M unlike .dbd.C=Z), 27 (for M
unlike .dbd.C=Z), 29, 31 when for the substituents X.dbd.W and
Y.dbd.V with the concrete substitution patterns when to each one of
the compounds following is assigned the substituent X of a first
line and the substituent Y below it of the following line.
[0295] In the compounds 21, 25 and 26 both residues may here be
alike or independent of one another: --S--, --O--, --NR-- or
.dbd.C=Z with Z.dbd.S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11,
S12, S13, S14, S15, S16, S17, S18, S19, S20 or S21.
[0296] The residues R.sup.1 to R.sup.32 may be alike or unlike and
be selected from the group consisting of hydrogen, halogen, (in
particular --F, --C1), cyano, nitro, nitroso, sulfamide
(unsubstituted or substituted, in particular C1-C6 mono or dialkyl
substituted), carboxy, C1-C7 carbalkoxy, C1-C7 sulfo, sulfohalogen
(in particular --F or --C1), halogen carbonyl (in particular --F or
--C1), carbamoyl (unsubstituted or substituted, in particular C1-C6
N monosubstituted or alike or independently of one another N--C1-C6
disubstituted), formyl, amidineformyl, C1-C6 alkylsulfanyl, C1-C6
alkylsulfonyl, C1-C25 hydrocarbon, preferably C1-C14 hydrocarbon or
C1 to C10 or C1 up to 6 hydrocarbon, where one or more or all of
the carbon atoms of the group may be substituted with one or more
of the above-mentioned residues, where the hydrocarbon may be
saturated, unsaturated or an aromatic hydrocarbon. The hydrocarbon
groups may in each instance in particular be perhalogenated,
perchlorinated or perfluorinated (in particular trifluoromethyl).
The hydrocarbon groups may be linear or branched or cyclic, for
example cyclohexyl or cyclopentyl. One or more carbon atoms may in
each instance be replaced by heteroatoms, in particular N, O, S,
--(O)S(O)-- or P(R). The (hetero) hydrocarbon residues may be
cyclically linked with one another or with a quinoid or other ring,
for example a (hetero)aryl ring.
[0297] In particular, the residues R.sup.1 to R.sup.32 may be one
of the groups acetyl-, trifluoroacetyl-, benzoyl-,
pentafluorobenzoyl-, naphthoyl- or alkoxycarbonyl-, where the alkyl
residue may be an alkyl with one up to six or to ten, in particular
up to four, C atoms linked together unbranched or branched, as well
as trialkyl-phosphoryl with alkyl residues, which likewise may
consist of a chain with up to five or six or eight carbon atoms
linked together unbranched or branched or cyclically or
triarylphosphoryl with aryl residues with preferably 6 to 14 C
atoms, in particular up to 10 C atoms. In addition, the residues
R.sup.1-R.sup.32, which may be alike or unlike, may be either aryl
or heteroaryl, such as for example phenyl, naphthyl, anthranyl,
pyridyl, quinoxalyl, pyrazoyl, oxazolyl, 1,3,2-dioxaborinyl or
1,3,4 oxdiazolyl, which may be substituted either by hydrogen or an
aryl of low molecular weight with one to eight saturated carbon
atoms, which may be linked together unbranched or branched or
cyclically, preferably however by halogen, primarily fluorine or
chlorine, trichloromethyl, perfluoroalkyl with one to six carbon
atoms, in particular trifluoromethyl, but alternatively by cyano,
nitro, nitroso, sulfo, carboxyl, carbalkoxy, halogen carbonyl,
carbamoyl, formyl, amidineformyl, alkylsulfanyl and alkylsulfonyl,
where here again the alkyl residues may consist of a chain with up
to five or six or up to eight carbon atoms linked together
unbranched or branched or cyclically, as well as by
trialkylphosphoryl with alkyl residues, which likewise may consist
of a chain with up to five or six or up to eight carbon atoms
linked together unbranched or branched. In particular, the aryl or
heteroaryl residues may be perhalogenated, in particular
perfluorinated.
[0298] The residues R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 in
the compounds 3, 3b, 3c or formulas IV, V or VI may be alike or
unlike for unlike n or m.
[0299] The residues R.sup.1 to R.sup.32, which are linked with a
quinoid or aromatic system of a compound used according to the
invention and are arranged adjacent to one another and are
separated by two, three or four atoms of the quinoid or aromatic
skeletal structure, may be linked together with formation of a
carbocyclic, in particular aromatic ring, or heterocyclic, in
particular heterocarbocyclic ring. This applies in particular to
the compounds 1 to 33, but alternatively to other quinones or
quinone derivatives used according to the invention. This applies
for example pairwise in each instance, alternatively or
simultaneously to the residues R.sup.1, R.sup.2 and/or R.sup.3,
R.sup.4 of the compounds 1, 3, 3b, 7, 8, 9, 10, 11, 12, 23, 24, 25,
27, 28, the residues R.sup.1, R.sup.2; R.sup.2, R.sup.3; R.sup.4,
R.sup.5 and/or R.sup.5, R.sup.6 of compound 2, the residues
R.sup.1, R.sup.2; R.sup.3, R.sup.4; R.sup.5, R.sup.6; R.sup.7,
R.sup.8 of compound 3, the residues R.sup.5, R.sup.6; R.sup.7,
R.sup.8 of compounds 28, 29 or others. The bridging groups of atoms
may in particular form a group that is selected from
[0300] -L.sup.1-C(R.sup.1).dbd.C(R2)-L with L=0, S, NR or
CR.sup.14R.sup.15,
[0301] or --C(X)C(Y)--C(R.sup.1).dbd.C(R.sup.2).dbd.
[0302] or --C(.dbd.X)C(R.sup.3).dbd.C(R.sup.4)--C(.dbd.Y)--
[0303] or --C(.dbd.X)-L-C(.dbd.Y) with L=0, S, NR,
CR.sup.14R.sup.15
[0304] with X and Y as defined above and preferably selected from
the group 14
[0305] where the residues R.sup.13 of the various groups may be
unlike. The bridging groups of atoms may in particular be provided
when X and/or Y are=0 or =8 or .dbd.C(CN).sub.2. In particular, L
may then be -0- or -8- or --NR--.
[0306] However, every two adjacent residues from R.sup.1-R.sup.32
may alternatively be linked together by a carboxy --(CO)-- or a
carbimide group --(CNR)--, where the analogous substitution pattern
applies for this R as for R.sup.1-R.sup.30. However, it is
alternatively possible that two adjacent residues R are linked
together by carbon atoms or heteroatoms in such a way that a new
carbocyclic or heterocyclic element is fused to the respective
basic cyclic skeleton. For example, in compound type 1 the residues
R.sup.1 and R.sup.2 as well as R.sup.3 and R.sup.4 stand for a
fused benzo or naphtho residue, but alternatively for a fused
thiophene, furan, 1,3,4-oxdiazole, pyridine, pyrazine, triazine,
tetrazine, pyrane, thiopyrane, dithiine, phosphorine, phthalic acid
anhydride, phthalic acid imide or dithiazole residue, where these
residues again may be exclusively or partially substituted by
additional electron-attracting groupings, such as halogen,
including preferably fluorine or chlorine, trifluoromethyl or
cyano, nitro, nitroso, sulfo, carboxy, carbalkoxy, halogen
carbonyl, carbamoyl, formyl, amidineformyl. The same applies,
mutatis mutandis, to the residues R.sup.1 and R.sup.2 or R.sup.2
and R.sup.3 or for the residues R.sup.4 and R.sup.5 or R.sup.5 and
R.sup.6 in compound type 2 as well as to the residues R.sup.1 and
R.sup.2, R.sup.3 and R.sup.4, R.sup.5 and R.sup.6 as well as
R.sup.7 and R.sup.8 in compound type 3, as well as to the residues
R.sup.2 and R.sup.3 or R.sup.5 and R.sup.6 in the compound types 4
and 5, as well as to the corresponding pairs of residues R of the
other compounds, which are close enough together to form a 5 or
6-membered ring.
[0307] The bridged trans-diketo form of compound 8 may for example
result in the structures 28 or 29. In the formula 26 the carboxylic
acid anhydride acid may alternatively be replaced by a substituted
nitrogen group .dbd.N--R.sup.1 and hence form a carboxylic acid
imide structure.
[0308] The aromatic residues, with which the quinoid systems may be
substituted and/or anellated, may be perhalogenated, in particular
perfluorinated, perchlorinated or perfluorochlorinated. Optionally
a number, for example up to one-half or more, of the halogen atoms
may be replaced by hydrogen. The same may also alternatively or
simultaneously apply to the residues R of the quinoid systems.
Instead of halogen atoms, CN groups may alternatively be provided
on the aromatic residues and/or the quinoid systems.
[0309] Two quinoid systems Ch1 and Ch2 may in each instance be
linked together with formation of a compound Ch1-ZB--Ch2 by a
residue ZB, where the quinoid residues Ch1 and Ch2 may be linked
together mesomerically or be mesomerically independent of one
another. The quinoid residues Ch1 and Ch2 may be alike or unlike
and may be selected from the group of compounds 1 to 4 and 5 to 33,
while optionally additional quinoid systems may alternatively be
linked together, for example with formation of structures such as
Ch1-ZB1-Ch2-35 ZB2-Ch3, where Ch1, Ch2, Ch3 may be alike or unlike
and may in each instance represent the compounds 1 to 4 and 5 to
33, without being limited thereto. ZB 1 and ZB2 may be alike or
unlike.
[0310] The bridges -Z- may have 1, 2 to 4, up to 6 or up to 10 or
alternatively more bridge atoms, which may be carbon atoms or at
least in part heteroatoms.
[0311] When two quinoid compounds, as in formulas 5, 5b or 5c, are
linked together by a residue Z, this bridge -Z- may consist of
alkenylene, haloalkenylene, acetylene, alkylene, haloalkylene, in
particular perfluoroalkylene with one to eight saturated carbon
atoms, which may be linked together unbranched or branched, or of
arylene, hetarylene, which may be substituted either with hydrogen
or with alkyl residues of low molecular weight with one to six or
up to eight saturated carbon atoms, which may be linked together
unbranched or branched or cyclically, preferably however with
halogen, primarily fluorine or chlorine, trichloromethyl,
perfluoroalkyl with one to six carbon atoms, there in particular
trifluoromethyl, but alternatively cyano, nitro, nitroso, sulfo,
carboxy, carbalkoxy, halocarbonyl, carbamoyl, formyl,
amidineformyl, alkylsulfanyl and alkylsulfonyl, where the alkyl
residues here again may consist of a chain with up to eight carbon
atoms linked together unbranched or branched or cyclically, as well
as trialkylphosphoryl with alkyl residues, which likewise consist
of a chain with up to eight carbon atoms linked together unbranched
or branched, may be substituted. The alkenylene group and the
alkylene group may have one or more multiple C--C bonds. The bridge
atoms of group Z may consist only of unsaturated carbon atoms or
heteroatoms, where the said groups may be unsubstituted or
substituted. The bridge atoms of group Z may consist only of
saturated or aromatic carbon or heteroatoms, while the said groups
may be unsubstituted or substituted, so that the two quinoid
systems may be mesomerically linked together.
[0312] The bridge -Z- may comprise one or more groups, in
particular the groups below in the form -(Z)n-, for example with n
equal to 1, 2, 3 or 4 or more, which in each instance may be alike
or unlike one another.
[0313] Z may be selected from the group consisting of 15
[0314] and/or selected from the group consisting of 16
[0315] and/or selected from the group consisting of 17
[0316] where the bridges indicated alternatively include
substituted bridges such as for example --NR--, --(C.dbd.X)--,
--CR1=CR2-, and/or selected from the group consisting of carboxy
--(CO)--, carbimide --(CNR)--, thiophenylene, furanylene
1,3,4,-oxdiazolylene, triazine, tetrazinylene, pyranylene,
thiopyranylene, dithiinylene, phosphorinylene, phthalic acid
anhydride, phthalic acid imide and dithiazole residues.
[0317] The aromatic rings or carbon or heterobridges indicated may
in each instance be substituted or unsubstituted. X may be a singly
or doubly substituted carbon atom, a singly substituted nitrogen
atom or =0 or .dbd.S, preferably selected from one of the groups or
subgroups listed above.
[0318] The residues R.sup.1 and R.sup.2 may be unlike the residues
R.sup.1 and R.sup.2 of the basic structures of compounds 1 to
33.
[0319] In addition, it is possible for the two quinoid structures
to be linked together directly in any way.
[0320] Preparation of Quinoid Structures
[0321] All syntheses of quinoid compounds described below are
hereby fully included in the present invention by reference thereto
and are covered by it.
[0322] The corresponding substitution patterns are frequently
produced in the product to be oxidized. 1,4-quinones may best be
prepared by oxidation of the corresponding hydroquinone (W. T.
Sumerford, D. N. Dalton, J. Am. Chem. Soc. 1944, 66, 1330; J.
Miller, C. Vasquez, 1991 Patent US506836; K. Koch, J. Vitz, J.
Prakt. Chem. 2000, 342/8825-7) or the fluorinated and/or
chlorinated aromatic compounds (A. Roedig et al., Chem. B. 1974,
107, 558-65; 0. T. Osina, V. D. Steingarz, Zh. Org. Chem. 1974, 10,
329; V. D. Steingarz et al., Zh. Org. Chim. 1970, 6/4, 833).
[0323] 1,3-indanedione compounds have been synthesized by V.
Khodorkovsky et al. (V. Khodorkovsky et al., Tetrahedron Lett.
1999, 40,4851-4).
[0324] N,N'-dicyano-1,4-quinonediimines are accessible either by
the action of N,N'-bistrimethylsilylcarbodiimide on 1,4-quinone
compounds (A. Aumuller, S. Hunig, Liebigs Ann. Chem., 1986, 142-64)
or by oxidation of appropriate N,N'-dicyano-1,4-diamine compounds
(G. D. Adreetti , S. Bradamante, P. C. Pizzarri, G. A. Pagani, Mol.
Cryst. Liq. Cryst. 1985, 120, 309-14), where the
N,N'-dicyano-1,4-diamine compounds may be obtained by cyanization
of phenylene-1,4-diamine with cyanohalogenides or by
desulfurization of corresponding thiourea derivatives.
[0325] Simple tetracyanoquinone dimethanes may be prepared via
1,4-cyclo-hexanedione by condensation in benzene with ammonium
acetate buffer on the water separator and subsequent oxidation by
bromine (D. S. Acker, W. R. Hertler, J. Am. Chem. Soc. 1962, 84,
3370). In addition, Hertler and co-workers showed that these
compounds are capable of being synthesized via 1,4-xylene and its
analogs by side-chain bromination, substitution by means of
cyanide, condensation with carbonic diethyl ester, conversion of
the carboxylic acid methyl ester groupings to cyanide groups and
then oxidation (J. Org. Chem. 1963, 28, 2719).
[0326] Acceptor-substituted tetracyanoquinonedimethanes may be
prepared from the sodium salt of t-butyl-malonic acid dinitrile and
acceptor-substituted 1,4-dihalogen aromatic compounds (R. C.
Wheland, E. L. Martin, J. Org. Chem., 1975,40,3101).
[0327] In addition, tetracyanoquinonedimethanes have been prepared
from 1,4-dihalogen aromatic compounds Pd-catalyzed with
malodinitrile anion and subsequent oxidation (S. Takahashi et al.,
Tetrahedron Letters, 1985, 26, 1553).
[0328] Chinoide 1,4-polyphenylene E. A. Shalom, J. Y. Becker, I.
Agranat, Nouveau Journal de Chimie 1979, 3, 643-5.
[0329] Heteroanellated quinones have been prepared by the
multiple-step synthesis pathway. (B. Skibo et al., J. Med. 1991,
34, 2954-61; H. Bock, P. Dickmann, H. F. Herrmann, Z. Naturforsch.
1991, 46b, 326-8, J. Druey, P. Schmidt, Helv. Chim. Acta 1950, 140,
1080-7).
[0330] Bridged quinoid compounds have been prepared by M. Matstoka,
H. Oka, T. Kitao, Chemistry Letters, 1990, 2061-4; J. Dieckmann, W.
R. Hertler, R. E. Benson, J. A. C. S. 1963, 28, 2719-24; K.
Takahashi, S. Tarutani, J. C. S. Chem. Comm. 1994, 519-20; N. N.
Woroschzov, W. A. Barchasch, Doklady Akad. SSSR 1966, 166/3,
598.
[0331] Anellated TCNQ compounds have been prepared by M. Matsuoka,
H. Oka, T. Kitao, Chemistry Letters, 1990, 2061-4; B. S. Ong, B.
Koeshkerian, J. Org. Chem. 1984, 495002-3.
[0332] Pyrazino-TCNQ compounds may be prepared via
5,8-diiodoquinoxalines palladium-catalyzed with the sodium salt of
malodi nitril. (T. Miyashi et al., J. Org. Chem. 1992, 57,
6749-55).
[0333] Pyrazino-TCNQ compounds as well as other heteroanellated
derivatives may be prepared in a variety of ways (Y. Yamashita et
al., Chemistry Letters, 1986, 715-8, F. Wudl et al., J. Org. Chem.
1977, 421, 666-7).
[0334] Anellated DCNQI compounds may be synthesized via the
corresponding quinones according to Hunig (J. Tsunetsuga et al.,
Chemistry Letters, 2002, 1004-5).
[0335] Heteroanellated DCNQI compounds may be synthesized via the
corresponding quinones according to Hunig (T. Suzuki et al., J.
Org. Chem. 2001, 66, 216-24; N. Martin et al., J. Org. Chem. 1996,
61, 3041-54; K. Kobayashy et al., Chemistry Letters, 1991, 1033-6;
K. Kobayashy, K. Takahashi, J. Org. Chem. 2000, 65, 2577-9).
[0336] Heterocyclic quinoid derivatives may be prepared according
to N. F. Haley, J. C. S. Chem. Comm. 1979, 1031, F. Weyland, K.
Henkel Chem. B. 1943, 76, 818; H. J. Knackmuss, Angew. Chem. 1973,
85, 16; K. Fickentscher, Chem. B. 1969, 102, 2378-83, D. E. Burton
et al., J. Chem. Soc. (C) 1968, 1268-73.
[0337] Quinoid structures with unlike residues X, Y have been
synthesized by a variety of working groups (T. Itoh, N. Tanaka, S.
Iwatsuki, Macromolecules 1995, 28, 421-4; J. A. Hyatt, J. Org.
Chem. 1983, 48 129-31; M. R. Bryce et al., J. Org. Chem. 1992, 57,
1690-6; A. Schonberg, E. Singer, Chem. Ber. 1970, 103, 3871-4; S.
Iwatsuki, T. Itoh, H. Itoh, Chemistry Letters, 1988, 1187-90; T.
Itoh, K. Fujikawa, M. Kubo, J. Org. Chem. 1996, 61, 8329-31; S.
Iwatsuki, T. Itoh, T. Sato, T. Higuchi, Macromolecules, 1987, 20,
2651-4; T. Itoh et al., Macromolecule 2000, 33, 269-77; B. S. Ang,
B. Koeshkerian, J. Org. Chem. 1984, 495002-3; H. Junek, H. Hambock,
B. Hornischer, Mh. Chem. 1967, 98, 315-23; P. W. Pastors et al.,
Doklady Akad. SSSR 1972, 204, 874-5; A. R. Katritzky et al.,
Heterocyclic Chem. 1989, 26, 1541-5; N. N. Vorozhtsov, V. A.
Barkash, S. A. Anichkina, Doklady Akad. SSSR 1966, 166, 598).
[0338] Tetracetylquinonemethane compounds and their reduced forms
may be obtained via 1,4-benzoquinone and acetylacetone (J. Jenik,
Chemicky prumys. 198535/601547, R. J. Wikholm, J. Org. Chem. 1985,
50, 382-4; E. Bematek, S. Ramstad, Acta Chem. Scand. 1953, 7,
1351-6).
[0339] Ditrifluoroacetamides may be prepared by means of
trifluoroacetic acid via aromatic 1,4-diamines (R. Adams, J. M.
Stewart, J.A.C.S. 1952, 20, 3660-4). The dime may be obtained by
oxidation with Pb(IV)-acetate.
[0340] Additional diimide and amide structures have been prepared
by B. C. McKusick et al., J.A.C.S. 1958, 80, 2806-15.
Example 1
N,N'-Dicyano-2,5-dichloro-1,4-benzoquinonediimine
[0341] Suspend 3 units N,N'-dicyano-2,5-dichlorobenzene-1,4-diamine
in 200 units glacial acetic acid with stirring at 20.degree. C.,
add 13 units lead-(IV)-tetraacetate. Stir until all of the starting
material is oxidized. Suction off the precipitated yellow/brown
product and recrystallize in benzene. Yield: 64%, m.p.: 225.degree.
C.
Example 2
N,N'-Dicyano-2,3,5,6-tetrafluoro-1,4-benzoquinonediimine
[0342] 1.5 units 2,3,5,6-tetrafluoro-1,4-benzoquinone are reacted
with 7.6 units titanium tetrachloride in 70 units methylene
dichloride. The yellow complex formed is brought to reaction with
7.5 units bis-(trimethylsilyl)-carbodiimide in 15 units methylene
dichloride with stirring at room temperature and after 4 h is
placed on ice. The aqueous phase is extracted twice with methylene
dichloride. The combined organic phases are dried with magnesium
chloride, filtered, concentrated to small volume under vacuum and
precipitated with petroleum ether and suctioned off anew. The solid
obtained is recrystallized in a mixture of
toluene/methylcyclohexane. Yield: 48%, m.p.: 205.degree. C.
1,3,2-Dioxaborines
[0343] In addition, according to the invention, 1,3,2-dioxaborine
compounds may be used for doping semiconducting organic
materials.
[0344] The 1,3,2-dioxaborine compounds used according to the
invention may have the general formula L 18
[0345] wherein A is a bivalent residue, which may have one or more
carbon atoms, which may be partially or completely replaced by
heteroatoms, where m=0 or is a whole number greater than 0, for
example 1, 2, 3, 4, 5, 6 or greater, for example up to 10 or up to
20, and where X is a monodentate ligand, or two ligands X together
may form a bidentate ligand. Here the bridge Am may have up to 6,
up to 10 or up to 20 bridge atoms, which link the two
1,3,2-dioxaborine rings together, while the bridge atoms may in
particular be carbon atoms and/or heteroatoms.
[0346] The 1,3,2-dioxaborine compound/s used according to the
invention may have the general formula L1 19
[0347] where Q is a trivalent residue and where X is a monodentate
ligand or where two ligands X together form a bidentate ligand.
[0348] In addition, the 1,3,2-dioxaborine compounds used according
to the invention may have the general formula LII 20
[0349] which represents a sub-case of the formula L with m=0, where
the two 1,3,2-dioxaborines however are linked together
mesomerically.
[0350] In particular, the 1,3,2-dioxaborines proposed here as
dopants may have the general formulas 30-33 21
[0351] where in the formulas the various X and/or R1 to R3 may in
each instance be alike or unlike one another.
[0352] The symbols indicated signify the following:
[0353] the residues X, a monodentate ligand with a preferably
electronegative trapped atom, such as for example fluorine, alkoxy,
acyloxy, aryloxy or aroyloxy, a bidentate ligand whose trapped
atoms preferably represent oxygen, which via a bridge are linked
together with unlike groupings of atoms and a variable number of
bridge atoms, while preferably a 5 or 6-membered ring is produced
by the bridge, at least one atom or all atoms of the bridge
preferably being a carbon atom,
[0354] the residues R.sup.1-R.sup.6, which in each instance may be
independent of one another, either hydrogen, a hydrocarbon group,
which optionally may have one or more heteroatoms, in particular an
alkyl or cycloalkyl group, which advantageously may be substituted
partially or completely by fluorine or chlorine, in particular
perhalogenated, especially preferably perfluorinated, and
preferably consists of one to six or eight or ten carbon atoms
(preferably a maximum of ten carbon atoms), which are linked
together either branched or unbranched, an unsubstituted or
substituted aryl group Ar, including a heteroaryl group, which
likewise may advantageously be substituted by halogen, in
particular fluorine or chlorine, in particular perhalogenated, in
particular perfluorinated, but alternatively together, in adjacent
position to the 1,3,2-doxaborine skeleton with the carbon atoms
linking them, may form an aromatic, heteroaromatic or nonaromatic
molecular fragment, such as for example a benzo-, naphtho-,
anthraceno-, thieno-, furano-, benzothiopheno-, benzofurano-,
indolo-, carbazolo, quinolino-, tetrahydronaphtho- or
tetrahydroquinolino- fragment, where these fragments may in very
flexible fashion be substituted by halogens, such as fluorine or
chlorine, as well as by other heteroatom-containing groupings, such
as alkyoxy, aryloxy, dialkylamino or diarylamino groupings, the
grouping A, either a bond between the 1,3,2-dioxaborine residues or
alternatively a bridge with preferably up to ten atoms, where the
bridge may have carbon atoms or alternatively heteroatoms such as
for example 0, N, S or P, and where the carbon atoms may be
replaced partially or completely by heteroatoms. The bridge may
optionally have a plurality of or exclusively unsaturated bridge
atoms. The bridge preferably represents, like Q, a molecular
fragment mediating conjugation between the 1,3,2-dioxaborine
residues, for example in that all atoms of the bridge are
unsaturated, the grouping Q, either a trivalent residue such as a
nitrogen or phosphorus atom, a trialkylene- or triarylene and
triheteroaryleneamido- or phosphorus group. The bridge before Q
preferably represents a molecular fragment mediating conjugation
between the 1,3,2-dioxaborine residues.
[0355] If the residues X in the compounds of formulas L, LI or LII,
in particular in compounds of formula types 30-33, represent a
bidentate ligand, they are preferably the residues of organic
dicarboxylic acids, such as in particular oxalic acid or malonic
acid, succinic acid and glutaric acid, where these dicarboxylic
acids, with the exception of the compounds first mentioned, may
however be substituted in their alkylene groupings by alkyl or aryl
groupings, the residues of aromatic dicarboxylic acids, such as
phthalic acid and its derivatives preferably substituted in the
ring by halogen, organic hydroxy acids, such as salicylic acid and
its ring-substituted derivatives,
1-hydroxy-naphthaline-2-carboxylic acid,
2-hydroxy-naphthaline-1-carboxyl- ic acid, mandelic acid, tartaric
acid, benzylic acid and its derivatives substituted in phenyl
residues with 1,2-dioxyarene or dioxyhetarene residues, which are
derived from catechol and its derivatives substituted in the ring
or fused by benzo residues, but alternatively from
3,4-dioxythiophenenes, or residues of cyclic oxodicarboxylic acids,
such as quadratic, croconic acid or the like.
[0356] The groupings A and Q, whose task preferably is the
production of conjugation between the individual 1,3,2-dioxaborine
residues linking them, may have a great multiplicity of structures
and preferably represent a bivalent or trivalent grouping of atoms,
such as oxygen, sulfur or nitrogen or a plurality of bivalent or
trivalent aryl grouping(s) linked together in conjugative fashion,
heteroaryl groupings(s), polyenyl or polymethinyl grouping(s),
where the respective groupings may however bear additional
substituents, which in particular may be alkyl groups with 1 to 10
carbon atoms, which in addition however may be substituted by
fluorine or chlorine, in particular perhalogenated or
perfluorinated, unsubstituted or preferably may be aryl or
heteroaryl groupings modified by fluorine or chlorine as well as by
electron-attracting substituents, where the heteroatoms in the last
preferably are oxygen, sulfur or nitrogen and may occur
individually as well as alternatively in combination with one
another, or else alternatively may be incorporated in suitable
bridge groupings, such as cycloalkylene groupings or their
heterocyclic analogs.
[0357] If A or Q symbolizes an aryl grouping, in the case of A the
latter advantageously is one or more of the groupings 34-36 and in
the case of Q one or optionally alternatively a plurality of the
groupings 37-39, where these may be substituted by customary
substituents, which preferably bear electronegative trapped atoms,
and in the fragments of type 36 the residues R.sup.5 and R.sup.6,
which may be alike or unlike, may be either hydrogen, alkyl or
fluorine as well as chlorine, but preferably alternatively may on
the whole be a carbon atom substituted by n-, iso- or cycloalkyl
groups with 1-10 C atoms, where in compound 35 or 39 n preferably
may be a whole number between 1 and 4. W may be a trivalent group
or a trivalent atom such as in particular N or P or the group 42,
without being limited thereto. 22
[0358] If A or Q symbolizes a hetaryl group, in the case of A this
preferably represents a grouping of the general formula 40 or 41,
where optionally in the group A introductions according to formulas
40 and 41 may alternatively occur combined, and in the case of Q a
grouping of the general formula 42, in which the residues R7 and R8
may be any desired substituents, such as for example alkyl, aryl or
heteroaryl as well as halogen or alkoxy, aryloxy, dialkylamino or
diarylamino, and the groupings Z1-Z6 may be bivalent heteroatoms,
such as preferably oxygen, sulfur or unsubstituted or substituted
nitrogen or phosphorus, and n may be a whole number, preferably
between 1 and 4 or 6, in particular 1, 2 or 3. 23
[0359] The compounds according to the present invention of types
30-33 also include those in which the aforesaid bridge groupings
may alternatively be found in combination with one another, such as
is the case for example for an oxybiphenylene or thiophenylene unit
as well as an aminotriphenylene unit, where linkage with the
respective 1,3,2-dioxaborine system in any desired position to the
heteroatom, preferably however in 1A-linkage, is possible. The
compounds according to the present invention include those in
which, in addition to the said bridge groupings A and Q, one of the
residues trapped in the 1,3,2-dioxaborine system is drawn into the
respective bridge grouping, so that compounds of the general
formulas 43-46 are produced, in which the groupings X and
R.sup.1-R.sup.3 have the meanings indicated above and R4 has the
meaning corresponding to the residues R.sup.1-R.sup.3. 24
[0360] The symbol K stands for a grouping that links the two
flanking 1,3,2-dioxaborine-containing molecular structures,
preferably links them together conjugatively, which for example is
possible by direct fusion of the two flanking groupings or with
incorporation of an aryl or hetaryl fragment.
[0361] The following compounds illustrate, in exemplary fashion,
the 1,3,2-dioxaborines usable according to the invention.
252627282930
[0362] The compounds 31f to i represent compound of formula type L
with m=O.
[0363] The compounds 30g, 31a to e and 31j represent compounds of
formula type L with m=1, where in the case of compound 31 b A is
--C(.dbd.CR1 R2)- and m is equal to 1, while in the case of
compounds 31 d and j A is --CR1.dbd.CR2- and m is equal to 1.
[0364] Compounds 32a and b represent compounds of formula type L
1.
[0365] Compounds 31 k to n and o, p represent compounds of formula
type LII.
Preparation of 1,3,2-dioxaborines
[0366] 1,4-Bis-(2,2-difluoro-4-methyl-1,3,2-dioxaborinyl)-benzole:
31
[0367] To a solution of 1,4-diacetylbenzole (0.01 mol) in acetic
hydride (50 mL) boron trifluoride etherate (10 mL) is added by
drops, at room temperature while stirring. After standing overnight
the precipitated solid is suctioned off and washed with ether. F.
293-298.degree. C.
[0368] 5,
7-Bismethoxy-2,2-difluoro-4-methyl-B-(2,2-difluoro-4-methyl-1,3,-
2-dioxaborinyl)-benzo[d]1,3,2-dioxaborine: 32
[0369] To a solution of 1,3,5-trimethoxybenzole (0.1 mol) in acetic
anhydride (0.9 mol), bortrifluoride/acetic acid (0.3 mol) is added
by drops at room temperature with stirring. After standing
overnight the precipitated solid is suctioned off, washed with
ether and recrystallized in toluene/nitromethane. F.
217-219.degree. C.
[0370]
2,2,7,7-Tetrafluoro-2,7-dihydro-1,3,6,B-doxa-2,7-diborapyrene:
33
[0371] 1 g 5,8-dihydroxy-1 A-naphthoquinone and 1.5 ml BF3 etherate
were heated in dry toluene for 2 h on a water bath while stirring.
After cooling to room temperature, a red-brown crystalline
precipitate was deposited, which may be recrystallized in dry
glacial acetic acid. F. 163-165.degree. C.
[0372] 2,2,7,
7-Tetrafluoro-2,7-dihydro-1,3,6,B-doxa-2,7-dibora-benzo[e]py- rene:
34
[0373] 10 g quinizarine and 10 mL BF3 etherate were heated in dry
toluene for 2 h on the water bath with stirring. After cooling to
room temperature a red-brown crystalline precipitate is deposited,
which may be recrystallized in dry glacial acetic acid. F.
249-251.degree. C.
[0374] 2,2,8, 8-Tetrafluoro-2,
8-dihydro-1,3,7,9-tetraoxa-2,8-diboraperyle- ne: 35
[0375] 10 g 1,5-dihydroxy-9,10-anthraquinone and 10 mL BF3 etherate
were heated in dry toluene for 2 h on the water bath with stirring.
After cooling to room temperature, a red crystalline precipitate is
deposited, which may be recrystallized in dry glacial acetic acid.
F. >35.degree. C.
[0376]
Tris-[4-(2,2-difluoro-4-methyl-1,3,2-dioxaborinyl)-phenylamine:
36
[0377] To a solution of triphenylamine (0.1 mol) in acetic
anhydride (0.9 mol), bortrifluoride/acetic acid (0.3mol) is added
by drops at room temperature with stirring. After standing
overnight, the precipitated solid is suctioned off, washed with
ether and recrystallized in glacial acetic acid/nitromethane. F.
305-307.degree. C.
[0378]
1,3,5-Tris-(2,2-difluoro-4-methyl-1,3,2-dioxaborinyl)-benzole:
37
[0379] To a mixture of acetic anhydride (0.6 mol) and
bortrifluoride-acetic acid (0.2 mol), 1,3,5-triacetylbenole (0.05
mol) was slowly added by drops, while stirring at 45.degree. C. The
resulting mixture is stirred for another 8 hrs and then allowed to
cool. The product precipitated after addition of diethylether (100
mL) is suctioned off, washed with ethyl acetate and recrystallized
in nitromethane. F.>360.degree. C.
[0380]
7,9-Dimethyl-1,4,6,10-tetraoxa-5-bora-spiro[4,5Jdeca-7,9-diene-2,3--
dione: 38
[0381] Acetylacetone (0.1 mol), oxalic acid (0.1 mol) and boric
acid (0.1 mol) are heated in toluene (200 mL) until a clear
solution is produced and no more water is separated. After cooling,
the precipitated product is suctioned off and washed with
cyclohexane. F. 187-189.degree. C.
[0382]
8-Acetyl-7,9-dimethyl-1,4,6,10-tetraoxa-5-bora-spiro[4,5[d]eca-7,9--
diene-2,3-dione: 39
[0383] Triacetylmethane (0.1 mol) and bortrifluoride etherate (0.15
mol) are stirred in ether (200 mL) for 20 hrs at room temperature.
Then the precipitated product is suctioned off and washed with
cyclohexane. F.>250.degree. C.
[0384]
2,3-Benzo-7,9-bis-(4-chlorophenyl)-1,4,6,1O-tetraoxa-5-bora-spiro[4-
,5]deca-7,9-diene: 40
[0385] Pyrocatechol (0.1 mol), bis-(4-chlorobenzoyl)-methane (0.1
mol), and boric acid (0.1 mol) are heated in toluene (250 mL) until
a clear solution is obtained and no more water is separated. After
cooling the precipitated product is suctioned off and washed with
cyclohexane. F. 312-315.degree. C.
[0386] Matrix Materials
[0387] Suitable dopants for organic semiconducting materials, such
as hole- transport materials HT, which customarily are used in
OLEOs or organic solar cells, are described in the present
invention. The semiconducting materials preferably are
intrinsically hole-conducting. The following may apply for dopants
of the quinone type as well as of the dioxaborine type.
[0388] The matrix material may consist partially (>10 or >25
wt. %) or substantially (>50 wt. % or >75 wt. %) or
completely of a metal phthalocyanine complex, a porphyrin complex,
in particular metal porphyrin complex, an oligothiophene,
oligophenyl, oligophenylenevinylene or oligofluorene compound,
where the oligomer preferably comprises 2-500 or more, preferably
2-100 or 2-50 or 2-10 monomer units. Optionally, the oligomer may
alternatively comprise >4, >6 or >10 or more monomer
units, in particular alternatively for the regions indicated above,
i.e. for example 4 or 6-10 monomer units, 6 or 10-100 monomer units
or 10-500 monomer units. The monomers and oligomers may be
substituted or unsubstituted, where alternatively block or mixed
polymers in the said oligomers of a compound with a triarylamine
unit or a spiro-bifluoro compound may be present. The said matrix
materials may alternatively be present in combination with one
another, optionally alternatively in combination with other matrix
materials. The matrix materials may have electron-shifting
substituents such as alkyl or alkoxy residues, which have reduced
ionization energy or which reduce the ionization energy of the
matrix material.
[0389] The metal phthalocyanine complexes or porphyrin complexes
used as matrix materials may have a main group metal atom or a
metal atom of the B group. The metal atom Me may in each instance
be coordinated 4, 5 or 6 times, for example in the form of oxo
(Me=0), dioxo (0=Me=0), imine, diimine, hydroxo, dihydroxo, amino
or diamino complexes, without being limited thereto. The
phthalocyanine complex or porphyrin complex may in each instance be
partially hydrated, where however the mesomeric ring system
preferably is not disturbed. The phthalocyanine complexes may
contain as central atom for example magnesium, zinc, iron, nickel,
cobalt, magnesium, copper or vanadyl (.dbd.VO). The same or other
metal atoms and oxometal atoms may be present in the case of
porphyrin complexes. 101531 In particular, such dopable
hole-transport materials HT may be arylated benzidines, for example
N,N'-perarylated benzidines or other diamines such as types TFD
(where one, more or all of the aryl groups may have aromatic
heteroatoms), suitable arylated starburst compounds such as
N,N',N'-perarylated starburst compounds, such as the compound TDA T
A (where one, more or all of the aryl groups may have aromatic
heteroatoms). The aryl residues may in particular comprise, for
each of the compounds mentioned above, phenyl, naphthyl, pyridine,
quinoline, isoquinoline, peridazine, pyrimidine, pyrazine,
pyrazole, imidazole, oxazol, furan, pyrrole, indole or the like.
The phenyl groups of the respective compounds may be partially or
completely replaced by thiophene groups. 41
[0390] Preferably, the matrix material used consists completely of
a metal phthalocyanine complex, a porphyrin complex, a compound
having a triarylamine unit or a spiro-bifluorene compound.
[0391] It is understood that other suitable organic matrix
materials that have semiconducting properties, in particular
hole-conducting materials, may be used.
[0392] Doping 101561 Doping may in particular take place in such a
way that the molar ratio of matrix molecule to dopant, or in the
case of oligomeric matrix materials, the ratio of the number of
matrix monomers to dopant is 1:100000, preferably 1:1 to 1:10,000,
especially preferably 1:5 to 1:1000, for example 1:10 to 1:1 00,
for example about 1:50 to 1:100 or alternatively 1:25 to 1:50.
[0393] Evaporation of Dopants
[0394] Doping of the respective matrix material, indicated as
hole-conducting matrix material HT, with the dopants to be used
according to the present invention may be produced by one or a
combination of the following methods:
[0395] a) mixed evaporation under vacuum with one source for HT and
one for the dopant;
[0396] b) sequential deposition of HT and dopant with subsequent
in-diffusion of the dopant by heat treatment;
[0397] c) doping of a HT layer by a solution of dopant with
subsequent evaporation of the solvent by heat treatment; and
[0398] d) superficial doping of a HT layer by a layer of dopant
applied to the surface. Doping may be effected in such a way that
the dopant is evaporated in a precursor compound that releases the
dopant upon heating and/or irradiation. Irradiation may be effected
by means of electromagnetic radiation, in particular visible light,
UV light or IR light, for example laser light in each instance, or
alternatively by other types of radiation. The heat required for
evaporation may be substantially provided by irradiation,
alternatively the compounds or precursors or compound complexes
such as charge-transfer complexes to be evaporated may be
irradiated in certain bands, in order to facilitate, for example by
conversion into excited states, the evaporation of compounds by
dissociation of complexes. It is understood that the evaporation
conditions described below are directed to those conditions without
irradiation and uniform conditions of evaporation are to be used
for purposes of comparison.
[0399] The following for example may be used as precursor
compounds:
[0400] a) mixtures or stoichiometric or mixed crystalline compounds
in the dopant and an inert, non-volatile substance, e.g. a polymer,
molecular sieve, aluminum oxide, silica gel, oligomers or other
organic or inorganic substance with high evaporation temperature,
where the dopant is linked to this substance primarily by van der
Waals forces and/or hydrogen bridge linkage;
[0401] b) mixture or stoichiometric or mixed crystalline compound
of the dopant and one relatively electron donor-like, non-volatile
compound V, where relatively complete charge transfer occurs
between the dopant and the compound V, such as in charge-transfer
complexes with relatively electron-rich polyaromatic compounds or
heteroaromatic compounds or other organic or inorganic substance
with a high evaporation temperature; and
[0402] c) mixture or stoichiometric or mixed crystalline compound
of the dopant and a substance that is evaporated together with the
dopant and has an ionization energy like or higher than that of the
substance HT to be doped, so that the substance in the organic
matrix material forms no traps for holes. According to the present
invention, the substance may alternatively be identical with the
matrix material, for example, may represent a metal phthalocyanine
or benzidine derivative. Additional suitable volatile
co-substances, such as hydroquinones, 1,4-phenylenediamines or
1-amino-4-hydroxybenzes or other compounds, form quinhydrones or
other charge-transfer complexes.
[0403] Electronic Component
[0404] Use of the organic compounds according to the present
invention for the preparation of doped organic semiconducting
materials, which may be arranged, for example, in the form of
layers or electrical conduction pathways, permits a multiplicity of
electronic components or devices containing them to be produced. In
particular, the dopants according to the invention may be used for
the production of organic light-emitting diodes (OLEOs), organic
solar cells, organic diodes, in particular those with high
rectifying behavior such as 103-107, preferably 104-107 or 105-107,
or organic field-effect transistors. The dopants according to the
present invention allow the conductivity of the doped layers and/or
the charge-carrier injection of contacts into the doped layer to be
improved. In particular, in OLEOs the component may have a pin
structure or an inverse structure, without being limited thereto.
However, use of the dopants according to the present invention is
not limited to the advantageous examples mentioned above.
EXAMPLES
[0405] The invention is to be explained in detail by several
examples.
[0406] The compounds to be used according to the invention, in
particular the compounds indicated above by way of example in the
substance class of quinones or 1,3,2-dioxaborines described above,
are used in the following way as dopants for a variety of
hole-conductors, which in turn are utilized for the construction of
certain microelectronic or optoelectronic components, such as for
example an OLEO. The dopants may be simultaneously evaporated side
by side with the hole-transport materials of the matrix under high
vacuum (about 2.times.10.sup.-4 Pa) at high temperatures. A typical
substrate evaporation rate for the matrix material is 0.2 nm/s
(thickness about 1.5 g/cm.sup.3). Evaporation rates for the dopants
may vary between 0.001 and 0.5 nm/s at like assumed thickness, in
each instance according to the desired doping ratio. The
evaporation temperatures of the compounds in a substrate
evaporation means are indicated in the following, where F4TCNQ,
under otherwise identical conditions, has an evaporation
temperature of 80.degree. C. in order to deposit, in the same
specific unit of time (e.g. five seconds) the same layer thickness
(e.g. 1 nm) on the substrate as the dopants used according to the
invention.
[0407] In the following examples the current measurements were
performed over a 1 mm-long and about 0.5 mm-wide path of current in
the doped HT material at 1 V. Under these conditions ZnPc conducts
practically no electric current.
Example 1
[0408] Doping of ZnPc with
N,N'-dicyano-2,3,5,6-tetrafluoro-1,4-quinonedii- mine (F4DCNQI)
[0409] The evaporation temperature T(evap.) is 85.degree. C. The
two components matrix and dopant were deposited from vapor under
vacuum in a ratio of 50:1. Here the conductivity is
2.4.times.10.sup.-2 s/cm. Results are shown in FIG. 1 and Table 1
below.
1 TABLE 1 Layer Thickness Current (nm) (nA) 5 69.05 10 400.9 15
762.5 20 1147 25 1503.2 30 1874.4 35 2233.4 40 2618 45 3001.5 50
3427
Example 2
[0410] Doping of ZnPc with
N,N'-dicyan-2,5-dichloro-1,4-quinonediimine (C12DCNQI) the
evaporation temperature T(evap.) is 114.degree. C. The ratio of the
two compounds in the vapor-deposited layer is 1:50 in favor of the
matrix. A conductivity of 1.0.times.10.sup.-2 s/cm was measured in
the layer. Results are shown in FIG. 2 and Table 2 below.
2 TABLE 2 Layer Thickness Current (nm) (nA) 5 42.66 10 179.4 15
334.2 20 484 25 635.5 30 786 35 946 40 1091.5 45 1253 50 1409.8
Example 3
[0411] Doping of ZnPc with
N,N'-dicyano-2,5-dichloro-3,6-difluoro-1,4-quin- onediimine
(C12F2DCNQI)
[0412] The evaporation temperature T(evap.) is 118.degree. C. The
layer was vapor-deposited under vacuum at the ratio of 1:25 (dopant
matrix). A conductivity of 4.9.times.10.sup.-4 s/cm was measured
there. Results are shown in FIG. 3 and Table 3 below.
3 TABLE 3 Layer thickness Current (nm) (nA) 5 1.1648 10 4.7852 15
9.7211 20 15.582 25 21.985 30 28.866 35 35.45 40 42.249 45 49.747
50 57.86 55 66.012 60 74.335 65 82.449 70 90.251 75 97.968 80
106.14 85 114.58 90 122.84 95 131.1 100 139.59
Example 4
[0413] Doping of ZnPc with
N,N'-dicyano-2,3,5,6,7,8-hexafluoro-1,4-naphtho- -quinonediimine
(F6DCNNOI)
[0414] The evaporation temperature T(evap.) is 122.degree. C.
Dopant and matrix were vapor-deposited in the ratio of 1:25 on the
carrier under vacuum. A conductivity of 2.times.10.sup.-3 s/cm was
obtained. Results are shown in FIG. 4 and Table 4 below.
4 TABLE 4 Layer thickness Current (nm) (nA) 5 6.4125 10 26.764 15
52.096 20 79.286 25 107.22 30 135.36 35 165.63 40 199.68 45 234.01
50 267.59 55 300.85 60 333.18 65 365.28 70 397.44 75 431.58 80
464.29 85 498.18 90 529.63 95 560.48 100 590.82
Example 5
[0415] Doping of ZnPc with
1,4,5,8-tetrahydro-1,4,5,8-tetrathia-2,3,6,7-te-
tracyano-anthraquinone (CN4TTAQ).
[0416] The evaporation temperature T(evap.) is 170.degree. C. The
layer was vapor-deposited under vacuum at a ratio of 1:25 (dopant
matrix). A conductivity of 4.5.times.10.sup.-4 s/cm was measured.
Results are shown in FIG. 5 and Table 5 below.
5 TABLE 5 Layer Thickness Current (nm) (nA) 10 0.94 15 2.43 20 4.46
30 9.84 40 16.33 50 23.66 60 31.54 70 39.6 80 47.5 90 56 100
63.5
Example 6
[0417] Doping of ZnPc with
2,2,7,7-tetrafluoro-2,7-dihydro-1,3,6,8-tetraox-
a-2,7-dibora-4,9,10 11,12pentachloro-benzo[e]pyrene.
[0418] The evaporation temperature T(evap.) is 140.degree. C. The
layer was vapor-deposited under vacuum at the ratio of 1:25 (dopant
matrix). A conductivity of 2.8.times.10.sup.-5 s/cm was measured
there. Results are shown in FIG. 6 and Table 6 below.
6 TABLE 6 Layer Thickness Current (nm) (nA) 50 1.12 55 1.49 60 1.89
65 2.32 70 2.88 75 3.56 80 4.25 85 5 90 5.9 95 6.94 100 8.1
* * * * *