U.S. patent application number 13/504725 was filed with the patent office on 2012-08-16 for heteroleptic carbene complexes and the use thereof in organic electronics.
This patent application is currently assigned to BASF SE. Invention is credited to Herbert Friedrich Boerner, Korinna Dormann, Evelyn Fuchs, Thomas Gessner, Nicolle Langer, Christian Lennartz, Oliver Molt, Ingo Muenster, JianQiang Qu, Christian Schildknecht, Guenter Schmid, Volker Van Elsbergen, Gerhard Wagenblast, Soichi Watanabe.
Application Number | 20120205645 13/504725 |
Document ID | / |
Family ID | 43478148 |
Filed Date | 2012-08-16 |
United States Patent
Application |
20120205645 |
Kind Code |
A1 |
Fuchs; Evelyn ; et
al. |
August 16, 2012 |
HETEROLEPTIC CARBENE COMPLEXES AND THE USE THEREOF IN ORGANIC
ELECTRONICS
Abstract
The present invention relates to heteroleptic complexes
comprising a phenylimidazole or phenyltriazole unit bonded via a
carbene bond to a central metal atom, and phenylimidazole ligands
attached via a nitrogen-metal bond to the central atom, to OLEDs
which comprise such heteroleptic complexes, to light-emitting
layers comprising at least one such heteroleptic complex, to a
device selected from the group consisting of illuminating elements,
stationary visual display units and mobile visual display units
comprising such an OLED, to the use of such a heteroleptic complex
in OLEDs, for example as emitter, matrix material, charge transport
material and/or charge blocker.
Inventors: |
Fuchs; Evelyn; (Mannheim,
DE) ; Molt; Oliver; (Weinheim, DE) ; Dormann;
Korinna; (Bad Duerkheim, DE) ; Gessner; Thomas;
(Heidelberg, DE) ; Langer; Nicolle; (Heppenheim,
DE) ; Muenster; Ingo; (Boehl-Iggelheim, DE) ;
Qu; JianQiang; (Shanghai, CN) ; Lennartz;
Christian; (Schifferstadt, DE) ; Schildknecht;
Christian; (Mannheim, DE) ; Watanabe; Soichi;
(Mannheim, DE) ; Wagenblast; Gerhard; (Wachenheim,
DE) ; Schmid; Guenter; (Hemhofen, DE) ;
Boerner; Herbert Friedrich; (Aachen, DE) ; Van
Elsbergen; Volker; (Aachen, DE) |
Assignee: |
BASF SE
Ludwigshafen
DE
OSRAM OPTO SEMICONDUCTORS GmbH
Regensburg
DE
Koninklijke Philips Electronics N.V.
BA Eindhoven
NL
|
Family ID: |
43478148 |
Appl. No.: |
13/504725 |
Filed: |
October 28, 2010 |
PCT Filed: |
October 28, 2010 |
PCT NO: |
PCT/EP10/66400 |
371 Date: |
April 27, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61255499 |
Oct 28, 2009 |
|
|
|
Current U.S.
Class: |
257/40 ;
252/301.16; 257/E51.026; 548/103 |
Current CPC
Class: |
H01L 51/0094 20130101;
H01L 51/5048 20130101; H01L 51/0072 20130101; C07F 15/0086
20130101; H01L 51/5012 20130101; H01L 51/009 20130101; C07F 15/0033
20130101; H01L 51/0085 20130101 |
Class at
Publication: |
257/40 ; 548/103;
252/301.16; 257/E51.026 |
International
Class: |
H01L 51/54 20060101
H01L051/54; C09K 11/06 20060101 C09K011/06; C07F 15/00 20060101
C07F015/00 |
Claims
1. A heteroleptic complex of the general formula (I) ##STR00293##
in which M, A.sup.1, A.sup.2, n, m, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10,
R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are each defined as
follows: M is a metal atom selected from the group consisting of Ir
and Pt, A.sup.1, A.sup.2 are each independently N or C, n, m are
each independently 1 or 2, where, if M is Pt, the sum of n and m is
2, or, if M is Ir, the sum of n and m is 3, R.sup.1 is a linear or
branched alkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 1 to 20 carbon atoms, cycloalkyl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having 3 to 20 carbon atoms, substituted
or unsubstituted aryl radical optionally interrupted by at least
one heteroatom, optionally bearing at least one functional group
and having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 5 to 18 carbon atoms and/or heteroatoms, R.sup.2, R.sup.3
are each independently hydrogen, linear or branched alkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 1 to 20 carbon
atoms, cycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms, substituted or unsubstituted aryl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 6 to 30
carbon atoms, substituted or unsubstituted heteroaryl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 5 to 18 carbon
atoms and/or heteroatoms, R.sup.4, R.sup.5, R.sup.6, R.sup.7 are
each independently hydrogen, substituent with donor or acceptor
action, linear or branched alkyl radical optionally interrupted by
at least one heteroatom, optionally bearing at least one functional
group and having 1 to 20 carbon atoms, cycloalkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 3 to 20 carbon
atoms, substituted or unsubstituted aryl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having 6 to 30 carbon atoms, substituted
or unsubstituted heteroaryl radical optionally interrupted by at
least one heteroatom, optionally bearing at least one functional
group and having 5 to 18 carbon atoms and/or heteroatoms, or
R.sup.4 and R.sup.5 or R.sup.5 and R.sup.6 and/or R.sup.6 and
R.sup.7 together form a saturated, unsaturated or aromatic carbon
ring optionally interrupted by at least one heteroatom and having a
total of 5 to 30 carbon atoms or heteroatoms, R.sup.8, R.sup.9 are
each independently a free electron pair if A.sup.1 or A.sup.2 is N,
or, if A.sup.1 or A.sup.2 is C, hydrogen, linear or branched alkyl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 1 to 20
carbon atoms, cycloalkyl radical optionally interrupted by at least
one heteroatom, optionally bearing at least one functional group
and having 3 to 20 carbon atoms, substituted or unsubstituted aryl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 6 to 30
carbon atoms, substituted or unsubstituted heteroaryl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 5 to 18 carbon
atoms and/or heteroatoms, R.sup.10 linear or branched alkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 1 to 20 carbon
atoms, cycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms, substituted or unsubstituted aryl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 6 to 30
carbon atoms, substituted or unsubstituted heteroaryl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 5 to 18 carbon
atoms and/or heteroatoms R.sup.11, R.sup.12, R.sup.13, R.sup.14 are
each independently hydrogen, substituent with donor or acceptor
action, linear or branched alkyl radical optionally interrupted by
at least one heteroatom, optionally bearing at least one functional
group and having 1 to 20 carbon atoms, cycloalkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 3 to 20 carbon
atoms, substituted or unsubstituted aryl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having 6 to 30 carbon atoms, substituted
or unsubstituted heteroaryl radical optionally interrupted by at
least one heteroatom, optionally bearing at least one functional
group and having 5 to 18 carbon atoms and/or heteroatoms, or
R.sup.11 and R.sup.12 or R.sup.12 and R.sup.13 and/or R.sup.13 and
R.sup.14 together form a saturated, unsaturated or aromatic carbon
ring optionally interrupted by at least one heteroatom and having a
total of 5 to 30 carbon atoms and/or heteroatoms and/or R.sup.1 and
R.sup.14 together form a saturated or unsaturated, linear or
branched bridge optionally comprising heteroatoms, aromatic units,
heteroaromatic units and/or functional groups and having a total of
1 to 30 carbon atoms and/or heteroatoms, to which a substituted or
unsubstituted, five- to eight-membered ring comprising carbon atoms
and/or heteroatoms, preferably a six-membered aromatic ring, is
optionally fused, and/or if A.sup.1 is C, R.sup.7 and R.sup.8
together form a saturated or unsaturated, linear or branched bridge
optionally comprising heteroatoms, aromatic units, heteroaromatic
units and/or functional groups and having a total of 1 to 30 carbon
atoms and/or heteroatoms, to which a substituted or unsubstituted,
five- to eight-membered ring comprising carbon atoms and/or
heteroatoms, preferably a six-membered aromatic ring, is optionally
fused.
2. A heteroleptic complex according to claim 1, wherein M, A.sup.1,
A.sup.2, n, m, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13 and R.sup.14 are each defined as follows: M is Ir,
A.sup.1, A.sup.2 is C, n, m are each independently 1 or 2, where
the sum of n and m is 3, R.sup.1 is a linear or branched alkyl
radical having 1 to 20 carbon atoms, substituted or unsubstituted
aryl radical having 6 to 30 carbon atoms, substituted or
unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or
heteroatoms, R.sup.2, R.sup.3 are each independently hydrogen,
linear or branched alkyl radical having 1 to 20 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 30 carbon
atoms, substituted or unsubstituted heteroaryl radical having 5 to
18 carbon atoms and/or heteroatoms, R.sup.4, R.sup.5, R.sup.6,
R.sup.7 are each hydrogen or R.sup.4 and R.sup.5 or R.sup.5 and
R.sup.6 or R.sup.6 and R.sup.7 together form a saturated,
unsaturated or aromatic ring optionally interrupted by at least one
heteroatom and having a total of 5 to 30 carbon atoms and/or
heteroatoms, R.sup.8, R.sup.9 are each hydrogen, R.sup.10 is a
linear or branched alkyl radical having 1 to 20 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 30 carbon
atoms, and R.sup.11, R.sup.12, R.sup.13, R.sup.14 are each
independently hydrogen or linear or branched alkyl radical having 1
to 20 carbon atoms, and/or R.sup.1 and R.sup.14 together form a
saturated or unsaturated, linear or branched bridge optionally
comprising heteroatoms, aromatic units, heteroaromatic units and/or
functional groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms,
preferably a six-membered aromatic ring, is optionally fused,
and/or R.sup.7 and R.sup.8 together form a saturated or
unsaturated, linear or branched bridge optionally comprising
heteroatoms, aromatic units, heteroaromatic units and/or functional
groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms,
preferably a six-membered aromatic ring, is optionally fused.
3. A heteroleptic complex according to claim 1, wherein M, A.sup.1,
A.sup.2, n, m, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13 and R.sup.14 are each defined as follows: M is Ir,
A.sup.1, A.sup.2 are each N or C, where A.sup.1=N when A.sup.2=C
and A.sup.1=C when A.sup.2=N n, m are each independently 1 or 2,
where the sum of n and m is 3, R.sup.1 is a linear or branched
alkyl radical having 1 to 20 carbon atoms, substituted or
unsubstituted aryl radical having 6 to 30 carbon atoms, substituted
or unsubstituted heteroaryl radical having 5 to 18 carbon atoms
and/or heteroatoms, R.sup.2, R.sup.3 are each independently
hydrogen, linear or branched alkyl radical having 1 to 20 carbon
atoms, substituted or unsubstituted aryl radical having 6 to 30
carbon atoms, substituted or unsubstituted heteroaryl radical
having 5 to 18 carbon atoms and/or heteroatoms, R.sup.4, R.sup.5,
R.sup.6, R.sup.7 are each hydrogen or R.sup.4 and R.sup.5 or
R.sup.5 and R.sup.6 or R.sup.6 and R.sup.7 together form a
saturated, unsaturated or aromatic ring optionally interrupted by
at least one heteroatom and having a total of 5 to 30 carbon atoms
and/or heteroatoms, R.sup.8, R.sup.9 are each independently a free
electron pair if A.sup.1 or A.sup.2 is N, or, if A.sup.1 or A.sup.2
is C, hydrogen, linear or branched alkyl radical having 1 to 20
carbon atoms, substituted or unsubstituted aryl radical having 6 to
30 carbon atoms, substituted or unsubstituted heteroaryl radical
having 5 to 18 carbon atoms and/or heteroatoms, R.sup.10 linear or
branched alkyl radical having 1 to 20 carbon atoms, substituted or
unsubstituted aryl radical having 6 to 30 carbon atoms, and
R.sup.11, R.sup.12, R.sup.13, R.sup.14 hydrogen or linear or
branched alkyl radical having 1-20 carbon atoms and/or R.sup.1 and
R.sup.14 together form a saturated or unsaturated, linear or
branched bridge optionally comprising heteroatoms, aromatic units,
heteroaromatic units and/or functional groups and having a total of
1 to 30 carbon atoms and/or heteroatoms, to which a substituted or
unsubstituted, five- to eight-membered ring comprising carbon atoms
and/or heteroatoms, preferably a six-membered aromatic ring, is
optionally fused, and/or if A.sup.1 is C, R.sup.7 and R.sup.8
together form a saturated or unsaturated, linear or branched bridge
optionally comprising heteroatoms, aromatic units, heteroaromatic
units and/or functional groups and having a total of 1 to 30 carbon
atoms and/or heteroatoms, to which a substituted or unsubstituted,
five- to eight-membered ring comprising carbon atoms and/or
heteroatoms, preferably a six-membered aromatic ring, is optionally
fused.
4. A heteroleptic complex according to claim 1, wherein M, A.sup.1,
A.sup.2, n, m, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13 and R.sup.14 are each defined as follows: M is Ir, A.sup.1
is C, A.sup.2 is N or C, n, m are each independently 1 or 2, where
the sum of n and m is 3, R.sup.1 is a linear or branched alkyl
radical having 1 to 20 carbon atoms, substituted or unsubstituted
aryl radical having 6 to 30 carbon atoms, substituted or
unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or
heteroatoms, R.sup.2, R.sup.3 are each independently hydrogen,
linear or branched alkyl radical having 1 to 20 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 30 carbon
atoms, substituted or unsubstituted heteroaryl radical having 5 to
18 carbon atoms and/or heteroatoms, R.sup.4, R.sup.5, R.sup.6 are
each independently hydrogen, linear or branched alkyl radical
having 1 to 20 carbon atoms, substituted or unsubstituted aryl
radical having 6 to 30 carbon atoms, R.sup.7, R.sup.8 together form
an unsaturated C.sub.2 bridge, to which a substituted or
unsubstituted, five- to eight-membered ring comprising carbon atoms
and/or heteroatoms, may be fused, R.sup.9 is a free electron pair
if A.sup.2 is N or, if A.sup.2 is C, hydrogen, linear or branched
alkyl radical having 1 to 20 carbon atoms, substituted or
unsubstituted aryl radical having 6 to 30 carbon atoms, substituted
or unsubstituted heteroaryl radical having 5 to 18 carbon atoms
and/or heteroatoms, R.sup.10 is a linear or branched alkyl radical
having 1 to 20 carbon atoms, substituted or unsubstituted aryl
radical having 6 to 30 carbon atoms, and R.sup.11, R.sup.12,
R.sup.13, R.sup.14 are each independently hydrogen or linear or
branched alkyl radical having 1 to 20 carbon atoms, and/or R.sup.1
and R.sup.14 together form a saturated or unsaturated, linear or
branched bridge optionally comprising heteroatoms, aromatic units,
heteroaromatic units and/or functional groups and having a total of
1 to 30 carbon atoms and/or heteroatoms, to which a substituted or
unsubstituted, five- to eight-membered ring comprising carbon atoms
and/or heteroatoms, preferably a six-membered aromatic ring, is
optionally fused.
5. A heteroleptic complex according to any of claims 1 to 4,
wherein R.sup.1 is an aryl radical which has 6 to 30 carbon atoms
and is substituted in the ortho,ortho' positions in each case by a
linear or branched alkyl radical having 1 to 10 carbon atoms.
6. A heteroleptic complex according to any of claims 1 to 5,
wherein R.sup.1 and R.sup.14 together form a saturated or
unsaturated, linear or branched bridge optionally comprising
heteroatoms, aromatic units, heteroaromatic units and/or functional
groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms,
preferably a six-membered aromatic ring, is optionally fused.
7. A heteroleptic complex according to any of claims 1 to 5,
wherein R.sup.4 and R.sup.5, R.sup.5 and R.sup.6 or R.sup.6 and
R.sup.7 together form a cycle of the general formula (IIa) or (IIb)
##STR00294##
8. A heteroleptic complex according to any of claims 1 to 7 with
the specified definitions of M, A.sup.1, A.sup.2, n, m, R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8,
R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13 and R.sup.14, which
has one of the following configurations IIIa, IIIb, IVa or IVb:
##STR00295##
9. A process for preparing a heteroleptic complex according to any
of claims 1 to 8 by contacting at least one precursor compound
comprising the metal M and the at least one ligand which, in the
complexes of the general formula (I), is attached to M via
noncarbene bonds with at least one ligand which, in the complexes
of the general formula (I), is attached to M via at least one
carbene bond, or the ligand precursor thereof, for example a
corresponding imidazolium salt, or by contacting at least one
precursor compound comprising the metal M and a ligand which, in
the complexes of the general formula (I), is bonded to M via at
least one carbene bond with at least one ligand which, in the
complexes of the general formula (I), is attached to M via
noncarbene bonds.
10. An OLED comprising at least one heteroleptic complex according
to any of claims 1 to 8.
11. An OLED comprising a heteroleptic complex according to any of
claims 1 to 8, and at least one compound of the formula (X)
##STR00296## In which T is NR.sup.57, S, O or PR.sup.57, preferably
S or O, more preferably O; R.sup.57 is aryl, heteroaryl, alkyl,
cycloalkyl or heterocycloalkyl; Q' is --NR.sup.58R.sup.59,
--P(O)R.sup.60R.sup.61, --PR.sup.62R.sup.63, --S(O).sub.2R.sup.64,
--S(O)R.sup.65, --SR.sup.66 or --OR.sup.67, preferably
--NR.sup.58R.sup.59; more preferably ##STR00297## wherein R.sup.68,
R.sup.69 are each independently alkyl, cycloalkyl,
heterocycloalkyl, aryl or heteroaryl; preferably methyl,
carbazolyl, dibenzofuryl or dibenzothienyl; y, z are each
independently 0, 1, 2, 3 or 4, preferably 0 or 1; R.sup.55,
R.sup.56 are each independently alkyl, cycloalkyl,
heterocycloalkyl, aryl, heteroaryl, SiR.sup.70R.sup.71R.sup.72, a
group Q' or a group with donor or acceptor action; a'' 0, 1, 2, 3
or 4; b' 0, 1, 2 or 3; R.sup.58, R.sup.59 together with the
nitrogen atom form a cyclic radical which has 3 to 10 ring atoms
and may be unsubstituted or substituted by one or more
substitutents selected from alkyl, cycloalkyl, heterocycloalkyl,
aryl, heteroaryl and a group with donor or acceptor action and/or
may be fused to one or more further cyclic radicals having 3 to 10
ring atoms, where the fused radicals may be unsubstituted or
substituted by one or more substituents selected from alkyl,
cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with
donor or acceptor action; R.sup.70, R.sup.71, R.sup.72, R.sup.60,
R.sup.61, R.sup.62, R.sup.63, R.sup.64, R.sup.65, R.sup.66,
R.sup.67 are each independently aryl, heteroaryl, alkyl, cycloalkyl
or heterocycloalkyl, or two units of the general formula (X) are
bridged by a linear or branched, saturated or unsaturated bridge,
optionally interrupted by at least one heteroatom, by a bonding or
by O.
12. OLED according to claim 11 comprising at least one compound of
formula (XI) or (XI*) ##STR00298## wherein T is NR.sup.57, S, O or
PR.sup.57; R.sup.57 is aryl, heteroaryl, alkyl, cycloalkyl or
heterocycloalkyl; Q' is --NR.sup.58R.sup.59,
--P(O)R.sup.60R.sup.61, --PR.sup.62R.sup.63, --S(O).sub.2R.sup.64,
--S(O)R.sup.65, --SR.sup.66 or --OR.sup.67; R.sup.70, R.sup.71,
R.sup.72 are each independently aryl, heteroaryl, alkyl,
cycloalkyl, heterocycloalkyl, wherein of at least one of the
radicals R.sup.70, R.sup.71, R.sup.72 comprises at least two carbon
atoms or OR.sup.73, R.sup.55, R.sup.56 are each independently
alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, a group Q or
a group with donor or acceptor action; a', b' are for the compound
of formula (XI): each independently 0, 1, 2, 3; for the compound of
formula (XI*) a' is 0, 1, 2 and bis' 0, 1, 2, 3, 4; R.sup.58,
R.sup.59 together with the nitrogen atom form a cyclic radical
which has 2 to 10 ring atoms and may be unsubstituted or
substituted by one or more substitutents selected from alkyl,
cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with
donor or acceptor action and/or may be fused to one or more further
cyclic radicals having 3 to 10 ring atoms, where the fused radicals
may be unsubstituted or substituted by one or more substituents
selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl
and a group with donor or acceptor action; R.sup.73 is
independently SiR.sup.74R.sup.75R.sup.76, aryl, heteroaryl, alkyl,
cycloalkyl or heterocycloalkyl, optionally substituted with a group
OR.sup.77 R.sup.77 is independently SiR.sup.74R.sup.75R.sup.76,
aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, R.sup.60,
R.sup.61, R.sup.62, R.sup.63, R.sup.64, R.sup.65, R.sup.66,
R.sup.67, R.sup.74, R.sup.75, R.sup.76 are each independently aryl,
heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, or two units of
the general formulae (XI) and/or (XI*) are bridged by a linear or
branched, saturated or unsaturated bridge, optionally interrupted
by at least one heteroatom or by O, wherein said bridge is bonded
in the general formulae (XI) and/or (XI*) each time instead of
R.sup.71 to the Si-atoms.
13. OLED according to claim 12, wherein in the compounds of the
general formulae (XI) or (XI*) R.sup.70 and/or R.sup.71 and/or
R.sup.72 are aromatic units of the general formulae (XIi) and/or
(XIi*) ##STR00299## wherein R.sup.55, R.sup.56, Q', T, a' and b'
have the same meanings as in claim 12.
14. A light-emitting layer comprising at least one heteroleptic
complex according to any of claims 1 to 8.
15. An OLED comprising a light-emitting layer according to claim
14.
16. The OLED according to any of claim 10 to 13 or 15, which
comprises an electron-transporting layer comprising at least two
different materials, of which at least one material should be
electron-conductive.
17. The OLED according to claim 16, wherein the
electron-transporting layer comprises at least one phenanthroline
derivative.
18. The OLED according to claim 16, wherein the
electron-transporting layer comprises at least one phenanthroline
derivative and at least one alkali metal hydroxyquinolate
complex.
19. A device selected from the group consisting of illuminating
elements, stationary visual display units and mobile visual display
units, comprising at least one OLED according to any of claims 10
to 13 or 15 to 18.
20. The use of a heteroleptic complex according to any of claims 1
to 8 in OLEDs.
21. The use according to claim 20, wherein the heteroleptic
complexes are used as emitter, matrix material, charge transport
material and/or charge blocker.
Description
[0001] The present invention relates to heteroleptic complexes
comprising a phenylimidazole or phenyltriazole unit bonded via a
carbene bond to a central metal atom, and phenylimidazole ligands
attached via a nitrogen-metal bond to the central atom, to OLEDs
which comprise such heteroleptic complexes, to light-emitting
layers comprising at least one such heteroleptic complex, to a
device selected from the group consisting of illuminating elements,
stationary visual display units and mobile visual display units
comprising such an OLED, to the use of such a heteroleptic complex
in OLEDs, for example as emitter, matrix material, charge transport
material and/or charge blocker.
[0002] Organic Light-Emitting Diodes (OLEDs) exploit the property
of materials to emit light when they are excited by electrical
current. OLEDs are of particular interest as an alternative to
cathode ray tubes and liquid-crystal displays for production of
flat visual display units. Owing to the very compact design and the
intrinsically low power consumption, devices comprising OLEDs are
suitable especially for mobile applications, for example for
applications in cellphones, laptops, etc. In addition, white OLEDs
give great advantages over the illumination technologies known to
date, especially a particularly high efficiency.
[0003] The prior art proposes numerous materials, examples of which
include heteroleptic complexes with iridium as the central metal
atom, which emit light on excitation by electrical current.
[0004] WO 2006/121811 A1 discloses phosphorescent heteroleptic
metal complexes which comprise carbene ligands. The complexes
specified in WO 2006/121811 A1, for example iridium complexes, all
have benzimidazolocarbenes (benzimidazolylidenes) as carbene
ligands. Compounds which have imidazolocarbenes (imidazolylidenes)
or triazolocarbenes (triazolylidenes) as ligands are not disclosed
in WO 2006/121811 A1.
[0005] WO 2006/067074 A1 likewise discloses electroluminescent
heteroleptic metal complexes with carbene ligands. The noncarbene
ligands used include arylpyridines, arylpyrazoles and
aryltriazoles. Use of 2-phenyl-1H-imidazoles as noncarbene ligands
is not disclosed in WO 2006/067074 A1.
[0006] WO 2007/115981 discloses heteroleptic metal complexes
comprising both carbene ligands and heterocyclic noncarbene
ligands, a process for preparation thereof, and the use of these
compounds in OLEDs. The compounds disclosed by way of example in WO
2007/115981 do not comprise a combination of 2-phenyl-1H-imidazole
ligands with an imidazolocarbene (imidazolylidene) ligand or a
triazolocarbene (triazolylidene) ligand.
[0007] JP 2009057505 discloses optoelectronic components which
comprise compounds with tunable emission wavelength, high light
emission efficiency and long lifetime. The components according to
this document comprise metal complexes which, as well as two
ligands optionally joined to one another, comprise at least one
ligand attached to the metal atom firstly via a carbene bond and
secondly via a noncarbene bond. No combination of a
2-phenyl-1H-imidazole ligand with an imidazolocarbene
(imidazolylidene) ligand or a triazolocarbene (triazolylidene)
ligand is disclosed.
[0008] Even though compounds which exhibit electroluminescence in
the visible region, more particularly in the red, green and
especially blue region of the electromagnetic spectrum, for example
iridium complexes, are already known, the provision of alternative
compounds which possess high quantum yields and exhibit long diode
lifetimes is desirable. In the context of the present invention,
electroluminescence is understood to mean both electrofluorescence
and electrophosphorescence.
[0009] It is therefore an object of the present invention to
provide alternative iridium and platinum complexes which are
suitable for electroluminescence in the visible region, more
particularly in the red, green and especially blue region of the
electromagnetic spectrum, which enables the production of
full-color displays and white OLEDs. It is a further object of the
present invention to provide corresponding complexes which can be
used as a mixture with a host compound (matrix material) or in
substance, i.e. in the absence of host substances, as a
light-emitting layer in OLEDs. It is a further object of the
present invention to provide corresponding complexes which have a
high quantum yield and a high stability in diodes. The complexes
should be usable as emitter, matrix material, charge transport
material, especially hole transport material, or charge blocker in
OLEDs.
[0010] These objects are achieved in accordance with the invention
by heteroleptic complexes of the general formula (I)
##STR00001##
in which M, A.sup.1, A.sup.2, n, m, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10,
R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are each defined as
follows: [0011] M is a metal atom selected from the group
consisting of Ir and Pt, [0012] A.sup.1, A.sup.2 are each
independently N or C, [0013] n, m are each independently 1 or 2,
where, if M is Pt, the sum of n and m is 2, or, if M is Ir, the sum
of n and m is 3, [0014] R.sup.1 is a linear or branched alkyl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 1 to 20
carbon atoms, cycloalkyl radical optionally interrupted by at least
one heteroatom, optionally bearing at least one functional group
and having 3 to 20 carbon atoms, substituted or unsubstituted aryl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 6 to 30
carbon atoms, substituted or unsubstituted heteroaryl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 5 to 18 carbon
atoms and/or heteroatoms, [0015] R.sup.2, R.sup.3 are each
independently hydrogen, linear or branched alkyl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having 1 to 20 carbon atoms, cycloalkyl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 3 to 20
carbon atoms, substituted or unsubstituted aryl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having 6 to 30 carbon atoms, substituted
or unsubstituted heteroaryl radical optionally interrupted by at
least one heteroatom, optionally bearing at least one functional
group and having 5 to 18 carbon atoms and/or heteroatoms, [0016]
R.sup.4, R.sup.5, [0017] R.sup.6, R.sup.7 are each independently
hydrogen, substituent with donor or acceptor action, linear or
branched alkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 1 to 20 carbon atoms, cycloalkyl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having 3 to 20 carbon atoms, substituted
or unsubstituted aryl radical optionally interrupted by at least
one heteroatom, optionally bearing at least one functional group
and having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 5 to 18 carbon atoms and/or heteroatoms, or R.sup.4 and
R.sup.5 or R.sup.5 and R.sup.6 and/or R.sup.6 and R.sup.7 together
form a saturated, unsaturated or aromatic carbon ring optionally
interrupted by at least one heteroatom and having a total of 5 to
30 carbon atoms or heteroatoms, [0018] R.sup.8, R.sup.9 are each
independently a free electron pair if A.sup.1 or A.sup.2 is N, or,
if A.sup.1 or A.sup.2 is C, hydrogen, linear or branched alkyl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 1 to 20
carbon atoms, cycloalkyl radical optionally interrupted by at least
one heteroatom, optionally bearing at least one functional group
and having 3 to 20 carbon atoms, substituted or unsubstituted aryl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 6 to 30
carbon atoms, substituted or unsubstituted heteroaryl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 5 to 18 carbon
atoms and/or heteroatoms, [0019] R.sup.10 linear or branched alkyl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 1 to 20
carbon atoms, cycloalkyl radical optionally interrupted by at least
one heteroatom, optionally bearing at least one functional group
and having 3 to 20 carbon atoms, substituted or unsubstituted aryl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 6 to 30
carbon atoms, substituted or unsubstituted heteroaryl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 5 to 18 carbon
atoms and/or heteroatoms [0020] R.sup.11, R.sup.12, [0021]
R.sup.13, R.sup.14 are each independently hydrogen, substituent
with donor or acceptor action, linear or branched alkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 1 to 20 carbon
atoms, cycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms, substituted or unsubstituted aryl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 6 to 30
carbon atoms, substituted or unsubstituted heteroaryl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 5 to 18 carbon
atoms and/or heteroatoms, or R.sup.11 and R.sup.12 or R.sup.12 and
R.sup.13 and/or R.sup.13 and R.sup.14 together form a saturated,
unsaturated or aromatic carbon ring optionally interrupted by at
least one heteroatom and having a total of 5 to 30 carbon atoms
and/or heteroatoms and/or R.sup.1 and R.sup.14 together form a
saturated or unsaturated, linear or branched bridge optionally
comprising heteroatoms, aromatic units, heteroaromatic units and/or
functional groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms,
preferably a six-membered aromatic ring, is optionally fused,
and/or if A.sup.1 is C, R.sup.7 and R.sup.8 together form a
saturated or unsaturated, linear or branched bridge optionally
comprising heteroatoms, aromatic units, heteroaromatic units and/or
functional groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms,
preferably a six-membered aromatic ring, is optionally fused.
[0022] In the context of the present invention, the terms aryl
radical, unit or group, heteroaryl radical, unit or group, alkyl
radical, unit or group and cycloalkyl radical, unit or group are
each defined as follows, as long as no different meanings are
mentioned:
[0023] An aryl radical or group is understood to mean a radical
with a base skeleton of 6 to 30 carbon atoms, preferably 6 to 18
carbon atoms, which is formed from an aromatic ring or a plurality
of fused aromatic rings. Suitable base skeletons are, for example,
phenyl, benzyl, naphthyl, anthracenyl or phenanthrenyl. This base
skeleton may be unsubstituted, which means that all carbon atoms
which are substitutable bear hydrogen atoms, or may be substituted
at one, more than one or all substitutable positions of the base
skeleton. Suitable substituents are, for example, alkyl radicals,
preferably alkyl radicals having 1 to 8 carbon atoms, more
preferably methyl, ethyl, i-propyl or t-butyl, aryl radicals,
preferably C.sub.6-aryl radicals, which may in turn be substituted
or unsubstituted, heteroaryl radicals, preferably heteroaryl
radicals which comprise at least one nitrogen atom, more preferably
pyridyl radicals, alkenyl radicals, preferably alkenyl radicals
which bear one double bond, more preferably alkenyl radicals with
one double bond and 1 to 8 carbon atoms, or groups with donor or
acceptor action. Groups with donor action are understood to mean
groups which have a +I and/or +M effect, and groups with acceptor
action are understood to mean groups which have a -I and/or -M
effect. Suitable groups with donor or acceptor action are halogen
radicals, preferably F, Cl, Br, more preferably F, alkyl radicals,
alkoxy radicals, aryloxy radicals, carbonyl radicals, ester
radicals, amine radicals, amide radicals, CH.sub.2F groups,
CHF.sub.2 groups, CF.sub.3 groups, CN groups, thio groups or SCN
groups. The aryl radicals most preferably bear substituents
selected from the group consisting of methyl, ethyl, iso-propyl,
n-propyl, n-butyl, iso-butyl, tert-butyl, aryloxy, amine, thio
groups and alkoxy, or the aryl radicals are unsubstituted. The aryl
radical or the aryl group is preferably a C.sub.6-aryl radical
optionally substituted by at least one of the aforementioned
substituents. The C.sub.6-aryl radical more preferably has none,
one, two or three of the aforementioned substituents.
[0024] A heteroaryl radical or a heteroaryl group is understood to
mean radicals having 5 to 30 carbon atoms and/or heteroatoms, which
differ from the aforementioned aryl radicals in that at least one
carbon atom in the base skeleton of the aryl radicals is replaced
by a heteroatom. Preferred heteroatoms are N, O and S. Most
preferably, one or two carbon atoms of the base skeleton of the
aryl radicals are replaced by heteroatoms. The base skeleton is
especially preferably selected from electron-poor systems such as
pyridyl, pyrimidyl, pyrazyl and triazolyl, and five-membered
heteroaromatics such as pyrrole, furan, thiophene, imidazole,
pyrazole, triazole, oxazole and thiazole. The base skeleton may be
substituted at one, more than one or all substitutable positions of
the base skeleton. Suitable substituents are the same as have
already been specified above for the aryl groups.
[0025] An alkyl radical or an alkyl group is understood to mean a
radical having 1 to 20 carbon atoms, preferably 1 to 10 carbon
atoms, more preferably 1 to 8 carbon atoms. This alkyl radical may
be branched or unbranched and may optionally be interrupted by one
or more heteroatoms, preferably N, O or S. In addition, this alkyl
radical may be substituted by one or more of the substituents
already specified for the aryl groups. It is likewise possible that
the alkyl radical bears one or more aryl groups. All of the aryl
groups listed above are suitable. Particular preference is given to
the alkyl radicals selected from the group consisting of methyl,
ethyl, i-propyl, n-propyl, i-butyl, n-butyl, t-butyl, sec-butyl,
i-pentyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, i-hexyl and
sec-hexyl. Very particular preference is given to methyl, i-propyl,
tert-butyl.
[0026] A cycloalkyl radical or a cycloalkyl group is understood to
mean a cyclic radical having 3 to 20 carbon atoms, preferably 3 to
10 carbon atoms, more preferably 3 to 8 carbon atoms. This
cycloalkyl radical may optionally be interrupted by one or more
heteroatoms, preferably N, O or S. In addition, this cycloalkyl
radical may be unsubstituted or substituted, i.e. may be
substituted by one or more of the substituents already specified
for the aryl groups. It is likewise possible that the cycloalkyl
radical bears one or more aryl groups. All of the aryl groups
listed above are suitable.
[0027] The statements made for the aryl, heteroaryl, alkyl and
cycloalkyl radicals applies, in accordance with the invention,
independently to the radicals mentioned in the present application,
especially to the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13 and R.sup.14 radicals, where R.sup.8 and R.sup.9, in the
case that A.sup.1 and/or A.sup.2 is N, are a free electron pair,
which means that no substituent selected from the abovementioned
group is present on these ring nitrogen atoms. In the case that
A.sup.1 and/or A.sup.2 is C, R.sup.8 and R.sup.9 are each
independently hydrogen and/or the substituents specified.
[0028] In a preferred embodiment, M, A.sup.1, A.sup.2, n, m,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7,
R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13 and
R.sup.14 are each defined as follows:
[0029] According to the invention, M is Ir or Pt, preferably Ir. Ir
is present in the inventive heteroleptic complexes in the +3
oxidation state. Pt is present in the inventive heteroleptic
complexes in the +2 oxidation state.
[0030] According to the invention, A.sup.1 and A.sup.2 are each
independently C or N. Preference is given in accordance with the
invention to the following embodiments: [0031] 1. Both A.sup.1 and
A.sup.2 are C, i.e. the inventive heteroleptic complexes comprise
at least one phenylimidazole unit attached via a metal-carbene
bond. [0032] 2. In a further preferred embodiment, A.sup.1 and
A.sup.2 are each N or C, where A.sup.1=N when A.sup.2=C or
A.sup.1=C when A.sup.2 is N, i.e. one of A.sup.1 and A.sup.2 is N,
the other is C. In this embodiment, the inventive heteroleptic
complexes comprise at least one phenyltriazole unit attached via a
metal-carbene bond.
[0033] n and m are each independently 1 or 2, where, if M is Pt,
the sum of n and m is 2, or, if M is Ir, the sum of n and m is 3.
Therefore, if M is Pt, n and m are each 1. If M is Ir, preferably,
n=2 and m=1.
[0034] In a preferred embodiment, R.sup.1 is a linear or branched
alkyl radical having 1 to 20 carbon atoms, a substituted or
unsubstituted aryl radical having 6 to 30 carbon atoms, a
substituted or unsubstituted heteroaryl radical having 5 to 18
carbon atoms and/or heteroatoms.
[0035] R.sup.1 is more preferably a substituted or unsubstituted
aryl radical having 6 to 30 carbon atoms, most preferably a
substituted, especially ortho,ortho'- or
ortho,ortho',para-substituted, or unsubstituted phenyl radical. The
substituents are preferably alkyl radicals having 1 to 10,
especially 1 to 6, carbon atoms, for example methyl, ethyl, propyl,
butyl. Very particularly preferred R.sup.1 radicals are phenyl,
2,6-dimethylphenyl, 2,6-di-iso-propylphenyl or
2,4,6-trimethylphenyl, i.e. mesityl.
[0036] The present invention therefore relates more particularly to
an inventive heteroleptic complex where R.sup.1 is an aryl radical
which has 6 to 30 carbon atoms and is substituted in the
ortho,ortho' positions in each case by a linear or branched alkyl
radical having 1 to 10 carbon atoms.
[0037] In a preferred embodiment, R.sup.2, R.sup.3 are each
independently hydrogen, a linear or branched alkyl radical having 1
to 20 carbon atoms, a substituted or unsubstituted aryl radical
having 6 to 30 carbon atoms, a substituted or unsubstituted
heteroaryl radical having 5 to 18 carbon atoms and/or
heteroatoms.
[0038] In a preferred embodiment, R.sup.4, R.sup.5, R.sup.6,
R.sup.7 are each hydrogen or R.sup.4 and R.sup.5 or R.sup.5 and
R.sup.6 or R.sup.6 and R.sup.7, especially R.sup.5 and R.sup.6 or
R.sup.6 and R.sup.7, together form a saturated, unsaturated or
aromatic carbon ring optionally interrupted by at least one
heteroatom and having a total of 6 to 30 carbon atoms.
[0039] In a very particularly preferred embodiment of the inventive
heteroleptic complex, R.sup.4 and R.sup.5 or R.sup.5 and R.sup.6 or
R.sup.6 and R.sup.7 together form a cycle of the general formula
(IIa) or (IIb)
##STR00002##
[0040] In a further preferred embodiment, R.sup.8, R.sup.9 are each
independently a free electron pair if A.sup.1 or A.sup.2 is N, or,
if A.sup.1 or A.sup.2 is C, hydrogen or linear or branched alkyl
radical having 1 to 20 carbon atoms, substituted or unsubstituted
aryl radical having 6 to 30 carbon atoms or substituted or
unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or
heteroatoms, most preferably phenyl radical.
[0041] In a preferred embodiment, R.sup.10 is a linear or branched
alkyl radical having 1 to 20 carbon atoms, more preferably having 1
to 6 carbon atoms, or a substituted or unsubstituted aryl radical
having 6 to 30 carbon atoms, more preferably having 6 to 10 carbon
atoms. Examples of particularly preferred alkyl radicals for
R.sup.10 are methyl, ethyl, propyl, especially isopropyl, butyl,
especially tert-butyl, or pentyl. Examples of particularly
preferred aryl radicals for R.sup.10 are unsubstituted phenyl or
substituted phenyl, preferably substituted in the ortho position,
for example by alkyl radicals having 1 to 6 carbon atoms, for
example methyl, ethyl or propyl, especially isopropyl.
[0042] In a preferred embodiment, R.sup.11, R.sup.12, R.sup.13,
R.sup.14 are each independently hydrogen or a linear or branched
alkyl radical having 1 to 20 carbon atoms, more preferably
hydrogen.
[0043] In a further embodiment of the inventive heteroleptic
complexes, R.sup.1 and R.sup.14 together form a saturated or
unsaturated, linear or branched bridge optionally comprising
heteroatoms, aromatic units, heteroaromatic units and/or functional
groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms,
preferably a six-membered aromatic ring, is optionally fused. Most
preferably, R.sup.1 and R.sup.14 form an unsaturated bridge having
two carbon atoms, to which a six-membered aromatic ring is fused,
which is either unsubstituted or substituted by one or two alkyl
radicals having 1 to 6 carbon atoms, for example methyl or
ethyl.
[0044] In a further embodiment of the inventive heteroleptic
complexes, if A.sup.1 is C, R.sup.7 and R.sup.8 together form a
saturated or unsaturated, linear or branched bridge optionally
comprising heteroatoms, aromatic units, heteroaromatic units and/or
functional groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms,
preferably a six-membered aromatic ring, is optionally fused. Most
preferably, R.sup.7 and R.sup.8 form an unsaturated bridge having
two carbon atoms, to which a six-membered aromatic ring is fused,
which is either unsubstituted or substituted by one or two alkyl
radicals having 1 to 6 carbon atoms, for example methyl or
ethyl.
[0045] The present invention more preferably relates to inventive
heteroleptic complexes of the general formula (I) where M, A.sup.1,
A.sup.2, n, m, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13 and R.sup.14 are each defined as follows: [0046] M is Ir,
[0047] A.sup.1, A.sup.2 is C, [0048] n, m are each independently 1
or 2, where the sum of n and m is 3; preferably, n=2 and m=1,
[0049] R.sup.1 is a linear or branched alkyl radical having 1 to 20
carbon atoms, substituted or unsubstituted aryl radical having 6 to
30 carbon atoms, substituted or unsubstituted heteroaryl radical
having 5 to 18 carbon atoms and/or heteroatoms; preferably R.sup.1
is an unsubstituted or substituted aryl radical, [0050] R.sup.2,
R.sup.3 are each independently hydrogen, linear or branched alkyl
radical having 1 to 20 carbon atoms, substituted or unsubstituted
aryl radical having 6 to 30 carbon atoms, substituted or
unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or
heteroatoms; preferably R.sup.2 and R.sup.3 are each hydrogen,
[0051] R.sup.4, R.sup.5, [0052] R.sup.6, R.sup.7 are each hydrogen
[0053] or R.sup.4 and R.sup.5 or R.sup.5 and R.sup.6 or R.sup.6 and
R.sup.7 together form a saturated, unsaturated or aromatic ring
optionally interrupted by at least one heteroatom and having a
total of 5 to 30 carbon atoms and/or heteroatoms, [0054] R.sup.8,
R.sup.9 are each hydrogen, [0055] R.sup.10 is a linear or branched
alkyl radical having 1 to 20 carbon atoms, substituted or
unsubstituted aryl radical having 6 to 30 carbon atoms, and [0056]
R.sup.11, R.sup.12, [0057] R.sup.13, R.sup.14 are each
independently hydrogen or linear or branched alkyl radical having 1
to 20 carbon atoms, and/or R.sup.1 and R.sup.14 together form a
saturated or unsaturated, linear or branched bridge optionally
comprising heteroatoms, aromatic units, heteroaromatic units and/or
functional groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms,
preferably a six-membered aromatic ring, is optionally fused,
and/or R.sup.7 and R.sup.8 together form a saturated or
unsaturated, linear or branched bridge optionally comprising
heteroatoms, aromatic units, heteroaromatic units and/or functional
groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms,
preferably a six-membered aromatic ring, is optionally fused.
[0058] The abovementioned preferred and particularly preferred
embodiments apply correspondingly.
[0059] The present invention preferably further relates to
inventive heteroleptic complexes of the general formula (I) where
M, A.sup.1, A.sup.2, n, m, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11,
R.sup.12, R.sup.13 and R.sup.14 are each defined as follows: [0060]
M is Ir, [0061] A.sup.1, A.sup.2 are each N or C, where A.sup.1=N
when A.sup.2=C and A.sup.1=C when A.sup.2=N [0062] n, m are each
independently 1 or 2, where the sum of n and m is 3; preferably n=2
and m=1, [0063] R.sup.1 is a linear or branched alkyl radical
having 1 to 20 carbon atoms, substituted or unsubstituted aryl
radical having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms;
preferably R.sup.1 is a substituted or unsubstituted aryl radical,
[0064] R.sup.2, R.sup.3 are each independently hydrogen, linear or
branched alkyl radical having 1 to 20 carbon atoms, substituted or
unsubstituted aryl radical having 6 to 30 carbon atoms, substituted
or unsubstituted heteroaryl radical having 5 to 18 carbon atoms
and/or heteroatoms; preferably, R.sup.2 and R.sup.3 are each
hydrogen, [0065] R.sup.4, R.sup.5, [0066] R.sup.6, R.sup.7 are each
hydrogen or R.sup.4 and R.sup.5 or R.sup.5 and R.sup.6 or R.sup.6
and R.sup.7 together form a saturated, unsaturated or aromatic ring
optionally interrupted by at least one heteroatom and having a
total of 5 to 30 carbon atoms and/or heteroatoms, [0067] R.sup.8,
R.sup.9 are each independently a free electron pair if A.sup.1 or
A.sup.2 is N, or, if A.sup.1 or A.sup.2 is C, hydrogen, linear or
branched alkyl radical having 1 to 20 carbon atoms, substituted or
unsubstituted aryl radical having 6 to 30 carbon atoms, substituted
or unsubstituted heteroaryl radical having 5 to 18 carbon atoms
and/or heteroatoms, [0068] R.sup.10 linear or branched alkyl
radical having 1 to 20 carbon atoms, substituted or unsubstituted
aryl radical having 6 to 30 carbon atoms, and [0069] R.sup.11,
R.sup.12, [0070] R.sup.13, R.sup.14 hydrogen or linear or branched
alkyl radical having 1-20 carbon atoms and/or R.sup.1 and R.sup.14
together form a saturated or unsaturated, linear or branched bridge
optionally comprising heteroatoms, aromatic units, heteroaromatic
units and/or functional groups and having a total of 1 to 30 carbon
atoms and/or heteroatoms, to which a substituted or unsubstituted,
five- to eight-membered ring comprising carbon atoms and/or
heteroatoms, preferably a six-membered aromatic ring, is optionally
fused, and/or R.sup.7 and R.sup.8 together form a saturated or
unsaturated, linear or branched bridge optionally comprising
heteroatoms, aromatic units, heteroaromatic units and/or functional
groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms,
preferably a six-membered aromatic ring, is optionally fused.
[0071] The abovementioned preferred and particularly preferred
embodiments apply correspondingly.
[0072] The present invention preferably also relates to inventive
heteroleptic complexes of the general formula (I) where M, A.sup.1,
A.sup.2, n, m, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13 and R.sup.14 are each defined as follows: [0073] M is Ir,
[0074] A.sup.1 is C, [0075] A.sup.2 is N or C, [0076] n, m are each
independently 1 or 2, where the sum of n and m is 3; preferably n=2
and m=1, [0077] R.sup.1 is a linear or branched alkyl radical
having 1 to 20 carbon atoms, substituted or unsubstituted aryl
radical having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical having 5 to 18 carbon atoms and/or heteroatoms;
preferably, R.sup.1 is a substituted or unsubstituted aryl radical,
[0078] R.sup.2, R.sup.3 are each independently hydrogen, linear or
branched alkyl radical having 1 to 20 carbon atoms, substituted or
unsubstituted aryl radical having 6 to 30 carbon atoms, substituted
or unsubstituted heteroaryl radical having 5 to 18 carbon atoms
and/or heteroatoms; preferably R.sup.2 and R.sup.3 are each
hydrogen, [0079] R.sup.4, R.sup.5, [0080] R.sup.6 are each
independently hydrogen, linear or branched alkyl radical having 1
to 20 carbon atoms, substituted or unsubstituted aryl radical
having 6 to 30 carbon atoms, [0081] R.sup.7, R.sup.8 together form
an unsaturated C.sub.2 bridge, to which a substituted or
unsubstituted, five- to eight-membered ring comprising carbon atoms
and/or heteroatoms, may be fused, [0082] R.sup.9 is a free electron
pair if A.sup.2 is N or, if A.sup.2 is C, hydrogen, linear or
branched alkyl radical having 1 to 20 carbon atoms, substituted or
unsubstituted aryl radical having 6 to 30 carbon atoms, substituted
or unsubstituted heteroaryl radical having 5 to 18 carbon atoms
and/or heteroatoms, [0083] R.sup.10 is a linear or branched alkyl
radical having 1 to 20 carbon atoms, substituted or unsubstituted
aryl radical having 6 to 30 carbon atoms, and [0084] R.sup.11,
R.sup.12, [0085] R.sup.13, R.sup.14 are each independently hydrogen
or linear or branched alkyl radical having 1 to 20 carbon atoms,
and/or [0086] R.sup.1 and R.sup.14 together form a saturated or
unsaturated, linear or branched bridge optionally comprising
heteroatoms, aromatic units, heteroaromatic units and/or functional
groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms,
preferably a six-membered aromatic ring, is optionally fused.
[0087] The latter embodiment corresponds to the following general
formula (Ib):
##STR00003##
[0088] Very particularly preferred inventive heteroleptic complexes
of the general formula (I) have the ligands depicted in table 1,
especially preferably in the combinations shown:
TABLE-US-00001 TABLE 1 Ligands ##STR00004## ##STR00005## K1
##STR00006## ##STR00007## K2 ##STR00008## ##STR00009## K3
##STR00010## ##STR00011## K4 ##STR00012## ##STR00013## K5
##STR00014## ##STR00015## K6 ##STR00016## ##STR00017## K7
##STR00018## ##STR00019## K8 ##STR00020## ##STR00021## K9
##STR00022## ##STR00023## K10 ##STR00024## ##STR00025## K11
##STR00026## ##STR00027## K12 ##STR00028## ##STR00029## K13
##STR00030## ##STR00031## K14 ##STR00032## ##STR00033## K15
##STR00034## ##STR00035## K16 ##STR00036## ##STR00037## K17
##STR00038## ##STR00039## K18 ##STR00040## ##STR00041## K19
##STR00042## ##STR00043## K20 ##STR00044## ##STR00045## K21
##STR00046## ##STR00047## K22 ##STR00048## ##STR00049## K23
##STR00050## ##STR00051## K24 ##STR00052## ##STR00053## K25
##STR00054## ##STR00055## K26 ##STR00056## ##STR00057## K27
##STR00058## ##STR00059## K28 ##STR00060## ##STR00061## K29
##STR00062## ##STR00063## K30 ##STR00064## ##STR00065## K31
##STR00066## ##STR00067## K32 ##STR00068## ##STR00069## K33
##STR00070## ##STR00071## K34 ##STR00072## ##STR00073## K35
##STR00074## ##STR00075## K36 ##STR00076## ##STR00077## K37
##STR00078## ##STR00079## K38 ##STR00080## ##STR00081## K39
##STR00082## ##STR00083## K40 ##STR00084## ##STR00085## K41
##STR00086## ##STR00087## K42 ##STR00088## ##STR00089## K43
##STR00090## ##STR00091## K44 ##STR00092## ##STR00093## K45
##STR00094## ##STR00095## K46 ##STR00096## ##STR00097## K47
##STR00098## ##STR00099## K48 ##STR00100## ##STR00101## K49
##STR00102## ##STR00103## K50 ##STR00104## ##STR00105## K51
##STR00106## ##STR00107## K52 ##STR00108## ##STR00109## K53
##STR00110## ##STR00111## K54 ##STR00112## ##STR00113## K55
##STR00114## ##STR00115## K56 ##STR00116## ##STR00117## K57
##STR00118## ##STR00119## K58 ##STR00120## ##STR00121## K59
##STR00122## ##STR00123## K60 ##STR00124## ##STR00125## K61
##STR00126## ##STR00127## K62 ##STR00128## ##STR00129## K63
##STR00130## ##STR00131## K64 ##STR00132## ##STR00133## K65
##STR00134## ##STR00135## K66 ##STR00136## ##STR00137## K67
##STR00138## ##STR00139## K68 ##STR00140## ##STR00141## K69
##STR00142## ##STR00143## K70 ##STR00144## ##STR00145## K71
##STR00146## ##STR00147## K72 ##STR00148## ##STR00149## K73
##STR00150## ##STR00151## K74 ##STR00152## ##STR00153## K75
##STR00154## ##STR00155## K76 ##STR00156## ##STR00157## K77
##STR00158## ##STR00159## K78 ##STR00160## ##STR00161## K79
##STR00162## ##STR00163## K80 ##STR00164## ##STR00165## K81
##STR00166## ##STR00167## K82 ##STR00168## ##STR00169## K83
##STR00170## ##STR00171## K84 ##STR00172## ##STR00173## K85
##STR00174## ##STR00175## K86 ##STR00176## ##STR00177## K87
##STR00178## ##STR00179## K88 ##STR00180## ##STR00181## K89
##STR00182## ##STR00183## K90 ##STR00184## ##STR00185## K91
##STR00186## ##STR00187## K92 ##STR00188## ##STR00189## K93
##STR00190## ##STR00191## K94 ##STR00192## ##STR00193## K95
##STR00194## ##STR00195## K96 ##STR00196## ##STR00197##
in each case where M=Ir, n=2 and m=1.
[0089] Depending on the coordination number of the metal M present
in the inventive heteroleptic complexes of the general formula (I)
and the number of carbene ligands and noncarbene ligands used,
different isomers of the corresponding heteroleptic metal complexes
may be present with the same metal M and the same nature of the
carbene ligands and noncarbene ligands used.
[0090] For example, for octahedral iridium(III) complexes with two
noncarbene ligands and one carbene ligand, the following isomers S1
to S4 are possible, each of which may be present in the form of two
enantiomers (a and b):
##STR00198## ##STR00199##
[0091] In the present application, owing to the arrangement of the
two 2-phenyl-1H-imidazole ligands, the S1a/S1b and S2a/S2b isomers
are referred to as pseudo-meridional isomers and the S3a/S3b and
S4a/S4b isomers as pseudo-facial isomers.
[0092] It has been found in accordance with the invention that,
surprisingly, the S3 and S4 isomers, when used in OLEDs, give
particularly good results with regard to efficiency and lifetime
when used in diodes. The S3a/S3b and S4a/S4b isomers, i.e. the
pseudo-facial isomers, are therefore particularly preferred in
accordance with the invention.
[0093] More preferably, the inventive complexes of the general
formula (I) which comprise two noncarbene ligands and one carbene
ligand are present as pseudo-facial isomers.
[0094] For iridium(III) complexes with one noncarbene ligand and
two carbene ligands, the following isomers T1 to T4 are possible,
each of which may in turn be present in the form of two enantiomers
(a and b):
##STR00200## ##STR00201##
[0095] In the present application, owing to the arrangement of the
two phenylcarbene ligands, the T1a/T1b and T2a/T2b isomers are
referred to as pseudo-meridional isomers and the T3a/T3b and
T4a/T4b isomers as pseudo-facial isomers.
[0096] It has been found in accordance with the invention that,
surprisingly, the T3 and T4 isomers, when used in OLEDs, usually
give particularly good results with regard to efficiency and
lifetime when used in diodes. The T3a/T3b and T4a/T4b isomers, i.e.
the pseudo-facial isomers, are therefore particularly preferred in
accordance with the invention. More preferably, the inventive
complexes of the general formula (I) which comprise one noncarbene
ligand and two carbene ligands are present as pseudo-facial
isomers.
[0097] In the case of square-planar platinum(II) complexes with one
carbene ligand and one noncarbene ligand, the two isomers U1 and U2
are possible:
##STR00202##
[0098] In general, the different isomers of the heteroleptic metal
complexes of the formula (I) can be separated by processes known to
those skilled in the art, for example by chromatography,
sublimation or crystallization. The different isomers can generally
be interconverted by suitable reaction conditions (e.g. pH),
thermally or photochemically.
[0099] The present invention relates both to the individual isomers
or enantiomers of the heteroleptic complexes of the formula (I) and
to mixtures of different isomers or enantiomers in any desired
mixing ratio.
[0100] The present invention therefore relates, in a particularly
preferred embodiment, to the inventive heteroleptic complexes with
the general and preferred definitions specified for M, A.sup.1,
A.sup.2, n, m, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12,
R.sup.13 and R.sup.14, where these have one of the following
configurations IIIa, IIIb, IVa or IVb:
##STR00203## ##STR00204##
[0101] The present invention additionally also relates to a process
for preparing an inventive heteroleptic complex of the general
formula (I) by
contacting at least one precursor compound comprising the metal M
and the at least one ligand which, in the complexes of the general
formula (I), is attached to M via noncarbene bonds with at least
one ligand which, in the complexes of the general formula (I), is
attached to M via at least one carbene bond, or the ligand
precursor thereof, for example a corresponding imidazolium salt, or
by contacting at least one precursor compound comprising the metal
M and a ligand which, in the complexes of the general formula (I),
is bonded to M via at least one carbene bond with at least one
ligand which, in the complexes of the general formula (I), is
attached to M via noncarbene bonds.
[0102] In a preferred embodiment of the process according to the
invention, a complex comprising appropriate noncarbene ligands,
attached to the appropriate metal M, preferably iridium, and
appropriate carbene ligands, preferably in deprotonated form as the
free carbene or in the form of a protected carbene, for example as
the silver-carbene complex, are contacted. Suitable precursor
compounds comprise the appropriate substituents R.sup.1 to R.sup.14
which are to be present in the complexes of the general formula
(I).
[0103] Appropriate complexes comprising appropriate noncarbene
ligands attached to the appropriate metal M, preferably iridium,
are known to those skilled in the art. In addition to the
noncarbene ligands present in the complex of the general formula
(I), these complexes used as precursor compounds may comprise
further ligands known to those skilled in the art, for example
halides, preferably chloride. Further suitable ligands are, for
example 1,5-cyclooctadiene (COD), phosphines, cyanides, alkoxides,
pseudohalides and/or alkyl.
[0104] Particularly preferred complexes comprising appropriate
noncarbene ligands, attached to the appropriate metal M, are, for
example, compounds of the general formula (VI)
##STR00205##
with the abovementioned definitions of R.sup.1, R.sup.2, R.sup.3,
R.sup.11, R.sup.12, R.sup.13 and R.sup.14, where Y may
independently be F, Cl, Br, I, methoxy or carboxylate.
[0105] Particularly preferred precursor compounds for the carbene
ligands used in complexes of the general formula (I) correspond,
for example, to the general formulae (VII) or (VIII)
##STR00206##
with the abovementioned definitions of R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8, R.sup.9, R.sup.10 and A, where Z may be F, Cl,
Br, I, BF.sub.4, PF.sub.6, ClO.sub.4 or SbF.sub.6.
[0106] The carbene ligand precursors are deprotonated, preferably
before the reaction, for example, by basic compounds known to those
skilled in the art, for example basic metalates, basic metal
acetates, acetylacetonates or alkoxides, or bases such as
KO.sup.tBu, NaO.sup.tBu, LiO.sup.tBu, NaH, silylamides, Ag.sub.2O
and phosphazene bases. In a further preferred embodiment, the
carbene can also be released by removing volatile substances, for
example lower alcohols such as methanol, ethanol, for example at
elevated temperature and/or reduced pressure, from precursor
compounds of the carbene ligands. Corresponding processes are known
to those skilled in the art.
[0107] The contacting is preferably effected in a solvent. Suitable
solvents are known to those skilled in the art and are preferably
selected from the group consisting of aromatic or aliphatic
solvents, for example benzene or toluene, cyclic or acyclic ethers,
alcohols, esters, amides, ketones, nitriles, halogenated compounds
and mixtures thereof. Particularly preferred solvents are toluene,
xylenes, dioxane and THF.
[0108] The molar ratio of metal-noncarbene complex used to carbene
ligand precursor used is generally 1:10 to 10:1, preferably 1:1 to
1:5, more preferably 1:2 to 1:4.
[0109] The contacting is generally effected at a temperature of 20
to 200.degree. C., preferably 50 to 150.degree. C., more preferably
60 to 130.degree. C.
[0110] The reaction time depends on the desired carbene complex and
is generally 0.02 to 50 hours, preferably 0.1 to 24 hours, more
preferably 1 to 12 hours.
[0111] The complexes of the general formula (I) obtained after the
reaction can optionally be purified by processes known to those
skilled in the art, for example washing, crystallization or
chromatography, and optionally isomerized under conditions likewise
known to those skilled in the art, for example thermally or
photochemically.
[0112] The aforementioned heteroleptic complexes and mixtures
thereof are outstandingly suitable as emitter molecules in organic
light-emitting diodes (OLEDs). Variations in the ligands make it
possible to provide corresponding complexes which exhibit
electroluminescence in the red, green and especially in the blue
region of the electromagnetic spectrum. The inventive heteroleptic
complexes of the general formula (I) are therefore outstandingly
suitable as emitter substances, since they have emission
(electroluminescence) in the visible region of the electromagnetic
spectrum, for example at 400 to 800 nm, preferably 400 to 600 nm.
The inventive heteroleptic complexes make it possible to provide
compounds which have electroluminescence in the red, green and
especially in the blue region of the electromagnetic spectrum. It
is thus possible, with the aid of the inventive heteroleptic
complexes as emitter substances, to provide industrially usable
OLEDs.
[0113] Further the inventive heteroleptic complexes of the general
formula (I) are suitable as matrix material, charge transport
material, especially hole transport material, and/or charge blocker
material.
[0114] The inventive heteroleptic complex of the general formula
(I) are preferably suitable as emitter and/or hole transport
material, more preferably as emitter.
[0115] Particular properties of the inventive heteroleptic
complexes of the general formula (I) are particularly good
efficiencies and lifetimes when used in OLEDs.
[0116] The present application therefore further provides an OLED
comprising at least one inventive heteroleptic complex of the
general formula (I). The inventive heteroleptic complex of the
general formula (I) is preferably employed in the OLED as emitter,
matrix material, charge transport material, expecially hole
transport material, and/or hole blocker, more preferably as emitter
and/or hole transport material, particularly preferably as
emitter.
[0117] The present application also provides for the use of the
heteroleptic complexes of the general formula (I) as a
light-emitting layer in OLEDs, preferably as an emitter, matrix
material, charge transport material, especially hole transport
material, and/or charge blocker, more preferably as emitter and/or
hole transport material, particularly preferably as emitter.
[0118] Organic light-emitting diodes are in principle formed from a
plurality of layers: [0119] anode (1) [0120] hole-transporting
layer (2) [0121] light-emitting layer (3) [0122]
electron-transporting layer (4) [0123] cathode (5).
[0124] However, it is also possible, that the OLED does not
comprise all of the layers mentioned, an OLED formed from the
layers (1) (anode), (3) (light-emitting layer) and (5) (cathode) is
for example also useful, wherein the functions of the layers (2)
(hole-transport layer) and (4) (electron-transporting layer) are
taken over by the adjacent layers. OLEDs comprising the layers (1),
(2), (3) and (5) respectively the layers (1), (3), (4) and (5) are
also suitable.
[0125] The heteroleptic complexes of the general formula (I) are
preferably used as emitter molecules and/or matrix materials in the
light-emitting layer (3). The inventive heteroleptic complexes of
the general formula (I) can also be employed--in addition to the
application as emitter molecules and/or matrix materials in the
light-emitting layer (3) or instead of the application in the
light-emitting layer--as charge transport material in the
hole-transporting layer (2) or in the electron-transporting layer
(4) and/or as charge blocker, wherein the application as charge
transport material in the hole-transporting layer (2)
(hole-transport material) is preferred.
[0126] The present application therefore further provides a
light-emitting layer comprising at least one of the inventive
heteroleptic complexes of the general formula (I), preferably as
emitter molecule. Preferred heteroleptic complexes of the general
formula (I) have already been specified above.
[0127] The heteroleptic complexes of the general formula (I) used
in accordance with the invention may be present in the
light-emitting layer in substance, i.e. without further additions.
However, it is also possible that, in addition to the heteroleptic
complexes of the general formula (I) used in accordance with the
invention, further compounds are present in the light-emitting
layer. For example, a fluorescent dye may be present in order to
alter the emission color of the heteroleptic complex used as the
emitter molecule. In addition, a diluent material (matrix material)
may be used. This diluent material may be a polymer, for example
poly(N-vinylcarbazole) or polysilane. The diluent material may,
however, likewise be a small molecule, for example
4,4'-N,N'-dicarbazolebiphenyl (CDP) or tertiary aromatic amines.
When a diluent material is used, the proportion of the inventive
heteroleptic complexes of the general formula (I) used in the
light-emitting layer is generally less than 40% by weight,
preferably 3 to 30% by weight. The inventive heteroleptic complexes
of the general formula (I) are preferably used in a matrix. The
light-emitting layer thus preferably comprises at least one
inventive heteroleptic complex of the general formula (I) and at
least one matrix material as diluent material.
[0128] Suitable matrix materials are--in addition to the
aforementioned dilution materials--in principle the materials
specified hereinafter as hole and electron transport materials, and
also carbene complexes, for example the carbene complexes of the
formula (I) or the carbene complexes mentioned in WO 2005/019373.
Particularly suitable are carbazole derivatives, for example
4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl (CDBP),
4,4'-bis(carbazol-9-yl)biphenyl (CBP), 1,3-bis(N-carbazolyl)benzene
(mCP), and the matrix materials specified in the following
applications: WO2008/034758, WO2009/003919.
[0129] Further suitable matrix materials, which may be small
molecules or (co)polymers of the small molecules mentioned, are
specified in the following publications:
[0130] WO2007108459 (H-1 to H-37), preferably H-20 to H-22 and H-32
to H-37, most preferably H-20, H-32, H-36, H-37, WO2008035571 A1
(Host 1 to Host 6), JP2010135467 (compounds 1 to 46 and Host-1 to
Host-39 and Host-43), WO2009008100 compounds No. 1 to No. 67,
preferably No. 3, No. 4, No. 7 to No. 12, No. 55, No. 59, No. 63 to
No. 67, more preferably No. 4, No. 8 to No. 12, No. 55, No. 59, No.
64, No. 65, and No. 67, WO2009008099 compounds No. 1 to No. 110,
WO2008140114 compounds 1-1 to 1-50, WO2008090912 compounds 00-7 to
00-36 and the polymers of Mo-42 to Mo-51, JP2008084913 H-1 to H-70,
WO2007077810 compounds 1 to 44, preferably 1, 2, 4-6, 8, 19-22, 26,
28-30, 32, 36, 39-44, WO201001830 the polymers of monomers 1-1 to
1-9, preferably of 1-3, 1-7, and 1-9, WO2008029729 the (polymers
of) compounds 1-1 to 1-36, WO20100443342 HS-1 to HS-101 and BH-1 to
BH-17, preferably BH-1 to BH-17, JP2009182298 the (co)polymers
based on the monomers 1 to 75, JP2009170764, JP2009135183 the
(co)polymers based on the monomers 1-14, WO2009063757 preferably
the (co)polymers based on the monomers 1-1 to 1-26, WO2008146838
the compounds a-1 to a-43 and 1-1 to 1-46, JP2008207520 the
(co)polymers based on the monomers 1-1 to 1-26, JP2008066569 the
(co)polymers based on the monomers 1-1 to 1-16, WO2008029652 the
(co)polymers based on the monomers 1-1 to 1-52, WO2007114244 the
(co)polymers based on the monomers 1-1 to 1-18, JP2010040830 the
compounds HA-1 to HA-20, HB-1 to HB-16, HC-1 to HC-23 and the
(co)polymers based on the monomers HD-1 to HD-12, JP2009021336,
WO2010090077 the compounds 1 to 55, WO2010079678 the compounds H1
to H42, WO2010067746, WO2010044342 the compounds HS-1 to HS-101 and
Poly-1 to Poly-4, JP2010114180 the compounds PH-1 to PH-36,
US2009284138 the compounds 1 to 111 and H1 to H71, WO2008072596 the
compounds 1 to 45, JP2010021336 the compounds H-1 to H-38,
preferably H-1, WO2010004877 the compounds H-1 to H-60,
JP2009267255 the compounds 1-1 to 1-105, WO2009104488 the compounds
1-1 to 1-38, WO2009086028, US2009153034, US2009134784, WO2009084413
the compounds 2-1 to 2-56, JP2009114369 the compounds 2-1 to 2-40,
JP2009114370 the compounds 1 to 67, WO2009060742 the compounds 2-1
to 2-56, WO2009060757 the compounds 1-1 to 1-76, WO2009060780 the
compounds 1-1 to 1-70, WO2009060779 the compounds 1-1 to 1-42,
WO2008156105 the compounds 1 to 54, JP2009059767 the compounds 1 to
20, JP2008074939 the compounds 1 to 256, JP2008021687 the compounds
1 to 50, WO2007119816 the compounds 1 to 37, WO2010087222 the
compounds H-1 to H-31, WO2010095564 the compounds HOST-1 to
HOST-61, WO2007108362, WO2009003898, WO2009003919, WO2010040777,
US2007224446 and WO06128800.
[0131] In a particularly preferred embodiment, one or more
compounds of the general formula (X) specified hereinafter are used
as matrix material. Preferred embodiments of the compounds of the
general formula (X) are likewise specified hereinafter.
[0132] The matrix materials mentioned above as well as the
compounds of the general formula (X) mentioned below are not only
applicable as matrix material in the light-emitting layer, but also
as matrix materials in other layers of an OLED, for example in the
electron-transport layer and/or in the hole transport layer. It is
also possible, to apply two or more different matrix materials
mentioned before and/or compounds of the general formula (X)
mentioned below as matrix materials.
[0133] In order to obtain particularly efficient OLEDs, the HOMO
(highest occupied molecular orbital) of the hole-transporting layer
should be aligned to the work function of the anode, and the LUMO
(lowest unoccupied molecular orbital) of the electron-transporting
layer should be aligned to the work function of the cathode.
[0134] The present application further provides an OLED comprising
at least one inventive light-emitting layer. The further layers in
the OLED may be formed from any material which is typically used in
such layers and is known to those skilled in the art.
[0135] Suitable materials for the aforementioned layers (anode,
cathode, hole and electron injection materials, hole and electron
transport materials and hole and electron blocker materials, matrix
materials, fluorescence and phosphorescence emitters) are known to
those skilled in the art and are specified, for example, in H.
Meng, N. Herron, Organic Small Molecule Materials for Organic
Light-Emitting Devices in Organic Light-Emitting Materials and
Devices, eds: Z. Li, H. Meng, Taylor & Francis, 2007, Chapter
3, pages 295 to 411.
[0136] The anode is an electrode which provides positive charge
carriers. It may be composed, for example, of materials which
comprise a metal, a mixture of different metals, a metal alloy, a
metal oxide or a mixture of different metal oxides. Alternatively,
the anode may be a conductive polymer. Suitable metals comprise the
metals of groups 11, 4, 5 and 6 of the Periodic Table of the
Elements, and also the transition metals of groups 8 to 10. When
the anode is to be transparent, mixed metal oxides of groups 12, 13
and 14 of the Periodic Table of the Elements are generally used,
for example indium tin oxide (ITO). It is likewise possible that
the anode (1) comprises an organic material, for example
polyaniline, as described, for example, in Nature, Vol. 357, pages
477 to 479 (Jun. 11, 1992). At least either the anode or the
cathode should be at least partly transparent in order to be able
to emit the light formed.
[0137] Suitable hole transport materials for layer (2) of the
inventive OLED are disclosed, for example, in Kirk-Othmer
Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages
837 to 860, 1996. Either hole-transporting molecules or polymers
may be used as the hole transport material. Customarily used
hole-transporting molecules are selected from the group consisting
of 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (.alpha.-NPD),
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine
(TPD), 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC),
N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl)bip-
henyl]-4,4'-diamine (ETPD),
tetrakis(3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA),
.alpha.-phenyl-4-N,N-diphenylaminostyrene (TPS),
p-(diethylamino)benzaldehyde diphenylhydrazone (DEH),
triphenylamine (TPA),
bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane
(MPMP),
1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyr-
azoline (PPR or DEASP), 1,2-trans-bis(9H-carbazol-9-yl)-cyclobutane
(DCZB),
N,N,N',N'-tetrakis(4-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
(TTB), fluorene compounds such as
2,2',7,7'-tetra(N,N-di-tolyl)amino-9,9-spirobifluorene (spiro-TTB),
N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-9,9-spirobifluorene
(spiro-NPB) and
9,9-bis(4-(N,N-bis-biphenyl-4-yl-amino)phenyl-9H-fluorene,
benzidine compounds such as
N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)benzidine and porphyrin
compounds such as copper phthalocyanines. Customarily used
hole-transporting polymers are selected from the group consisting
of polyvinylcarbazoles, (phenylmethyl)polysilanes and polyanilines.
It is likewise possible to obtain hole-transporting polymers by
doping hole-transporting molecules into polymers such as
polystyrene and polycarbonate. Suitable hole-transporting molecules
are the molecules already mentioned above.
[0138] In addition--in one embodiment--it is possible to use
carbene complexes as hole conductor materials, in which case the
band gap of the at least one hole conductor material is generally
greater than the band gap of the emitter material used. In the
context of the present invention, band gap is understood to mean
the triplet energy. Suitable carbene complexes are, for example,
the inventive carbene complexes of the general formula (I), carbene
complexes as described in WO 2005/019373 A2, WO 2006/056418 A2, WO
2005/113704, WO 2007/115970, WO 2007/115981 and WO 2008/000727. One
example of a suitable carbene complex is Ir(DPBIC).sub.3 with the
formula:
##STR00207##
[0139] It is likewise possible to use mixtures in the
hole-transporting layer, in particular mixtures which lead to
electrical p-doping of the hole-transporting layer. p-Doping is
achieved by the addition of oxidizing materials. These mixtures
may, for example, be the following mixtures: mixtures of the
abovementioned hole transport materials with at least one metal
oxide, for example MoO.sub.2, MoO.sub.3, WO.sub.x, ReO.sub.3,
and/or preferably MoO.sub.3 and/or ReO.sub.3, more preferably
ReO.sub.3 or mixtures comprising the aforementioned hole transport
materials and one or more compounds selected from V.sub.2O.sub.5,
7,7,8,8-tetracyanoquinodimethane (TCNQ),
2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane
(F.sub.4-TCNQ),
2,5-bis(2-hydroxyethoxy)-7,7,8,8-tetracyanoquinodimethane,
bis(tetra-n-butylammonium)tetracyanodiphenoquino-dimethane,
2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene,
11,11,12,12-tetracyanonaphtho-2,6-quinodimethane,
2-fluoro-7,7,8,8-tetracyanoquino-dimethane,
2,5-difluoro-7,7,8,8-tetracyanoquinodimethane,
dicyanomethylene-1,3,4,5,7,8-hexafluoro-6H-naphthalen-2-ylidene)malononit-
rile (F.sub.6-TNAP), Mo(tfd).sub.3 (from Kahn et al., J. Am. Chem.
Soc. 2009, 131 (35), 12530-12531), compounds as mentioned in EP 1
988 587 and in EP 2 180 029 and with quinone compounds as mentioned
in EP 09153776.1.
[0140] Suitable electron-transporting materials for layer (4) of
the inventive OLEDs comprise metals chelated with oxinoid
compounds, such as tris(8-hydroxyquinolato)aluminum (Alq.sub.3),
compounds based on phenanthroline such as
2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA=BCP),
4,7-diphenyl-1,10-phenanthroline (Bphen),
4,7-diphenyl-1,10-phenanthroline (DPA) or phenanthroline
derivatives disclosed in EP1786050 or in EP1097981, and azole
compounds such as
2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and
3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ).
Layer (4) may serve both to ease the electron transport and as a
buffer layer or as a barrier layer in order to prevent quenching of
the exciton at the interfaces of the layers of the OLED. Layer (4)
preferably improves the mobility of the electrons and reduces
quenching of the exciton.
[0141] It is likewise possible to use mixtures of at least two
materials in the electron-transporting layer, in which case at
least one material is electron-conducting. Preferably, in such
mixed electron-transporting layers, at least one phenanthroline
compound is used. More preferably, in mixed electron-transporting
layers, in addition to at least one phenanthroline compound, alkali
metal hydroxyquinolate complexes, for example Liq, are used. In
addition, it is possible to use mixtures which lead to electrical
n-doping of the electron-transporting layer. n-Doping is achieved
by the addition of reducing materials. These mixtures may, for
example, be mixtures of the abovementioned electron transport
materials with alkali/alkaline earth metals or alkali/alkaline
earth metal salts, for example Li, Cs, Ca, Sr, Cs.sub.2CO.sub.3,
with alkali metal complexes, for example 8-hydroxyquinolatolithium
(Liq), and with Y, Ce, Sm, Gd, Tb, Er, Tm, Yb, Li.sub.3N,
Rb.sub.2CO.sub.3, dipotassium phthalate, W(hpp).sub.4 from EP
1786050, or with compounds as described in EP1837926 B1.
[0142] The present invention therefore also relates to an inventive
OLED which comprises an electron-transporting layer comprising at
least two different materials, of which at least one material
should be electron-conductive.
[0143] In a preferred embodiment, the present invention relates to
an inventive OLED wherein the electron-transporting layer comprises
at least one phenanthroline derivative.
[0144] In a further preferred embodiment, the invention relates to
an inventive OLED wherein the electron-transporting layer comprises
at least one phenanthroline derivative and at least one alkali
metal hydroxyquinolate complex.
[0145] In a further preferred embodiment, the invention relates to
an inventive OLED wherein the electron-transporting layer comprises
at least one phenanthroline derivative and
8-hydroxyquinolatolithium.
[0146] Some of the materials mentioned above as hole transport
materials and electron-transporting materials can fulfill several
functions. For example, some of the electron-transporting materials
are simultaneously hole-blocking materials if they have a low-lying
HOMO.
[0147] The charge-transporting layers may also be electronically
doped in order to improve the transport properties of the materials
used, in order firstly to make the layer thickness more generous
(avoidance of pinholes/short circuits) and in order secondly to
minimize the operating voltage of the device. The hole transport
materials may for example be doped with electron acceptors,
phthalocyanines respectively arylamines like TPD or TDTA may be for
example doped with tetrafluorotetracyano-chinodimethane (F4-TCNQ).
Electronic doping is known to those skilled in the art and is
disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol.
94, No. 1, 1. July 2003 (p-doped organic layers); A. G. Werner, F.
Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett.,
Vol. 82, No. 25, 23. June 2003 and Pfeiffer et al., Organic
Electronics 2003, 4, 89-103 and K. Walzer, B. Maennig, M. Pfeiffer,
K. Leo, Chem. Soc. Rev. 2007, 107, 1233.
[0148] The cathode (5) is an electrode which serves to introduce
electrons or negative charge carriers. The cathode may be any metal
or nonmetal which has a lower work function than the anode.
Suitable materials for the cathode are selected from the group
consisting of alkali metals of group 1, for example Li, Cs,
alkaline earth metals of group 2, metals of group 12 of the
Periodic Table of the Elements, comprising the rare earth metals
and the lanthanides and actinides. In addition, metals such as
aluminum, indium, calcium, barium, samarium and magnesium, and
combinations thereof, may be used. In addition, lithium-comprising
organometallic compounds such as 8-hydroxyquinolatolithium (Liq) or
LiF or at least one of the following compounds (Cs.sub.2CO.sub.3,
KF, CsF or NaF may be applied between the organic layer and the
cathode as an electron injection layer in order to reduce the
operating voltage.
[0149] The OLED of the present invention may additionally comprise
further layers which are known to those skilled in the art. For
example, a layer which eases the transport of the positive charge
and/or matches the band gaps of the layers to one another may be
applied between the layer (2) and the light-emitting layer (3).
Alternatively, this further layer may serve as a protective layer.
In an analogous manner, additional layers may be present between
the light-emitting layer (3) and the layer (4) in order to ease the
transport of the negative charge and/or to match the band gaps
between the layers to one another. Alternatively, this layer may
serve as a protective layer.
[0150] In a preferred embodiment, the inventive OLED, in addition
to the layers (1) to (5), comprises at least one of the further
layers mentioned below: [0151] a hole injection layer between the
anode (1) and the hole-transporting layer (2); [0152] a blocking
layer for electrons between the hole-transporting layer (2) and the
light-emitting layer (3); [0153] a blocking layer for holes between
the light-emitting layer (3) and the electron-transporting layer
(4); [0154] an electron injection layer between the
electron-transporting layer (4) and the cathode (5).
[0155] As already mentioned above, however, it is also possible
that the OLED does not have all of the layers (1) to (5) mentioned;
for example, an OLED comprising layers (1) (anode), (3)
(light-emitting layer) and (5) (cathode) is likewise suitable, in
which case the functions of layers (2) (hole-transporting layer)
and (4) (electron-transporting layer) are assumed by the adjoining
layers. OLEDs having layers (1), (2), (3) and (5) or layers (1),
(3), (4) and (5) are likewise suitable.
[0156] Those skilled in the art know how suitable materials have to
be selected (for example on the basis of electrochemical
investigations). Suitable materials for the individual layers are
known to those skilled in the art and disclosed, for example, in WO
00/70655.
[0157] In addition, it is possible that some or all of the layers
(1), (2), (3), (4) and (5) have been surface-treated in order to
increase the efficiency of charge carrier transport. The selection
of the materials for each of the layers mentioned is preferably
determined by obtaining an OLED having a high efficiency.
[0158] The inventive OLED can be produced by methods known to those
skilled in the art. In general, the OLED is produced by successive
vapor deposition of the individual layers onto a suitable
substrate. Suitable substrates are, for example, glass, inorganic
materials like ITO or IZO or polymer films. For the vapor
deposition, customary techniques may be used, such as thermal
evaporation, chemical vapor deposition (CVD), physical vapor
deposition (PVD) and others.
[0159] In an alternative process, the organic layers may be coated
from solutions or dispersions in suitable solvents, in which case
coating techniques known to those skilled in the art are
employed.
[0160] Suitable coating techniques are, for example, spin-coating,
the casting method, the Langmuir-Blodgett ("LB") method, the inkjet
printing method, dip-coating, letterpress printing, screen
printing, doctor blade printing, roller printing, reverse roller
printing, offset lithography printing, flexographic printing, web
printing, spray coating, coating by a brush or pad printing, and
the like. Among the processes mentioned, in addition to the
aforementioned vapor deposition, preference is given to
spin-coating, the inkjet printing method and the casting method
since they are particularly simple and inexpensive to perform. In
the case that layers of the OLED are obtained by the spin-coating
method, the casting method or the inkjet printing method, the
coating can be obtained using a solution prepared by dissolving the
composition in a concentration of 0.0001 to 90% by weight in a
suitable organic solvent such as benzene, toluene, xylene,
tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide,
acetone, acetonitrile, anisole, dichloromethane, dimethyl
sulfoxide, water and mixtures thereof.
[0161] It is also possible that all layers of the OLED are prepared
with the same coating technique. It is further also possible that
two or more coating techniques are carried out in the production of
the layers of the OLED.
[0162] In general, the different layers have the following
thicknesses: anode (2) 500 to 5000 .ANG., preferably 1000 to 2000
.ANG. (angstrom); hole-transporting layer (3) 50 to 1000 .ANG.,
preferably 200 to 800 .ANG.; light-emitting layer (4) 10 to 1000
.ANG., preferably 100 to 800 .ANG.; electron-transporting layer (5)
50 to 1000 .ANG., preferably 200 to 800 .ANG.; cathode (6) 200 to
10 000 .ANG., preferably 300 to 5000 .ANG.. The position of the
recombination zone of holes and electrons in the inventive OLED and
thus the emission spectrum of the OLED may be influenced by the
relative thickness of each layer. This means that the thickness of
the electron transport layer should preferably be selected such
that the electron/hole recombination zone is within the
light-emitting layer. The ratio of the layer thicknesses of the
individual layers in the OLED is dependent upon the materials used.
The layer thicknesses of any additional layers used are known to
those skilled in the art.
[0163] In a preferred embodiment, the present invention also
relates to an OLED comprising at least one inventive heteroleptic
complex of the general formula (I), and at least one compound of
the general formula (X)
##STR00208##
in which [0164] T is NR.sup.57, S, O or PR.sup.57, preferably S or
O, more preferably O; [0165] R.sup.57 is aryl, heteroaryl, alkyl,
cycloalkyl or heterocycloalkyl; [0166] Q' is --NR.sup.58R.sup.59,
--P(O)R.sup.60R.sup.61, --PR.sup.62R.sup.63, --S(O).sub.2R.sup.64,
--S(O)R.sup.65, --SR.sup.66 or --OR.sup.67, preferably
--NR.sup.58R.sup.59; more preferably
[0166] ##STR00209## [0167] in which [0168] R.sup.66, R.sup.69 are
each independently alkyl, cycloalkyl, heterocycloalkyl, aryl or
heteroaryl; preferably methyl, carbazolyl, dibenzofuryl or
dibenzothienyl; [0169] y, z are each independently 0, 1, 2, 3 or 4,
preferably 0 or 1; [0170] R.sup.55, R.sup.56 are each independently
alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl,
SiR.sup.70R.sup.71R.sup.72, a Q' group or a group with donor or
acceptor action; [0171] a'' is 0, 1, 2, 3 or 4; [0172] b' is 0, 1,
2 or 3; [0173] R.sup.58, R.sup.59 form, together with the nitrogen
atom, a cyclic radical which has 3 to 10 ring atoms and may be
unsubstituted or substituted by one or more substituents selected
from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a
group with donor or acceptor action, and/or may be fused to one or
more further cyclic radicals having 3 to 10 ring atoms, where the
fused radicals may be unsubstituted or substituted by one or more
substituents selected from alkyl, cycloalkyl, heterocycloalkyl,
aryl, heteroaryl and a group with donor or acceptor action; [0174]
R.sup.70, R.sup.71, R.sup.72, R.sup.60, R.sup.61, R.sup.62,
R.sup.63, R.sup.64, R.sup.65, R.sup.66, R.sup.67 [0175] are each
independently aryl, heteroaryl, alkyl, cycloalkyl or
heterocycloalkyl,
Or
[0176] two units of the general formula (X) are bridged to one
another via a linear or branched, saturated or unsaturated bridge
optionally interrupted by at least one heteroatom, via a bond or
via O.
[0177] Preference is given to compounds of the formula (X) in
which: [0178] T is S or O, preferably O, and [0179] Q' is
[0179] ##STR00210## [0180] in which [0181] R.sup.68, R.sup.69 are
each independently alkyl, cycloalkyl, heterocycloalkyl, aryl or
heteroaryl; preferably methyl, carbazolyl, dibenzofuryl or
dibenzothienyl; [0182] y, z are each independently 0, 1, 2, 3 or 4,
preferably 0 or 1.
[0183] Particularly preferred compounds of the formula (X) have the
following formula (Xa):
##STR00211##
in which the symbols and indices Q', T, R.sup.55, R.sup.56, a'' and
b' are each as defined above.
[0184] Very particularly preferred compounds of the formula (X)
have the formula (Xaa):
##STR00212##
in which the symbols and indices R.sup.68, R.sup.69 y, z, T,
R.sup.55, R.sup.56, a'' and b' are each as defined above.
[0185] In a very particularly preferred embodiment, in formula
(Xaa): [0186] T is O or S, preferably O; [0187] a'' is 1; [0188] b'
is 0; [0189] y, z are each independently 0 or 1; and [0190]
R.sup.68, R.sup.69 are each independently methyl, carbazolyl,
dibenzofuryl or dibenzothienyl [0191] R.sup.55 is substituted
phenyl, carbazolyl, dibenzofuryl or dibenzothienyl.
[0192] In a further preferred embodiment, the compounds of the
formula (X) have the formula (XI) or (XI*):
##STR00213## [0193] in which [0194] T is NR.sup.57, S, O or
PR.sup.57; [0195] R.sup.57 is aryl, heteroaryl, alkyl, cycloalkyl
or heterocycloalkyl; [0196] Q' is --NR.sup.58R.sup.59,
--P(O)R.sup.60R.sup.61, --PR.sup.62R.sup.63, --S(O).sub.2R.sup.64,
--S(O)R.sup.65, --SR.sup.66 or --OR.sup.67; [0197] R.sup.70,
R.sup.71, R.sup.72 are each independently aryl, heteroaryl, alkyl,
cycloalkyl, heterocycloalkyl, where at least one of the R.sup.70,
R.sup.71, R.sup.72 radicals comprises at least two carbon atoms, or
OR.sup.73, [0198] R.sup.55, R.sup.56 are each independently alkyl,
cycloalkyl, heterocycloalkyl, aryl, heteroaryl, a Q group or a
group with donor or acceptor action; [0199] a', b' for the compound
of the formula (XI): are each independently 0, 1, 2, 3; for the
compound of the formula (XI*), a' is 0, 1, 2 and b' is 0, 1, 2, 3,
4; [0200] R.sup.58, R.sup.59 form, together with the nitrogen atom,
a cyclic radical which has 3 to 10 ring atoms and may be
unsubstituted or substituted by one or more substituents selected
from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a
group with donor or acceptor action and/or may be fused to one or
more further cyclic radicals having 3 to 10 ring atoms, where the
fused radicals may be unsubstituted or substituted by one or more
substituents selected from alkyl, cycloalkyl, heterocycloalkyl,
aryl, heteroaryl and a group with donor or acceptor action; [0201]
R.sup.73 are each independently SiR.sup.74R.sup.75R.sup.76, aryl,
heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, optionally
substituted by an OR.sup.77 group, [0202] R.sup.77 are each
independently SiR.sup.74R.sup.75R.sup.76, aryl, heteroaryl, alkyl,
cycloalkyl or heterocycloalkyl, [0203] R.sup.60, R.sup.61,
R.sup.62, R.sup.63, R.sup.64, R.sup.65, R.sup.66, R.sup.67,
R.sup.74, R.sup.75, R.sup.76 [0204] are each independently aryl,
heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, or two units of
the general formulae (XI) and/or (XI*) are bridged to one another
via a linear or branched, saturated or unsaturated bridge
optionally interrupted by at least one heteroatom or via O, where
this bridge in the general formulae (XI) and/or (XI*) is in each
case attached to the silicon atoms in place of R.sup.71.
[0205] The compounds of the general formula (X) can be used as a
matrix (diluent material), hole/exciton blocker, electron/exciton
blocker, electron transport material or hole transport material in
combination with the heteroeleptic complexes claimed, which then
preferably serve as emitters. Inventive OLEDs which include both at
least one compound of the formula (X) and a compound of the formula
(I) exhibit particularly good efficiencies and lifetimes. Depending
on the function in which the compound of the formula (X) is used,
it is present in pure form or in different mixing ratios. In a
particularly preferred embodiment, one or more compounds of the
formula (X) are used as matrix material in the light-emitting
layer.
[0206] For the compounds of the general formula (X), especially for
the R.sup.55 to R.sup.77 radicals:
[0207] The terms aryl radical or group, heteroaryl radical or
group, alkyl radical or group, cycloalkyl radical or group,
heterocycloalkyl radical or group, alkenyl radical or group,
alkynyl radical or group, and groups with donor and/or acceptor
action are each defined as follows:
[0208] An aryl radical (or group) is understood to mean a radical
having a base skeleton of 6 to 30 carbon atoms, preferably 6 to 18
carbon atoms, which is formed from an aromatic ring or a plurality
of fused aromatic rings. Suitable base skeletons are, for example,
phenyl, naphthyl, anthracenyl or phenanthrenyl, indenyl or
fluorenyl. This base skeleton may be unsubstituted (which means
that all carbon atoms which are substitutable bear hydrogen atoms),
or may be substituted at one, more than one or all substitutable
positions of the base skeleton.
[0209] Suitable substituents are, for example, deuterium, alkoxy
radicals, aryloxy radicals, alkylamino groups, arylamino groups,
carbazolyl groups, silyl groups, SiR.sup.78R.sup.79R.sup.80,
suitable silyl groups SiR.sup.78R.sup.79R.sup.80 being specified
below, alkyl radicals, preferably alkyl radicals having 1 to 8
carbon atoms, more preferably methyl, ethyl or i-propyl, aryl
radicals, preferably C.sub.6-aryl radicals, which may in turn be
substituted or unsubstituted, heteroaryl radicals, preferably
heteroaryl radicals which comprise at least one nitrogen atom, more
preferably pyridyl radicals and carbazolyl radicals, alkenyl
radicals, preferably alkenyl radicals which bear one double bond,
more preferably alkenyl radicals having one double bond and 1 to 8
carbon atoms, alkynyl radicals, preferably alkynyl radicals having
one triple bond, more preferably alkynyl radicals having one triple
bond and 1 to 8 carbon atoms or groups with donor or acceptor
action. Suitable groups with donor or acceptor action are specified
below. The substituted aryl radicals most preferably bear
substituents selected from the group consisting of methyl, ethyl,
isopropyl, alkoxy, heteroaryl, halogen, pseudohalogen and amino,
preferably arylamino. The aryl radical or the aryl group is
preferably a C.sub.6-C.sub.18-aryl radical, more preferably a
C.sub.6-aryl radical, which is optionally substituted by at least
one or more than one of the aforementioned substituents. The
C.sub.6-C.sub.18-aryl radical, preferably C.sub.6-aryl radical,
more preferably has none, one, two, three or four, most preferably
none, one or two, of the aforementioned substituents.
[0210] A heteroaryl radical or a heteroaryl group is understood to
mean radicals which differ from the aforementioned aryl radicals in
that at least one carbon atom in the base skeleton of the aryl
radicals is replaced by a heteroatom, and in that the base skeleton
of the heteroaryl radicals preferably has 5 to 18 ring atoms.
Preferred heteroatoms are N, O and S. Heteroaryl radicals suitable
with particular preference are nitrogen-containing heteroaryl
radicals. Most preferably, one or two carbon atoms of the base
skeleton are replaced by heteroatoms, preferably nitrogen. The base
skeleton is especially preferably selected from systems such as
pyridine, pyrimidine and five-membered heteroaromatics such as
pyrrole, furan, pyrazole, imidazole, thiophene, oxazole, thiazole,
triazole. In addition, the heteroaryl radicals may be fused ring
systems, for example benzofuryl, benzothienyl, benzopyrrolyl,
dibenzofuryl, dibenzothienyl, phenanthrolinyl, carbazolyl radicals,
azacarbazolyl radicals or diazacarbazolyl radicals. The base
skeleton may be substituted at one, more than one or all
substitutable positions of the base skeleton. Suitable substituents
are the same as have already been specified for the aryl
groups.
[0211] An alkyl radical or an alkyl group is understood to mean a
radical having 1 to 20 carbon atoms, preferably 1 to 10 carbon
atoms, more preferably 1 to 8, most preferably 1 to 4 carbon atoms.
This alkyl radical may be branched or unbranched and optionally be
interrupted by one or more heteroatoms, preferably Si, N, O or S,
more preferably N, O or S. In addition, this alkyl radical may be
substituted by one or more of the substituents specified for the
aryl groups. In addition, the alkyl radicals present in accordance
with the invention may have at least one halogen atom, for example
F, CI, Br or I, especially F. In a further embodiment, the alkyl
radicals present in accordance with the invention may be fully
fluorinated. It is likewise possible that the alkyl radical bears
one or more (hetero)aryl groups. In the context of the present
application, for example, benzyl radicals are thus substituted
alkyl radicals. In this context, all of the (hetero)aryl groups
listed above are suitable. The alkyl radicals are more preferably
selected from the group consisting of methyl, ethyl, isopropyl,
n-propyl, n-butyl, iso-butyl and tert-butyl, very particular
preference being given to methyl and ethyl.
[0212] A cycloalkyl radical or a cycloalkyl group is understood to
mean a radical having 3 to 20 carbon atoms, preferably 3 to 10
carbon atoms, more preferably 3 to 8 carbon atoms. This base
skeleton may be unsubstituted (which means that all carbon atoms
which are substitutable bear hydrogen atoms) or substituted at one,
more than one or all substitutable positions of the base skeleton.
Suitable substituents are the groups already mentioned above for
the aryl radicals. It is likewise possible that the cycloalkyl
radical bears one or more (hetero)aryl groups. Examples of suitable
cycloalkyl radicals are cyclopropyl, cyclopentyl and
cyclohexyl.
[0213] A heterocycloalkyl radical or a heterocycloalkyl group is
understood to mean radicals which differ from the aforementioned
cycloalkyl radicals in that at least one carbon atom in the base
skeleton of the cycloalkyl radicals is replaced by a heteroatom.
Preferred heteroatoms are N, O and S. Most preferably, one or two
carbon atoms of the base skeleton of the cycloalkyl radicals are
replaced by heteroatoms. Examples of suitable heterocycloalkyl
radicals are radicals derived from pyrrolidine, piperidine,
piperazine, tetrahydrofuran, dioxane.
[0214] An alkenyl radical or an alkenyl group is understood to mean
a radical which corresponds to the aforementioned alkyl radicals
having at least two carbon atoms, with the difference that at least
one C--C single bond of the alkyl radical is replaced by a C--C
double bond. The alkenyl radical preferably has one or two double
bonds.
[0215] An alkynyl radical or an alkynyl group is understood to mean
a radical which corresponds to the aforementioned alkyl radicals
having at least two carbon atoms, with the difference that at least
one C--C single bond of the alkyl radical is replaced by a C--C
triple bond. The alkynyl radical preferably has one or two triple
bonds.
[0216] An SiR.sup.78R.sup.79R.sup.80 group is understood to mean a
silyl radical in which
[0217] R.sup.78, R.sup.79 and R.sup.80 are each independently
alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or
OR.sup.73.
[0218] An SiR.sup.74R.sup.75R.sup.76 group is understood to mean a
silyl radical in which
[0219] R.sup.74, R.sup.75 and R.sup.76 are each independently
alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or
OR.sup.73.
[0220] In the context of the present application, a group or a
substituent with donor or acceptor action is understood to mean the
following groups:
[0221] Groups with donor action are understood to mean groups which
have a +I and/or +M effect, and groups with acceptor action are
understood to mean groups which have a --I and/or -M effect.
Preferred suitable groups are selected from
C.sub.1-C.sub.20-alkoxy, C.sub.6-C.sub.30-aryloxy,
C.sub.1-C.sub.20-alkylthio, C.sub.6-C.sub.30-arylthio,
SiR.sup.81R.sup.82R.sup.83, OR.sup.73, halogen radicals,
halogenated C.sub.1-C.sub.20-alkyl radicals, carbonyl
(--CO(R.sup.81)), carbonylthio (--C.dbd.O(SR.sup.81)), carbonyloxy
(--C.dbd.O(OR.sup.81)), oxycarbonyl (--OC.dbd.O(R.sup.81)),
thiocarbonyl (--SC.dbd.O(R.sup.81)), amino (--NR.sup.81R.sup.82),
pseudohalogen radicals, amido (--C.dbd.O(NR.sup.81)),
--NR.sup.81C.dbd.O(R.sup.83), phosphonate (--P(O)(OR.sup.81).sub.2,
phosphate (--OP(O)(OR.sup.81).sub.2), phosphine
(--PR.sup.81R.sup.82), phosphine oxide (--P(O)R.sup.81.sub.2),
sulfate (--OS(O).sub.2OR.sup.81), sulfoxide (--S(O)R.sup.81),
sulfonate (--S(O).sub.2OR.sup.81), sulfonyl (--S(O).sub.2R.sup.81,
sulfonamide (--S(O).sub.2NR.sup.81R.sup.82), NO.sub.2, boronic
esters (--OB(OR.sup.81).sub.2), imino (--C.dbd.NR.sup.81R.sup.82)),
borane radicals, stannane radicals, hydrazine radicals, hydrazone
radicals, oxime radicals, nitroso groups, diazo groups, vinyl
groups, sulfoximines, alanes, germanes, boroximes and
borazines.
[0222] The R.sup.81, R.sup.82 and R.sup.83 radicals mentioned in
the aforementioned groups with donor or acceptor action are each
independently:
substituted or unsubstituted C.sub.1-C.sub.20-alkyl or substituted
or unsubstituted C.sub.6-C.sub.30-aryl, or OR.sup.76, suitable and
preferred alkyl and aryl radicals having been specified above. The
R.sup.81, R.sup.82 and R.sup.83 radicals are more preferably
C.sub.1-C.sub.6-alkyl, e.g. methyl, ethyl or i-propyl, or phenyl.
In a preferred embodiment--in the case of
SiR.sup.81R.sup.82R.sup.83--R.sup.81, R.sup.82 and R.sup.83 are
preferably each independently substituted or unsubstituted
C.sub.1-C.sub.20-alkyl or substituted or unsubstituted aryl,
preferably phenyl.
[0223] Preferred substituents with donor or acceptor action are
selected from the group consisting of:
C.sub.1- to C.sub.20-alkoxy, preferably C.sub.1-C.sub.6-alkoxy,
more preferably ethoxy or methoxy; C.sub.6-C.sub.30-aryloxy,
preferably C.sub.6-C.sub.10-aryloxy, more preferably phenyloxy;
SiR.sup.81R.sup.82R.sup.83 where R.sup.81, R.sup.82 and R.sup.83
are preferably each independently substituted or unsubstituted
alkyl or substituted or unsubstituted aryl, preferably phenyl; more
preferably, at least one of the R.sup.81, R.sup.82 and R.sup.83
radicals is substituted or unsubstituted phenyl, suitable
substituents having been specified above; halogen radicals,
preferably F, Cl, more preferably F, halogenated
C.sub.1-C.sub.20-alkyl radicals, preferably halogenated
C.sub.1-C.sub.6-alkyl radicals, most preferably fluorinated
C.sub.1-C.sub.6-alkyl radicals, e.g. CF.sub.3, CH.sub.2F, CHF.sub.2
or C.sub.2F.sub.5; amino, preferably dimethylamino, diethylamino or
diarylamino, more preferably diarylamino; pseudohalogen radicals,
preferably CN, --C(O)OC.sub.1-C.sub.4-alkyl, preferably --C(O)OMe,
P(O)R.sub.2, preferably P(O)Ph.sub.2.
[0224] Very particularly preferred substituents with donor or
acceptor action are selected from the group consisting of methoxy,
phenyloxy, halogenated C.sub.1-C.sub.4-alkyl, preferably CF.sub.3,
CH.sub.2F, CHF.sub.2, C.sub.2F.sub.5, halogen, preferably F, CN,
SiR.sup.81R.sup.82R.sup.83, suitable R.sup.81, R.sup.82 and
R.sup.83 radicals already having been specified, diarylamino
(NR.sup.84R.sup.85 where R.sup.84, R.sup.85 are each
C.sub.6-C.sub.30-aryl), --C(O)OC.sub.1-C.sub.4-alkyl, preferably
--C(O)OMe, P(O)Ph.sub.2.
[0225] Halogen groups are preferably understood to mean F, Cl and
Br, more preferably F and Cl, most preferably F.
[0226] Pseudohalogen groups are preferably understood to mean CN,
SCN and OCN, more preferably CN.
[0227] The aforementioned groups with donor or acceptor action do
not rule out the possibility that further radicals and substituents
mentioned in the present application, but not included in the above
list of groups with donor or acceptor action, have donor or
acceptor action.
[0228] The aryl radicals or groups, heteroaryl radicals or groups,
alkyl radicals or groups, cycloalkyl radicals or groups,
heterocycloalkyl radicals or groups, alkenyl radicals or groups and
groups with donor and/or acceptor action may--as mentioned
above--be substituted or unsubstituted. In the context of the
present application, an unsubstituted group is understood to mean a
group in which the substitutable atoms of the group bear hydrogen
atoms. In the context of the present application, a substituted
group is understood to mean a group in which one or more
substitutable atom(s) bear(s) a substituent in place of a hydrogen
atom at least at one position. Suitable substituents are the
substituents specified above for the aryl radicals or groups.
[0229] When radicals having the same numbering occur more than once
in the compounds according to the present application, these
radicals may each independently have the definitions specified.
[0230] The T radical in the compounds of the formula (X) is
NR.sup.57, S, O or PR.sup.57, preferably NR.sup.57, S or O, more
preferably O or S, most preferably O.
[0231] The R.sup.57 radical is aryl, heteroaryl, alkyl, cycloalkyl
or heterocycloalkyl, preferably aryl, heteroaryl or alkyl, more
preferably aryl, where the aforementioned radicals may be
unsubstituted or substituted. Suitable substituents have been
specified above. R.sup.65 is more preferably phenyl which may be
substituted by the aforementioned substituents or unsubstituted.
R.sup.57 is most preferably unsubstituted phenyl.
[0232] The Q' group in the compounds of the formula (X) is
--NR.sup.58R.sup.59, --P(O)R.sup.60R.sup.61, --PR.sup.62R.sup.63,
--S(O).sub.2R.sup.64, --S(O)R.sup.65, --SR.sup.66 or --OR.sup.67;
preferably NR.sup.58R.sup.59, --P(O)R.sup.60R.sup.61 or
--OR.sup.67, more preferably --NR.sup.58R.sup.59.
[0233] The R.sup.58 to R.sup.67 and R.sup.74 to R.sup.76 radicals
are each defined as follows: [0234] R.sup.58, R.sup.59 form,
together with the nitrogen atom, a cyclic radical which has 3 to 10
ring atoms and may be unsubstituted or substituted by one or more
substituents selected from alkyl, cycloalkyl, heterocycloalkyl,
aryl, heteroaryl and a group with donor or acceptor action and/or
may be fused to one or more further cyclic radicals having 3 to 10
ring atoms, where the fused radicals may be unsubstituted or
substituted by one or more substituents selected from alkyl,
cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with
donor or acceptor action; [0235] R.sup.60, R.sup.61, R.sup.62,
R.sup.63, R.sup.64, R.sup.65, R.sup.66, R.sup.67, R.sup.74,
R.sup.75, R.sup.76 [0236] are each independently aryl, heteroaryl,
alkyl, cycloalkyl or heterocycloalkyl, preferably aryl or
heteroaryl, where the radicals may be unsubstituted or substituted
by one or more of the radicals selected from alkyl, cycloalkyl,
heterocycloalkyl, aryl, heteroaryl and a group with donor or
acceptor action, more preferably unsubstituted or substituted
phenyl, suitable substituents having been specified above, for
example tolyl or a group of the formula
[0236] ##STR00214## [0237] in which the T group and the R.sup.70,
R.sup.71 and R.sup.72 radicals are each independently as defined
for the compounds of the formula (XI) or (XI*). R.sup.69, R.sup.61,
R.sup.62, R.sup.63, R.sup.64, R.sup.65, R.sup.66 and R.sup.67 are
most preferably each independently phenyl, tolyl or a group of the
formula
##STR00215##
[0237] in which T is NPh, S or O.
[0238] Examples of --NR.sup.58R.sup.59 groups suitable with
preference are selected from the group consisting of pyrrolyl,
2,5-dihydro-1-pyrrolyl, pyrrolidinyl, indolyl, indolinyl,
isoindolinyl, carbazolyl, azacarbazolyl, diazacarbazolyl,
imidazolyl, imidazolinyl, benzimidazolyl, pyrazolyl, indazolyl,
1,2,3-triazolyl, benzotriazolyl, 1,2,4-triazolyl, tetrazolyl,
1,3-oxazolyl, 1,3-thiazolyl, piperidyl, morpholinyl,
9,10-dihydroacridinyl and 1,4-oxazinyl, where the aforementioned
groups may be unsubstituted or substituted by one or more
substituents selected from alkyl, cycloalkyl, heterocycloalkyl,
aryl, heteroaryl and a group with donor or acceptor action; the
--NR.sup.6R.sup.7 group is preferably selected from carbazolyl,
pyrrolyl, indolyl, imidazolyl, benzimidazolyl, azacarbazolyl and
diazacarbazolyl, where the aforementioned groups may be
unsubstituted or substituted by one or more substituents selected
from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a
group with donor or acceptor action; the --NR.sup.58R.sup.59 group
is more preferably carbazolyl which may be unsubstituted or
substituted by one or more substituents selected from alkyl,
cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with
donor or acceptor action.
[0239] Particularly preferred --NR.sup.58R.sup.59 groups are:
##STR00216## [0240] in which [0241] R.sup.68, R.sup.69 are each
independently alkyl, cycloalkyl, heterocycloalkyl, aryl or
heteroaryl; preferably methyl, carbazolyl, dibenzofuryl or
dibenzothienyl; [0242] y, z are each independently 0, 1, 2, 3 or 4,
preferably 0 or 1; for example:
##STR00217##
[0243] Particularly preferred --P(O)R.sup.60R.sup.61 groups
are:
##STR00218##
[0244] A particularly preferred PR.sup.62R.sup.63 group is:
##STR00219##
[0245] Particularly preferred groups --S(O).sub.2R.sup.64 and
--S(O)R.sup.65 are:
##STR00220##
[0246] Particularly preferred groups --SR.sup.66 and --OR.sup.67
are:
##STR00221##
[0247] R.sup.55, R.sup.56 in the compounds of the formula (X) are
each independently alkyl, cycloalkyl, heterocycloalkyl, aryl,
heteroaryl, a further A group or a group with donor or acceptor
action; preferably each independently alkyl, aryl, heteroaryl or a
group with donor or acceptor action. For example, R.sup.55 or
R.sup.56 may each independently be:
##STR00222##
[0248] In the compounds of the formula (X) a'' R.sup.55 groups
and/or b' R.sup.56 groups may be present, where a'' and b' are:
a'' is 0, 1, 2, 3 or 4; preferably independently 0, 1 or 2; b' is
0, 1, 2 or 3; preferably independently 0, 1 or 2.
[0249] Most preferably at least a'' or b' is 0, very especially
preferably a'' and b' are each 0 or a'' is 1 and b' is 0.
[0250] R.sup.73 in the compounds of the general formula (XI) is
generally independently SiR.sup.74R.sup.75R.sup.76, aryl,
heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, optionally
substituted by an OR.sup.77 group.
[0251] R.sup.77 in compounds of the general formula (XI) is
generally independently aryl, heteroaryl, alkyl, cycloalkyl or
heterocycloalkyl.
[0252] The OR.sup.77 substituent optionally present may generally
be present in the radicals mentioned at all sites which appear
suitable to the person skilled in the art.
[0253] In a further embodiment, two units of the general formula
(XI) and/or (XI*) are bridged to one another via a linear or
branched, saturated or unsaturated bridge optionally interrupted by
at least one heteroatom or via O, where this bridge in the general
formula (XI) and/or (XI*) is in each case attached to the silicon
atoms in place of R.sup.71.
[0254] This bridge is preferably selected from the group consisting
of --CH.sub.2--, --C.sub.2H.sub.4--, --C.sub.4H.sub.8--,
--C.sub.6H.sub.12--, --C.sub.8H.sub.16--, --C.sub.9H.sub.18--,
--CH(C.sub.8H.sub.17)CH.sub.2--, --C.sub.2H.sub.4(CF.sub.2).sub.8
C.sub.2H.sub.4--, --C.ident.C--,
-1,4-(CH.sub.2).sub.2-phenyl-(CH.sub.2).sub.2--,
1,3-(CH.sub.2).sub.2-phenyl-(CH.sub.2).sub.2--, -1,4-phenyl-,
-1,3-phenyl-, --O--, --O--Si(CH.sub.3).sub.2--O--,
--O--Si(CH.sub.3).sub.2--O--Si(CH.sub.3).sub.2--O--, --O--.
[0255] In a preferred embodiment of the present application, the
compounds of the general formula (X) have the general formula
(XIa), (XIb), (XIc), (XId) or (XIe), i.e. they are preferred
embodiments of the compounds of the general formula (XI) or
(XI*):
##STR00223##
in which the Q', T, R.sup.70, R.sup.71, R.sup.72, R.sup.55,
R.sup.56 radicals and groups, and a' and b', are each as defined
above.
[0256] In another embodiment preferred in accordance with the
invention, R.sup.70, R.sup.71 or R.sup.72 in the compounds of the
general formula (XI) or (XI*) are aromatic units of the general
formulae (XIi) and/or (XIi*)
##STR00224##
where R.sup.55, R.sup.56, Q', T, a' and b' are each as defined
above.
[0257] The present invention therefore relates, in one embodiment,
to an inventive OLED where R.sup.70, R.sup.71 or R.sup.72 in the
compounds of the general formula (XI) or (XI*) are aromatic units
of the general formulae (XIi) and/or (XIi*)
##STR00225##
where R.sup.56, R.sup.56, Q', T, a' and b' are each as defined
above.
[0258] In a preferred embodiment, the present invention relates to
an OLED wherein the compound of the general formula (XI) or (XI*)
is selected from the following group:
##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230##
##STR00231## ##STR00232## ##STR00233##
[0259] In these particularly preferred compounds of the general
formula (XI) or (XI*): [0260] T is S or O, and [0261] R' is H or
CH.sub.3; and [0262] R.sup.70, R.sup.71, R.sup.72 are each phenyl,
carbazolyl, dibenzofuran or dibenzothiophene.
[0263] Further particularly suitable compounds of the general
formula (XI) or (XI*) are:
##STR00234## ##STR00235## ##STR00236## ##STR00237##
[0264] In these particularly preferred compounds of the general
formula (XI) or (XI*) too, T is O or S, preferably O.
[0265] Further inventive compounds of the general formula (XI) or
(XI*) correspond to the following formula (XII)
##STR00238##
[0266] In the general formula (XII), R.sup.70, R.sup.71, R.sup.72
are each defined as follows:
TABLE-US-00002 Nr R.sup.70 R.sup.71 R.sup.72 1 methyl methyl ethyl
2 methyl methyl i-propyl 3 methyl methyl n-propyl 4 methyl methyl
n-butyl 5 methyl methyl i-butyl 6 methyl methyl t-butyl 7 methyl
methyl n-pentyl 8 methyl methyl n-hexyl 9 methyl methyl
--CH.sub.2CH.sub.2C(CH.sub.3).sub.3 10 methyl methyl
n-C.sub.8H.sub.17 11 methyl methyl i-C.sub.8H.sub.17 12 methyl
methyl n-C.sub.10H.sub.21 13 methyl methyl n-C.sub.12H.sub.25 16
methyl methyl n-C.sub.18H.sub.37 17 methyl methyl
n-C.sub.30H.sub.61 19 methyl methyl cyclohexyl 20 methyl methyl
C(CH.sub.3).sub.2Ph 21 methyl methyl
--C(CH.sub.3).sub.2CH(CH.sub.3).sub.2 22 methyl methyl
--CCH.sub.2CH(CH.sub.3)(C.sub.2H.sub.5) 23 methyl methyl
--CH.sub.2CH(C.sub.10H.sub.21).sub.2 24 methyl methyl
--CH.sub.2CH(C.sub.12H.sub.25).sub.2 25 methyl methyl
--CH.sub.2CH.sub.2(C.sub.3F.sub.6)CF.sub.3 26 methyl methyl
--CH.sub.2CH.sub.2(C.sub.7F.sub.14)CF.sub.3 27 methyl methyl
--CH.sub.2CH.sub.2(C.sub.5F.sub.10)CF.sub.3 29 methyl methyl
--CH.sub.2CH.sub.2CF.sub.3 30 methyl methyl phenyl 31 methyl methyl
2-biphenyl 32 methyl methyl p-tolyl 33 methyl methyl C.sub.6F.sub.5
34 methyl methyl 3,5-(cf.sub.3).sub.2phenyl 35 methyl methyl
--ch.sub.2c(ch.sub.3).sub.2phenyl 36 methyl methyl 9-fluorenyl 37
methyl methyl 3,6-di(tert-butyl)-9-fluorenyl 15 methyl methyl
R.sup.86 38 methyl methyl --OMe 39 methyl methyl --OEt 40 methyl
methyl 2,4,6-t-butylphenoxy 41 methyl methyl --O--tBu (tert-butoxy)
42 methyl methyl --OSiEt.sub.3 43 methyl ethyl ethyl 44 methyl
ethyl phenyl 45 methyl ethyl R.sup.86 46 methyl n-propyl n-propyl
47 methyl n-propyl phenyl 48 methyl n-propyl R.sup.86 49 methyl
i-propyl i-propyl 50 methyl i-propyl phenyl 51 methyl i-propyl
R.sup.86 52 methyl n-butyl n-butyl 53 methyl n-butyl phenyl 54
methyl n-butyl R.sup.86 55 methyl i-butyl i-butyl 56 methyl i-butyl
phenyl 57 methyl i-butyl R.sup.86 58 methyl t-butyl t-butyl 59
methyl t-butyl phenyl 60 methyl t-butyl R.sup.86 61 methyl n-pentyl
n-Pentyl 62 methyl n-pentyl n-hexyl 63 methyl n-pentyl phenyl 64
methyl n-pentyl R.sup.86 65 methyl n-hexyl hexyl 66 methyl n-hexyl
phenyl 67 methyl n-hexyl R.sup.86 68 methyl n-heptyl R.sup.86 69
methyl n-octyl R.sup.86 70 methyl n-decyl R.sup.86 71 methyl
n-C.sub.12H.sub.25 R.sup.86 72 methyl n-C.sub.18H.sub.37 R.sup.86
73 methyl n-C.sub.22H.sub.45 R.sup.86 74 methyl n-C.sub.30H.sub.61
R.sup.86 75 methyl cyclopentyl cyclopentyl 76 methyl cyclopentyl
phenyl 77 methyl cyclopentyl R.sup.86 78 methyl cyclohexyl
cyclohexyl 79 methyl cyclohexyl phenyl 80 methyl cyclohexyl
R.sup.86 81 methyl --CF.sub.2CHF.sub.2 R.sup.86 82 methyl
--CH.sub.2CH.sub.2CF.sub.3 R.sup.86 83 methyl
--CH.sub.2CH.sub.2(CF.sub.2).sub.3CF.sub.3 R.sup.86 84 methyl
--CH.sub.2CH.sub.2(CF.sub.2).sub.5CF.sub.3 R.sup.86 85 methyl
--CH.sub.2CH.sub.2(CF.sub.2).sub.7CF.sub.3 R.sup.86 86 methyl
phenyl phenyl 87 methyl phenyl p-tolyl 89 methyl phenyl mesityl 90
methyl phenyl R.sup.86 91 methyl p-tolyl p-tolyl 92 methyl p-tolyl
R.sup.86 93 methyl mesityl mesityl 94 methyl mesityl R5 95 methyl
R.sup.86 R.sup.86 96 methyl methoxy methoxy 97 methyl ethoxy ethoxy
98 methyl --OSiEt3 --OSiEt3 99 methyl
--O--SiMe.sub.2--CH.sub.2CH.sub.2(CF.sub.2).sub.4CF.sub.3
--O--SiMe.sub.2--CH.sub.2CH.sub.2(CF.sub.2).sub.4CF.sub.3 100 ethyl
ethyl ethyl 101 ethyl ethyl n-propyl 102 ethyl ethyl i-propyl 103
ethyl ethyl n-butyl 104 ethyl ethyl i-butyl 105 ethyl ethyl t-butyl
106 ethyl ethyl phenyl 107 ethyl ethyl R5 108 ethyl phenyl phenyl
109 ethyl phenyl R.sup.86 110 ethyl R.sup.86 R.sup.86 111 ethyl
ethoxy ethoxy 112 n-propyl n-propyl n-propyl 113 n-propyl n-propyl
phenyl 114 n-propyl n-propyl R.sup.86 115 n-propyl phenyl phenyl
116 n-propyl phenyl R.sup.86 117 n-propyl R.sup.86 R.sup.86 118
i-propyl i-propyl i-propyl 119 i-propyl i-propyl phenyl 120
i-propyl i-propyl R.sup.86 121 i-propyl i-propyl 2-biphenyl 122
i-propyl i-propyl ethoxy 123 i-propyl phenyl phenyl 124 i-propyl
phenyl R.sup.86 125 i-propyl R.sup.86 R.sup.86 126 n-butyl n-butyl
n-butyl 127 n-butyl n-butyl phenyl 128 n-butyl n-butyl R.sup.86 129
n-butyl n-hexyl R.sup.86 130 n-butyl phenyl phenyl 131 n-butyl
phenyl R.sup.86 132 n-butyl R.sup.86 R.sup.86 133 sec-butyl
sec-butyl sec-butyl 134 sec-butyl sec-butyl phenyl 135 sec-butyl
sec-butyl R.sup.86 136 sec-butyl phenyl phenyl 137 sec-butyl phenyl
R.sup.86 138 sec-butyl R.sup.86 R.sup.86 139 i-butyl i-butyl
i-butyl 140 i-butyl i-butyl n-C.sub.8H.sub.17 141 i-butyl i-butyl
n-C.sub.18H.sub.37 142 i-butyl i-butyl phenyl 143 i-butyl i-butyl
R.sup.86 144 i-butyl phenyl phenyl 145 i-butyl phenyl R.sup.86 146
i-butyl R.sup.86 R.sup.86 147 t-butyl t-butyl t-butyl 148 t-butyl
t-butyl n-C.sub.8H.sub.17 149 t-butyl t-butyl phenyl 150 t-butyl
t-butyl R.sup.86 151 t-butyl phenyl phenyl 152 t-butyl phenyl R5
153 t-butyl R.sup.86 R.sup.86 154 n-pentyl n-pentyl n-pentyl 155
n-pentyl n-pentyl phenyl 156 n-pentyl n-pentyl R.sup.86 157
n-pentyl phenyl phenyl 158 n-pentyl phenyl R.sup.86 159 n-pentyl
R.sup.86 R.sup.86 160 cyclopentyl cyclopentyl cyclopentyl 161
cyclopentyl cyclopentyl phenyl 162 cyclopentyl cyclopentyl R.sup.86
163 cyclopentyl phenyl phenyl 164 cyclopentyl phenyl R.sup.86 165
cyclopentyl R.sup.86 R.sup.86 166 n-hexyl n-hexyl n-hexyl 167
n-hexyl n-hexyl phenyl 168 n-hexyl n-hexyl R.sup.86 169 n-hexyl
phenyl phenyl 170 n-hexyl phenyl R.sup.86 171 n-hexyl R.sup.86
R.sup.86 172 --CH.sub.2CH.sub.2C(CH.sub.3).sub.3
--CH.sub.2CH.sub.2C(CH.sub.3).sub.3
--CH.sub.2CH.sub.2C(CH.sub.3).sub.3 173
--CH.sub.2CH.sub.2C(CH.sub.3).sub.3
--CH.sub.2CH.sub.2C(CH.sub.3).sub.3 R.sup.86 174
--CH.sub.2CH.sub.2C(CH.sub.3).sub.3 R.sup.86 R.sup.86 175 t-hexyl
t-hexyl t-hexyl 176 t-hexyl t-hexyl R.sup.86 177 t-hexyl R.sup.86
R.sup.86 178 n-heptyl n-heptyl n-heptyl 179 n-heptyl n-heptyl
R.sup.86 180 n-heptyl R.sup.86 R.sup.86 181 n-octyl n-octyl n-octyl
182 n-octyl n-octyl R.sup.86 183 n-octyl R.sup.86 R.sup.86 184
i-octyl i-octyl i-octyl 185 i-octyl i-octyl R.sup.86 186 i-octyl
R.sup.86 R.sup.86 187 n-nonyl n-nonyl n-nonyl 188 n-nonyl n-nonyl
R.sup.86 189 n-nonyl R.sup.86 R.sup.86 190 cyclohexyl cyclohexyl
cyclohexyl 191 cyclohexyl cyclohexyl R.sup.86 192 cyclohexyl
R.sup.86 R.sup.86 193 cyclooctyl cyclooctyl cyclooctyl 194
cyclooctyl cyclooctyl R.sup.86 195 cyclooctyl R.sup.86 R.sup.86 196
n-C.sub.10H.sub.21 n-C.sub.10H.sub.21 n-C.sub.10H.sub.21 197
n-C.sub.10H.sub.21 n-C.sub.10H.sub.21 R.sup.86 198
n-C.sub.10H.sub.21 R.sup.86 R.sup.86 199 n-C.sub.11H.sub.23
n-C.sub.11H.sub.23 n-C.sub.10H.sub.23 200 n-C.sub.11H.sub.23
n-C.sub.11H.sub.23 R.sup.86 201 n-C.sub.11H.sub.23 R.sup.86
R.sup.86 202 n-C.sub.12H.sub.25 n-C.sub.12H.sub.25
n-C.sub.12H.sub.25 203 n-C.sub.12H.sub.25 n-C.sub.12H.sub.25
R.sup.86 204 n-C.sub.12H.sub.25 R.sup.86 R.sup.86 205
n-C.sub.14H.sub.29 n-C.sub.14H.sub.29 n-C.sub.14H.sub.29 206
n-C.sub.14H.sub.29 n-C.sub.14H.sub.29 R.sup.86 207
n-C.sub.14H.sub.29 R.sup.86 R.sup.86 208 n-C.sub.16H.sub.33
n-C.sub.16H.sub.33 n-C.sub.16H.sub.33 209 n-C.sub.16H.sub.33
n-C.sub.16H.sub.33 R.sup.86 210 n-C.sub.16H.sub.33 R.sup.86
R.sup.86 211 n-C.sub.18H.sub.37 n-C.sub.18H.sub.37 R.sup.86 212
n-C.sub.18H.sub.37 R.sup.86 R.sup.86 213 n-C.sub.18H.sub.37 OEt OEt
214 n-C.sub.18H.sub.37 R.sup.86 OMe 215 n-C.sub.20H.sub.41
n-C.sub.20H.sub.41 n-C.sub.20H.sub.41 216 n-C.sub.20H.sub.41
n-C.sub.20H.sub.41 R.sup.86 217 n-C.sub.20H.sub.41 R.sup.86
R.sup.86 218 n-C.sub.22 H.sub.45 n-C.sub.22H.sub.45
n-C.sub.22H.sub.45 219 n-C.sub.22H.sub.45 n-C.sub.22H.sub.45
R.sup.86 220 n-C.sub.22H.sub.45 R.sup.86 R.sup.86 221
n-C.sub.26H.sub.53 n-C.sub.26H.sub.53 n-C.sub.26H.sub.53 222
n-C.sub.26H.sub.53 n-C.sub.26H.sub.53 R.sup.86 223
n-C.sub.26H.sub.53 R.sup.86 R.sup.86 224 n-C.sub.30H.sub.61
n-C.sub.30H.sub.61 n-C.sub.30H.sub.61 225 n-C.sub.30H.sub.61
n-C.sub.30H.sub.61 R.sup.86 226 n-C.sub.30H.sub.61 R.sup.86
R.sup.86 227 --CH.sub.2-cyclohexyl --CH.sub.2-cyclohexyl R.sup.86
228 --CH.sub.2CH.sub.2CF.sub.3 --CH.sub.2CH.sub.2CF.sub.3
--CH.sub.2CH.sub.2CF.sub.3 229 --CH.sub.2CH.sub.2CF.sub.3
--CH.sub.2CH.sub.2CF.sub.3 R.sup.86 230 --CH.sub.2CH.sub.2CF.sub.3
R.sup.86 R.sup.86 231 --CH.sub.2CH.sub.2(CF.sub.2).sub.3CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.3C.sub.F3
--CH.sub.2CH.sub.2(CF.sub.2).sub.3CF.sub.3 232
--CH.sub.2CH.sub.2(CF.sub.2).sub.3CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.3CF3 R.sup.86 233
--CH.sub.2CH.sub.2(CF.sub.2).sub.3CF.sub.3 R.sup.86 R.sup.86 234
--CH.sub.2CH.sub.2(CF.sub.2).sub.5CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.5CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.5CF.sub.3 235
--CH.sub.2CH.sub.2(CF.sub.2).sub.5CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.5CF.sub.3 R.sup.86 236
--CH.sub.2CH.sub.2(CF.sub.2).sub.5CF.sub.3 R.sup.86 R.sup.86 237
--CH.sub.2CH.sub.2(CF.sub.2).sub.7CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.7CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.7CF.sub.3 238
--CH.sub.2CH.sub.2(CF.sub.2).sub.7CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.7CF.sub.3 R.sup.86 239
--CH.sub.2CH.sub.2(CF.sub.2).sub.7CF.sub.3 R.sup.86 R.sup.86 240
--CH.sub.2CH.sub.2(CF.sub.2).sub.9CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.9CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.9CF.sub.3 241
--CH.sub.2CH.sub.2(CF.sub.2).sub.9CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.9CF.sub.3 R.sup.86 242
--CH.sub.2CH.sub.2(CF.sub.2).sub.9CF.sub.3 R.sup.86 R.sup.86 243
--CH.sub.2CH.sub.2(CF.sub.2).sub.11CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.11CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.11CF.sub.3 244
--CH.sub.2CH.sub.2(CF.sub.2).sub.11CF.sub.3
--CH.sub.2CH.sub.2(CF.sub.2).sub.11CF.sub.3 R.sup.86 245
--CH.sub.2CH.sub.2(CF.sub.2).sub.11CF.sub.3 R.sup.86 R.sup.86 246
--CF.sub.2CHF.sub.2 --CF.sub.2CHF.sub.2 --CF.sub.2CHF.sub.2 247
--CF.sub.2CHF.sub.2 --CF.sub.2CHF.sub.2 R.sup.86 248
--CF.sub.2CHF.sub.2 R.sup.86 R.sup.86 249
--(CF.sub.2).sub.3CHF.sub.2 --(CF.sub.2).sub.3CHF.sub.2
--(CF.sub.2).sub.3CHF.sub.2 250 --(CF.sub.2).sub.3CHF.sub.2
--(CF.sub.2).sub.3CHF.sub.2 R.sup.86 251
--(CF.sub.2).sub.3CHF.sub.2 R86 R.sup.86 14 phenyl phenyl phenyl
252 phenyl phenyl p-tolyl 253 phenyl phenyl m-tolyl 254 phenyl
phenyl o-tolyl 255 phenyl phenyl 2-xylyl 256 phenyl phenyl 5-xylyl
257 phenyl phenyl mesityl 258 phenyl phenyl 9-fluorenyl 18 phenyl
phenyl R.sup.86 259 phenyl phenyl --O--tBu (tert-butoxy) 260 phenyl
p-tolyl p-tolyl 261 phenyl m-tolyl m-tolyl 262 phenyl o-tolyl
o-tolyl 263 phenyl 2-xylyl 2-xylyl 264 phenyl 5-xylyl 5-xylyl 265
phenyl mesityl mesityl 266 phenyl R.sup.86 R.sup.86 267 phenyl
ethoxy ethoxy 268 p-tolyl p-tolyl p-tolyl 269 p-tolyl p-tolyl
R.sup.86 270 p-tolyl R.sup.86 R.sup.86 271 m-tolyl m-tolyl m-tolyl
272 m-tolyl m-tolyl R.sup.86 273 o-tolyl o-tolyl o-tolyl 274
o-tolyl o-tolyl R.sup.86 275 2-xylyl 2-xylyl 2-xylyl 276 2-xylyl
2-xylyl R.sup.86 277 5-xylyl 5-xylyl 5-xylyl 278 5-xylyl 5-xylyl
R.sup.86 279 mesityl mesityl mesityl 280 mesityl mesityl R.sup.86
281 C.sub.6F.sub.5 C.sub.6F.sub.5 C.sub.6F.sub.5 282 C.sub.6F.sub.5
C.sub.6F.sub.5 R.sup.86 283 C.sub.6F.sub.5 R.sup.86 R.sup.86 284
R.sup.86 R.sup.86 R.sup.86 285 R.sup.86 ethoxy ethoxy 286 R.sup.86
n-butoxy n-butoxy 287 R.sup.86 R.sup.86 methoxy 288 R.sup.86
R.sup.86 ethoxy 289 R.sup.86 R.sup.86 osime.sub.3 290 R.sup.86
R.sup.86 --(CH.sub.2).sub.11O--(CH.sub.2).sub.2OCH.sub.3 291
methoxy methoxy methoxy 292 ethoxy ethoxy ethoxy 293 i-propoxy
i-propoxy i-propoxy 294 t-butoxy t-butoxy t-butoxy 295 OSiMe.sub.3
OSiMe.sub.3 osime.sub.3 296 cyclobutyl methyl 297 cyclobutyl
R.sup.86 298 cyclobutyl p-methoxyphenyl 299 cyclopentyl methyl 300
cyclopentyl R.sup.86 301 cyclohexyl methyl 302 cyclohexyl
R.sup.86
[0267] In this table,
##STR00239##
[0268] Particularly preferred compounds in which two units of the
general formulae (XI) and/or (XI*) are bridged to one another via a
linear or branched, saturated or unsaturated bridge optionally
interrupted by at least one heteroatom or via O, where this bridge
in the general formulae (XI) and/or (XI*) is in each case attached
to the silicon atoms in place of R.sup.71, correspond to the
general formula (XIII)
##STR00240##
[0269] In formula (XIII), U, R.sup.70, R.sup.71, R.sup.72,
R.sup.87, R.sup.88 and R.sup.89 are each defined as follows:
TABLE-US-00003 Nr. R70 R71 R72 R87 R88 R89 U 303 methyl R.sup.86
R.sup.86 methyl R5 R.sup.86 --CH.sub.2-- 304 methyl methyl R.sup.86
methyl methyl R.sup.86 --CH.sub.2-- 305 R.sup.86 R.sup.86 R.sup.86
R.sup.86 R.sup.86 R.sup.86 --CH.sub.2-- 306 methyl R.sup.86
R.sup.86 methyl R5 R.sup.86 --C.sub.2H.sub.4-- 307 methyl methyl
R.sup.86 methyl methyl R.sup.86 --C.sub.2H.sub.4-- 308 R.sup.86
R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86 --C.sub.2H.sub.4-- 309
methyl R.sup.86 R.sup.86 methyl R.sup.86 R.sup.86
--C.sub.3H.sub.6-- 310 methyl methyl R.sup.86 methyl methyl
R.sup.86 --C.sub.3H.sub.6-- 311 R.sup.86 R.sup.86 R.sup.86 R.sup.86
R.sup.86 R.sup.86 --C.sub.3H.sub.6-- 312 methyl R.sup.86 R.sup.86
methyl R.sup.86 R.sup.86 --C.sub.4H.sub.8-- 313 methyl methyl
R.sup.86 methyl methyl R.sup.86 --C.sub.4H.sub.8-- 314 R.sup.86
R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86 --C.sub.4H.sub.8-- 315
methyl R.sup.86 R.sup.86 methyl R.sup.86 R.sup.86
--C.sub.6H.sub.12-- 316 methyl methyl R.sup.86 methyl methyl
R.sup.86 --C.sub.6H.sub.1.sub.2-- 317 R.sup.86 R.sup.86 R.sup.86
R.sup.86 R.sup.86 R.sup.86 --C.sub.6H.sub.1.sub.2-- 318 methyl
R.sup.86 R.sup.86 methyl R.sup.86 R.sup.86 --C.sub.8H.sub.16-- 319
methyl methyl R.sup.86 methyl methyl R.sup.86 --C.sub.8H.sub.16--
320 R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86
--C.sub.8H.sub.16-- 321 methyl R.sup.86 R.sup.86 methyl R.sup.86
R.sup.86 --C.sub.9H.sub.18-- 322 methyl methyl R.sup.86 methyl
methyl R.sup.86 --C.sub.9H.sub.18-- 323 R.sup.86 R.sup.86 R.sup.86
R.sup.86 R.sup.86 R.sup.86 --C.sub.9H.sub.18-- 324 R.sup.86
R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86
--CH(C.sub.8H.sub.17)CH.sub.2-- 325 methyl R.sup.86 R.sup.86 methyl
R.sup.86 R.sup.86 --C.sub.2H.sub.4(CF.sub.2).sub.8 C.sub.2H.sub.4--
326 methyl methyl R.sup.86 methyl methyl R.sup.86
--C.sub.2H.sub.4(CF.sub.2).sub.8 C.sub.2H.sub.4-- 327 R.sup.86
R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86
--C.sub.2H.sub.4(CF.sub.2).sub.8 C.sub.2H.sub.4-- 328 methyl
R.sup.86 R.sup.86 methyl R.sup.86 R.sup.86 --C.ident.C-- 329 methyl
methyl R.sup.86 methyl methyl R.sup.86 --C.ident.C-- 330 R.sup.86
R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86 --C.ident.C-- 331
methyl R.sup.86 R.sup.86 methyl R.sup.86 R.sup.86
-1,4-(CH.sub.2).sub.2- phenyl- (CH.sub.2).sub.2-- 332 methyl methyl
R.sup.86 methyl methyl R.sup.86 -1,4-(CH.sub.2).sub.2- phenyl-
(CH.sub.2).sub.2-- 333 R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86
R.sup.86 -1,4-(CH.sub.2).sub.2- phenyl- (CH.sub.2).sub.2-- 334
methyl R.sup.86 R.sup.86 methyl R.sup.86 R.sup.86
-1,3-(CH.sub.2).sub.2- phenyl- (CH.sub.2).sub.2-- 335 methyl methyl
R.sup.86 methyl methyl R.sup.86 -1,3-(CH.sub.2).sub.2- phenyl-
(CH.sub.2).sub.2-- 336 R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86
R.sup.86 -1,3-(CH.sub.2).sub.2- phenyl- (CH.sub.2).sub.2-- 337
methyl R.sup.86 R.sup.86 methyl R.sup.86 R.sup.86
-1,4-(CH.sub.2).sub.3- phenyl- (CH.sub.2).sub.3-- 338 methyl methyl
R.sup.86 methyl methyl R.sup.86 -1,4-(CH.sub.2).sub.3- phenyl-
(CH.sub.2).sub.3-- 339 R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86
R.sup.86 -1,4-(CH.sub.2).sub.3- phenyl- (CH.sub.2).sub.3-- 340
methyl R.sup.86 R.sup.86 methyl R.sup.86 R.sup.86
-1,3-(CH.sub.2).sub.3- phenyl- (CH.sub.2).sub.3-- 341 methyl methyl
R.sup.86 methyl methyl R.sup.86 -1,3-(CH.sub.2).sub.3- phenyl-
(CH.sub.2).sub.3-- 342 R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86
R.sup.86 -1,3-(CH.sub.2).sub.3- phenyl- (CH.sub.2).sub.3-- 343
methyl R.sup.86 R.sup.86 methyl R.sup.86 R.sup.86 -1,4-phenyl- 344
methyl methyl R.sup.86 methyl methyl R.sup.86 -1,4-phenyl- 345
R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86 -1,4-phenyl-
346 methyl R.sup.86 R.sup.86 methyl R.sup.86 R.sup.86 -1,3-phenyl-
347 methyl methyl R.sup.86 methyl methyl R.sup.86 -1,3-phenyl- 348
R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86 R.sup.86 -1,3-phenyl-
28 methyl methyl R.sup.86 methyl methyl R.sup.86 --O-- 349 methyl
R.sup.86 R.sup.86 methyl R.sup.86 R.sup.86 --O-- 350 methyl methyl
R.sup.86 methyl methyl R.sup.86 --O--Si(CH.sub.3).sub.2-- O-- 351
methyl methyl R.sup.86 methyl methyl R.sup.86 --O--
Si(CH.sub.3)(Ph)-- O-- 352 methyl methyl R.sup.86 methyl methyl
R.sup.86 --O--Si(CH.sub.3).sub.2-- O--Si(CH.sub.3).sub.2-- O-- 353
methyl methyl R.sup.86 methyl methyl R.sup.86
--O--Si(CH.sub.3).sub.2-- O--Si(CH.sub.3).sub.2--
O--Si(CH.sub.3).sub.2-- O-- 354 methyl --OSiMe.sub.3 R.sup.86
methyl --OSiMe.sub.3 R.sup.86 --O-- 355 methyl phenyl R.sup.86
methyl phenyl R.sup.86 --O-- 356 i-propyl i-propyl R.sup.86
i-propyl i-propyl R.sup.86 --O-- 357 cyclopentyl cyclopentyl
R.sup.86 cyclopentyl cyclopentyl R.sup.86 --O-- 358 phenyl phenyl
R.sup.86 phenyl phenyl R.sup.86 --O-- 359 phenyl R.sup.86 R.sup.86
phenyl R.sup.86 R.sup.86 --O-- 360 R.sup.86 R.sup.86 R.sup.86
R.sup.86 R.sup.86 R.sup.86 --O--
[0270] In this table,
##STR00241##
[0271] Further suitable compounds of the formula (XI) and/or (XI*)
are specified hereinafter. R therein is independently Me, phenyl or
R.sup.86, where at least one R radical is R.sup.86:
##STR00242##
[0272] In a very particularly preferred embodiment, the present
invention relates to an OLED which, as well as at least one
metal-carbene complex of the general formula (I), comprises at
least one compound of the general formula (X), in which case the
compound of the formula (X) is most preferably at least one of the
compounds specified below:
##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247##
##STR00248##
[0273] In the aforementioned compounds, T is O or S, preferably O.
When more than one T occurs in the molecule, all T groups have the
same definition.
[0274] In addition to the compounds of the formula (X), according
to the present invention, it is also possible to use crosslinked or
polymeric materials comprising repeat units based on the general
formula (X) in crosslinked or polymerized form together with at
least one heteroeleptic complex of the general formula (I). Like
the compounds of the general formula (X), the latter are preferably
used as matrix materials.
[0275] The crosslinked or polymeric materials have outstanding
solubility in organic solvents, excellent film-forming properties
and relatively high glass transition temperatures. In addition,
high charge carrier mobilities, high stabilities of color emission
and long operating times of the corresponding components can be
observed when crosslinked or polymeric materials according to the
present invention are used in organic light-emitting diodes
(OLEDs).
[0276] The crosslinked or polymerized materials are particularly
suitable as coatings or in thin films since they are thermally and
mechanically stable and relatively defect-free.
[0277] The crosslinked or polymerized materials comprising repeat
units based on the general formula (X) can be prepared by a process
comprising steps (a) and (a): [0278] (a) preparation of a
crosslinkable or polymerizable compound of the general formula (X)
where at least one of the a'' R.sup.55 radicals or at least one of
the b' R.sup.56 radicals is a crosslinkable or polymerizable group
attached via a spacer, and [0279] (b) crosslinking or
polymerization of the compound of the general formula (X) obtained
from step (a).
[0280] The crosslinked or polymerized materials may be
homopolymers, which means that exclusively units of the general
formula (X) are present in crosslinked or polymerized form. They
may also be copolymers, which means that further monomers are
present in addition to the units of the general formula (X), for
example monomers with hole-conducting and/or electron-conducting
properties, in crosslinked or polymerized form.
[0281] In a further preferred embodiment of the inventive OLED, it
comprises an emission layer comprising at least one inventive
heteroeleptic complex of the general formula (I), at least one
matrix material of the formula (X), and optionally at least one
further hole-transporting matrix material.
[0282] The inventive OLEDs can be used in all devices in which
electroluminescence is useful. Suitable devices are preferably
selected from stationary and mobile visual display units and
illumination means. The present invention therefore also relates to
a device selected from the group consisting of stationary visual
display units and mobile visual display units and illumination
means, comprising an inventive OLED.
[0283] Stationary visual display units are, for example, visual
display units of computers, televisions, visual display units in
printers, kitchen appliances and advertising panels, illuminations
and information panels. Mobile visual display units are, for
example, visual display units in cellphones, laptops, digital
cameras, mp-3 players, smartphones, vehicles, and destination
displays on buses and trains.
[0284] In addition, the inventive heteroleptic complexes of the
general formula (I) can be used in OLEDs with inverse structure.
The inventive complexes are preferably used in turn in these
inverse OLEDs in the light-emitting layer. The structure of inverse
OLEDs and the materials typically used therein are known to those
skilled in the art.
[0285] A further embodiment of the present invention is a white
OLED comprising at least one heteroleptic complex of the general
formula (I). In a preferred embodiment, the heteroleptic complex of
the general formula (I) is employed in the white OLED as emitter
material. Preferred embodiments of the heteroleptic complex of the
general formula (I) are mentioned before. Beside the at least one
heteroleptic complex of the general formula (I) the white OLED may
comprise at least one compound of the formula (X). The compound of
formula (X) is preferably employed as matrix material. Preferred
compounds of the formula (X) are mentioned before.
[0286] In order to obtain white light, the OLED must generate light
which colors the entire visible range of the spectrum. However,
organic emitters normally emit only in a limited portion of the
visible spectrum--i.e. are colored. White light can be generated by
the combination of different emitters. Typically, red, green and
blue emitters are combined. However, the prior art also discloses
other methods for formation of white OLEDs, for example the triplet
harvesting approach. Suitable structures for white OLEDs or methods
for formation of white OLEDs are known to those skilled in the
art.
[0287] The present invention also relates to an organic electronic
component, preferably an organic light-emitting diode (OLED),
organic photovoltaic cell (OPV), organic filed-effect transistor
(OFET) or light-emitting electrochemical cell (LEEC), comprising a
least one inventive heteroleptic complex of the general formula
(I).
EXAMPLES
[0288] The examples which follow, especially the methods,
materials, conditions, process parameters, apparatus and the like,
detailed in the examples, are intended to support the present
invention, but not to restrict the scope of the present
invention.
[0289] N-(2,6-Diisopropylphenyl)-2-phenylimidazole L1 is
synthesized analogously to example 14 in WO2006/121811. The
synthesis of
5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole C1 is
effected according to D. Enders, K. Breuer, G. Raabe, J. Runsink,
J. H. Teles, J.-P. Melder, K. Ebel, S. Brode, Angew. Che--m. 1995,
107, 9, 1119-1122 or D. Enders, K. Breuer, U. Kallfass, T.
Balensiefer, Synthesis 2003, 8, 1292-1295.
3-(2,6-Dimethylphenyl)-7-methylimidazo[1,2-f]phenanthridine L3 is
synthesized analogously to example 10 in WO 2007/095118. The
synthesis of the ligand precursor
1-isopropyl-1,2,4-triazolo[4,3-f]phenanthridinium iodide C3 is
effected as described in WO 2009/050281. The synthesis of the
exciton and hole blocker 2,8-bis(triphenylsilyl)-dibenzofuran LB1
is disclosed in synthesis example 4g in WO 2009/003898.
[0290] All experiments are performed in protective gas
atmosphere.
Example 1
.mu.-Dichloro dimer D1
##STR00249##
[0292] 3.50 g (11.5 mmol) of
1-(2,6-diisopropylphenyl)-2-phenyl-1H-imidazole L1 are initially
charged in 200 ml of 2-ethoxyethanol/water (ratio 3/1) and admixed
with 1.84 g (5.2 mmol) of iridium(III) chloride trihydrate. The
reaction mixture is heated at reflux for 18 h. After cooling, 50 ml
of distilled water are added. The precipitate is filtered off,
washed with distilled water and dried. This gives 3.50 g (80%) of
.mu.-dichloro dimer D1 as a yellow powder.
[0293] .sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz):
[0294] .delta.=0.95 (d, .sup.3J.sub.H,H=6.9 Hz, 12H), 1.18 (d,
.sup.3J.sub.H,H=6.9 Hz, 12H), 1.27 (d, .sup.3J.sub.H,H=6.9 Hz,
12H), 1.34 (d, .sup.3J.sub.H,H=6.9 Hz, 12H), 2.80-2.91 (m, 8H),
6.08 (d, .sup.3J.sub.H,H=7.7 Hz, 4H), 6.24 (d, .sup.3J.sub.H,H=7.7
Hz, 4H), 6.39 (pt, .sup.3J.sub.H,H=7.5 Hz, 4H), 6.53 (pt,
.sup.3J.sub.H,H=7.5 Hz, 4H), 6.97 (d, J.sub.H,H=1.5 Hz, 4H),
7.39-7.45 (m, 8H), 7.59 (t, .sup.3J.sub.H,H=7.8 Hz, 4H), 7.67 (d,
J.sub.H,H=1.5 Hz, 4H).
Complex Em1-s:
##STR00250##
[0296] 2.37 g (7.2 mmol) of
5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole Cl are
heated to 90.degree. C. under reduced pressure for 18 h. After
cooling to room temperature, first 100 ml of anhydrous toluene and
then a suspension of 3.00 g (1.8 mmol) of chloro dimer D1 and 150
ml of anhydrous toluene are added. The mixture is heated to
90.degree. C. for 2 h. The white precipitate formed (1.15 g,
imidazolium chloride C1*) is filtered off. The filtrate is washed
with 3.times.40 ml of saturated NaHCO.sub.3 solution and 1.times.40
ml of distilled water, dried over MgSO.sub.4 and freed of the
solvent under reduced pressure. The residue is washed with
2.times.50 ml of methanol, recrystallized from methylene
chloride/methanol and then recrystallized from nitromethane. This
gives 3.2 g of the complex Em1-s as a yellow powder (82%).
##STR00251##
[0297] Em1-s: The configuration of Em1-s corresponds to the
configuration of the pseudo-meridional isomer S1a or S1b. Em1-s is
present as the racemate; for crystal structure see FIG. 1, only one
enantiomer is depicted, large sphere=C, small sphere=H. Sample for
the x-ray structure analysis is crystallized from nitromethane
(nitromethane still present in the crystals).
[0298] .sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz):
[0299] .delta.=0.88 (d, .sup.3J.sub.H,H=6.8 Hz, 3H), 0.91 (d,
.sup.3J.sub.H,H=6.9 Hz, 9H), 1.14 (d, .sup.3J.sub.H,H=6.9 Hz, 3H),
1.16 (d, .sup.3J.sub.H,H=6.8 Hz, 3H), 1.20 (d, .sup.3J.sub.H,H=6.9
Hz, 3H), 1.28 (d, .sup.3J.sub.H,H=6.9 Hz, 3H), 2.08 (sept,
.sup.3J.sub.H,H=6.7 Hz, 1H), 2.65-2.77 (m, 3H), 6.08-6.15 (m, 3H),
6.19-6.25 (m, 2H), 6.42-6.45 (m, 1H), 6.50-6.52 (m, 2H), 6.67 (s,
b, 2H), 6.71 (dt, .sup.3J.sub.H,H=7.4 Hz, J=1.2 Hz, 1H), 6.75 (d,
J=1.5 Hz, 1H), 6.79-6.87 (m, 6H), 7.00-7.07 (m, 2H), 7.28-7.43 (m,
9H), 7.50 (t, .sup.3J.sub.H,H=7.8 Hz, 1H), 7.56 (t,
.sup.3J.sub.H,H=7.8 Hz, 1H), 7.71 (d, .sup.3J.sub.H,H=7.5 Hz,
1H).
[0300] Photoluminescence (in a film, 2% in PMMA):
.lamda..sub.max=460, 490 nm, CIE: (0.19; 0.34)
Example 2
Complex Em1-i
[0301] ##STR00252## [0302] racemic in each case, only one
enantiomer of each depicted
[0303] A solution of 1.6 g of complex Em1-s in 200 ml of
3-methoxypropionitrile is irradiated at room temperature with a
blacklight blue lamp for 5 h (Osram, L18W/73,
.lamda..sub.max=370-380 nm). The solvent is removed under reduced
pressure. The residue is washed with methanol and recrystallized
from methylene chloride/methanol. This gives 1.2 g of Em1-i as a
lemon yellow powder (75%).
[0304] The configuration of Em1-i corresponds to the configuration
IVa or IVb of the pseudo-facial isomer S4a or S4b. Em1-i is present
as the racemate; for crystal structure see FIG. 2, the sample for
the x-ray structure analysis is crystallized from cyclohexane/ethyl
acetate (cyclohexane still present in the crystals).
[0305] .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz):
[0306] .delta.=0.46 (d, .sup.3J.sub.H,H=6.8 Hz, 3H), 0.75 (d,
.sup.3J.sub.H,H=6.8 Hz, 3H), 0.81 (d, .sup.3J.sub.H,H=6.8 Hz, 3H),
1.01 (d, .sup.3J.sub.H,H=6.8 Hz, 3H), 1.09 (d, .sup.3J.sub.H,H=6.9
Hz, 3H), 1.14 (d, .sup.3J.sub.H,H=6.9 Hz, 3H), 1.17 (d,
.sup.3J.sub.H,H=6.9 Hz, 3H), 1.26 (d, .sup.3J.sub.H,H=6.8 Hz, 3H),
1.50 (sept, .sup.3J.sub.H,H=6.8 Hz, 1H), 2.49-2.60 (m, 3H), 6.01
(d, J=1.3 Hz, 1H), 6.10 (t, .sup.3J.sub.H,H=8.2 Hz, 2H), 6.34 (d,
J=1.4 Hz, 1H), 6.38 (d, .sup.3J.sub.H,H=7.2 Hz, 1H), 6.41-6.45 (m,
2H), 6.57-6.73 (m, 5H), 6.85 (d, J=1.4 Hz, 1H), 6.96-7.00 (m, 1H),
7.11 (d, J=1.4 Hz, 1H), 7.17-7.42 (m, 14H), 7.46 (t,
.sup.3J.sub.H,H=7.8 Hz, 1H), 7.54 (t, .sup.3J.sub.H,H=7.8 Hz, 1H),
7.68 (d, .sup.3J.sub.H,H=8.2 Hz, 1H).
[0307] Photoluminescence (in a film, 2% in PMMA):
.lamda..sub.max=456, 488 nm, CIE: (0.21; 0.37)
[0308] The photoluminescence quantum yield of the facial isomer
Em1-i is 1.36 times the quantum yield of the meridional isomer
Em1-s.
Example 3
4-Bromodibenzofuran
##STR00253##
[0310] 100.00 g (99%, 588.6 mmol) of dibenzofuran are dissolved in
800 ml of anhydrous THF and admixed at -40.degree. C. with 400 ml
(640.0 mmol) of n-BuLi (1.6M in hexane). The cooling bath is
removed. The reaction solution is allowed to come to room
temperature in a water bath within approx. 30 min and stirred for a
further two hours. Thereafter, it is cooled to -78.degree. C. and a
solution of 160.34 g (99%, 844.9 mmol, 73.55 ml) of
1,2-dibromoethane in 80 ml of anhydrous THF is added dropwise. The
cooling bath is removed, and the mixture is allowed to come to room
temperature in a water bath within approx. 30 min and stirred for a
further two hours. Subsequently, 60 ml of saturated sodium chloride
solution are added cautiously (slightly exothermic reaction,
temperature rise 1-2.degree. C.). The organic phase is removed and
freed of the solvent under reduced pressure. The oily red-brown
residue is taken up in 900 ml of dichloromethane and washed
successively with 500 ml of HCl solution (1 N) and 400 ml of water.
The organic phase is dried over magnesium sulfate and freed of the
solvent under reduced pressure. In the course of cooling, a
yellowish solid precipitates out, which is comminuted in a mortar
and washed on a frit with 2.times.150 ml of isopropanol. After
drying, 120.36 g of beige powder are obtained (according to GC and
NMR: DBF/Br-DBF ratio=10/90, corresponds to 111.93 g of Br-DBF/76%
yield). After removing the solvent, a further 15.84 g of a mixture
of dibenzofuran and 4-bromodibenzofuran (comprises a further
approx. 7.8 g/5% Br-DBF) are obtained from the isopropanol
solution. This mixture can likewise be used in the further
stages.
[0311] .sup.1H NMR (CDCl.sub.3, 500 MHz):
[0312] .delta.=7.92 (d, .sup.3J.sub.H,H=7.8 Hz, 1H), 7.86 (dd,
.sup.3J.sub.H,H=7.7 Hz, .sup.4J.sub.H,H=1.0 Hz, 1H), 7.65 (d,
.sup.3J.sub.H,H=8.2 Hz, 1H), 7.61 (dd, .sup.3J.sub.H,H.sup.=7.8 Hz,
.sup.4J.sub.H,H=1.1 Hz, 1H), 7.50 (dt, .sup.3J.sub.H,H=8.2 Hz,
J.sub.H,H.sup.=1.3 Hz, 1H), 7.37 (dt, .sup.3J.sub.H,H=7.8 Hz,
J.sub.H,H=0.8 Hz, 1H), 7.21 (t, .sup.3J.sub.H,H=7.8 Hz, 1H).
1-Dibenzofuran-4-yl-1H-imidazole
##STR00254##
[0314] 119.00 g of the first stage (comprise 110.66 g, 447.9 mmol
of 4-bromodibenzofuran) are dissolved in 700 ml of
dimethylformamide and admixed successively with 37.15 g (545.7
mmol) of imidazole, 15.80 g (83.0 mmol) of copper(I) iodide and
83.20 g (602.0 mmol) of potassium carbonate. The mixture is stirred
at 150.degree. C. for 48 h, in the course of which a further 3.75 g
(55.1 mmol) of imidazole are added after 24 h and a further 1.93 g
(28.3 mmol) after 44 h. Thereafter, the mixture is cooled to room
temperature and the insoluble constituents are filtered off. The
filtrate is concentrated to dryness. The residue is taken up in 500
ml of methylene chloride, washed successively with 150 ml of
ammonia solution (25%) and 150 ml of water, dried over magnesium
sulfate and concentrated. This gives 82.23 g of crude product,
which is used in the next stage without further purification (78%
crude yield).
3-Dibenzofuran-4-yl-1-methyl-3H-imidazol-1-ium iodide C2
##STR00255##
[0316] 82.03 g (350.1 mmol) of 1-dibenzofuran-4-yl-1H-imidazole
(crude product) are dissolved in 1 l of tetrahydrofuran and admixed
slowly with 246.06 g (1.733 mol) of methyl iodide. The mixture is
stirred at room temperature for 65 h. The precipitate formed is
filtered off, washed with 1 l of tetrahydrofuran and dried. This
gives 98.41 g (261.6 mmol, 75%) of beige powder.
[0317] .sup.1H NMR (DMSO, 500 MHz):
[0318] .delta.=10.00 (s, 1H, NCHN), 8.49 (t, J=1.9 Hz, 1H,
CH.sub.Aryl), 8.41 (dd, .sup.3J.sub.H,H=7.8 Hz, J=1.0 Hz, 1H,
CH.sub.Aryl), 8.32-8.30 (m, 1H, CH.sub.Aryl), 8.15 (t, J=1.8 Hz,
1H, CH.sub.Aryl), 7.96 (dd, .sup.3J.sub.H,H=7.9 Hz, J=1.0 Hz, 1H,
CH.sub.Aryl), 7.84 (d, .sup.3J.sub.H,H=8.4 Hz, 1H, CH.sub.Aryl),
7.69-7.65 (m, 2H, CH.sub.Aryl), 7.53 (dt, .sup.3J.sub.H,H=7.5 Hz,
J=0.9 Hz, 1H, CH.sub.Aryl), 4.12 (s, 3H, CH.sub.3).
Complex Em2-s:
##STR00256##
[0320] 1.01 g (2.7 mmol) of imidazolium iodide C2 and 0.31 g (1.3
mmol) of Ag.sub.2O are stirred in 200 ml of anhydrous acetonitrile
at room temperature for 18 h. Then the solvent is removed under
reduced pressure. The residue is taken up in 300 ml of anhydrous
THF and 1.50 g (0.9 mmol) of chloro dimer D1 are added. Thereafter,
the mixture is heated at reflux for 24 h. After cooling, the
reaction solution is filtered. The filtrate is freed of the solvent
under reduced pressure. The residue is washed with methanol and,
after drying, 1.2 g of the complex Em2-s are obtained as a yellow
powder (64%).
[0321] .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz):
[0322] .delta.=0.86 (d, .sup.3J.sub.H,H=6.9 Hz, 3H), 0.96 (d,
.sup.3J.sub.H,H=6.8 Hz, 3H), 1.00 (d, .sup.3J.sub.H,H=6.7 Hz, 3H),
1.02 (d, .sup.3J.sub.H,H=7.1 Hz, 3H), 1.03 (d, .sup.3J.sub.H,H=7.1
Hz, 3H), 1.06 (d, .sup.3J.sub.H,H=6.9 Hz, 3H), 1.21 (d,
.sup.3J.sub.H,H=7.0 Hz, 3H), 1.23 (d, .sup.3J.sub.H,H=7.0 Hz, 3H),
2.15 (sept, .sup.3J.sub.H,H=6.9 Hz, 1H), 2.39 (sept,
.sup.3J.sub.H,H=6.9 Hz, 1H), 2.77-2.85 (m, 2H), 3.34 (s, 3H), 6.17
(bd, .sup.3J.sub.H,H=7.8 Hz, 1H), 6.20 (bd, .sup.3J.sub.H,H=7.8 Hz,
1H), 6.41 (d, J=1.5 Hz, 1H), 6.44-6.52 (m, 2H), 6.54 (d, J=1.5 Hz,
1H), 6.67-6.79 (m, 5H), 6.89 (d, .sup.3J.sub.H,H=7.4 Hz, 1H), 6.95
(d, J=1.9 Hz, 1H), 7.16 (bd, .sup.3J.sub.H,H=7.3 Hz, 1H), 7.29-7.41
(m, 7H), 7.51-7.55 (m, 2H), 7.61 (bd, .sup.3J.sub.H,H=8.1 Hz, 1H),
7.89 (bd, .sup.3J.sub.H,H=8.3 Hz, 1H), 8.46 (d, J=1.9 Hz, 1H).
[0323] Photoluminescence (in a film, 2% in PMMA):
.lamda..sub.max=460, 491 nm, CIE: (0.18; 0.33)
Example 4
Complex Em2-i
##STR00257##
[0325] A solution of 0.90 g of complex Em2-s in 200 ml of
3-methoxypropionitrile is irradiated at room temperature with a
blacklight blue lamp for 3 h (Osram, L18W/73,
.lamda..sub.max=370-380 nm). The solvent is removed under reduced
pressure. The residue is carefully washed with methanol. This gives
0.63 g Em2-i as a yellow powder (70%).
[0326] The configuration of Em2-i corresponds to the configuration
IVa or IVb of the pseudo-facial isomer S4a or S4b. Em2-1 is present
as the racemate; for crystal structure see FIG. 3, the sample for
the x-ray structure analysis was crystallized from tetra
hydrofuran/n-hepta ne.
[0327] .sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz):
[0328] .delta.=0.72 (d, .sup.3J.sub.H,H=6.8 Hz, 3H), 0.85 (d,
.sup.3J.sub.H,H=6.8 Hz, 3H), 0.90 (d, .sup.3J.sub.H,H=6.8 Hz, 3H),
0.99 (d, .sup.3J.sub.H,H=6.9 Hz, 3H), 1.02 (d, .sup.3J.sub.H,H=6.8
Hz, 3H), 1.11 (d, .sup.3J.sub.H,H=6.9 Hz, 3H), 1.19 (d,
.sup.3J.sub.H,H=7.1 Hz, 3H), 1.21 (d, .sup.3J.sub.H,H=7.1 Hz, 3H),
1.90 (sept, .sup.3J.sub.H,H=6.8 Hz, 1H), 2.46 (sept,
.sup.3J.sub.H,H=6.8 Hz, 1H), 2.60 (sept, .sup.3J.sub.H,H=6.9 Hz,
1H), 2.77 (sept, .sup.3J.sub.H,H=6.9 Hz, 1H), 3.53 (s, 3H), 6.16
(bd, .sup.3J.sub.H,H=7.7 Hz, 2H), 6.38-6.56 (m, 5H), 6.65-6.69 (m,
2H), 6.76-6.84 (m, 4H), 6.99 (d, J=1.9 Hz, 1H), 7.22 (d,
.sup.3J.sub.H,H=7.7 Hz, 1H), 7.27-7.37 (m, 6H), 7.49-7.60 (m, 3H),
7.86 (bd, .sup.3J.sub.H,H=7.2 Hz, 1H), 8.38 (d, J=1.9 Hz, 1H).
[0329] Photoluminescence (in a film, 2% in PMMA):
.lamda..sub.max=462, 490 nm, CIE: (0.17; 0.29)
[0330] The photoluminescence quantum yield of the facial isomer
Em2-i is 1.44 times the quantum yield of the isomer Em2-s.
Example 5
Complex Em3-s
##STR00258##
[0332] 6.0 g (15.5 mmol) of
1-isopropyl-1,2,4-triazolo[4,3-f]phenanthridinium iodide C3 and 2.9
g (12.3 mmol) of Ag.sub.2O are stirred in 400 ml of dioxane at room
temperature for 40 h. Subsequently, 2.6 g (1.6 mmol) of chloro
dimer D1 are added and the mixture is heated to reflux for 24 h.
After cooling to room temperature, the precipitate is filtered off
and washed with dichloromethane. The combined filtrates are
concentrated to dryness and purified by column chromatography
(silica gel, dichloromethane). After drying, 2.1 g of Em3-s are
obtained as yellow powder (64%).
[0333] .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz):
[0334] .delta.=0.79 (d, 3H), 0.89 (d, 3H), 0.90 (d, 3H), 0.97 (d,
6H), 1.02 (d, 3H), 1.10 (d, 3H), 1.15 (d, 3H), 1.16 (d, 3H), 1.47
(d, 3H), 2.03 (sept, 1H), 2.47 (sept, 1H), 2.65 (sept, 1H), 2.76
(sept, 1H), 4.47 (sept, 1H), 6.13 (d, 1H), 6.21 (d, 1H), 6.35 (d,
1H), 6.46 (m.sub.c, 3H), 6.58 (dd, 2H), 6.65-6.76 (m, 3H), 6.93
(dd, 1H), 7.09 (dd, 1H), 7.15 (d, 1H), 7.25 (dd, 1H), 7.28-7.33 (m,
3H), 7.44-7.52 (m, 2H), 7.58 (dd, 1H), 7.67-7.76 (m, 2H), 8.39 (dd,
1H), 8.43 (d, 1H).
[0335] Photoluminescence (in a film, 2% in PMMA):
.lamda..sub.max=457, 489 nm, CIE: (0.18; 0.32)
Example 6
Complex Em3-i
##STR00259##
[0337] A suspension of 2.1 g of Em3-s in 2000 ml of acetonitrile is
irradiated with a moderate-pressure mercury immersion lamp at room
temperature for 8 h (TQ150 with Duran sheath). Subsequently, the
solvent is removed under reduced pressure. The residue was stirred
twice with acetone and filtered. 1.6 g of Em3-i were obtained as a
yellow powder (76%).
[0338] .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz):
[0339] .delta.=0.68 (d, 3H), 0.75 (d, 3H), 0.82 (d, 3H), 0.96 (d,
3H), 0.99 (d, 3H), 1.05 (d, 3H), 1.13 (d, 3H), 1.20 (d, 3H), 1.24
(d, 3H), 1.60 (d, 3H), 1.79 (sept, 1H), 2.42 (sept, 1H), 2.51
(sept, 1H), 2.76 (sept, 1H), 4.56 (sept, 1H), 6.10 (dd, 2H),
6.30-6.35 (m, 1H), 6.38-6.45 (m, 2H), 6.53 (d, 1H), 6.61 (dd, 1H),
6.68 (d, 1H), 6.73 (d, 1H), 6.74-6.78 (m, 2H), 6.79 (d, 1H), 6.96
(dd, 1H), 7.07-7.15 (m, 1H), 7.19 (d, 1H), 7.22 (d, 1H), 7.27-7.34
(m, 3H), 7.47 (dd, 1H), 7.49 (dd, 1H), 7.66-7.72 (m, 2H), 8.34 (d,
1H), 8.40 (d, 1H).
[0340] Photoluminescence (in a film, 2% in PMMA):
.lamda..sub.max=456, 487 nm, CIE: (0.19; 0.32)
[0341] The photoluminescence quantum yield of the isomer Em3-i is
1.21 times the quantum yield of the isomer Em3-s.
Example 7
4-Methyl-1,3-diphenyl-1H-[1,2,4]-triazolium iodide C4
##STR00260##
[0343] Stage 1: Benzonitrile (51.5 g, 0.50 mol) is admixed with
ethanol (anhydrous, 25 ml). Then a constant stream of HCl gas is
introduced over 2 h and the mixture is subsequently stirred at room
temp. for 48 h, in the course of which a solid forms. The solvent
is drawn off from the reaction mixture under reduced pressure (95
g).
[0344] Stages 2+3: 12 g of stage 1 (64.6 mmol) are again dissolved
in EtOH (120 ml), and phenylhydrazine (9.4 g, 84 mmol, 1.3 equiv.)
is added, in the course of which a solid forms. Triethylamine (22
ml, 162 mmol, 2.5 equiv.) is added and then the mixture is stirred
at room temp. for 16 h. The solvent is again removed from the
reaction mixture under reduced pressure at room temp., such that
the amidrazone formed remains, still moist. After the addition of
formic acid (200 ml), the mixture is heated to reflux for 3.5 h.
After a further 48 h at room temp., the mixture is cautiously added
to an aq. potassium carbonate solution (44%, 900 ml), cooled to
0.degree. C. After the addition of CH.sub.2Cl.sub.2 (500 ml), the
phases are separated, and the organic phase is dried over
Na.sub.2SO.sub.4 and concentrated under reduced pressure. The
sample is recrystallized from dichloromethane/petroleum ether, from
which slightly contaminated product is obtained (5.5 g, 40%). The
mother liquor is column-filtered (CH.sub.2Cl.sub.2/n-hexane), from
which a further batch of clean product is obtained (1.7 g,
12%).
[0345] Stage 4: The triazole of the preceding stage (1.5 g, 66
mmol) is dissolved in THF (anhydrous, 40 ml), admixed with MeI (14
ml) and heated to reflux for 5 days. The solid obtained is filtered
off, recrystallized repeatedly (CH.sub.2Cl.sub.2/n-hexane) and
dried (780 mg, 32%).
[0346] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2):
[0347] .delta.=4.26 (s, 3H), 7.53-7.71 (m, 6H), 7.74-7.76 (m, 2H),
8.09-8.11 (m, 2H), 12.27 (s, 1H).
Complex Em-4-s:
##STR00261##
[0349] 0.40 g (1.1 mmol) of imidazolium iodide C4 and 0.13 g (0.56
mmol) of Ag.sub.2O are stirred in 50 ml of anhydrous acetonitrile
at room temperature for 18 h. Then a solution of 0.61 g (0.37 mmol)
of chloro dimer D1 in 25 ml of anhydrous acetonitrile is added.
Thereafter, the mixture is heated to reflux for 6 h and then
stirred at room temperature for another 16 h. After cooling, the
reaction solution is filtered. The filtrate is freed of the solvent
under reduced pressure. After washing the residue with methanol,
0.2 g of the complex Em-4-s is obtained as a yellow powder
(26%).
[0350] .sup.1H NMR (500 MHz, CD.sub.2Cl.sub.2):
[0351] .delta.=0.91 (d, .sup.3J.sub.H,H=6.9 Hz, 3H), 0.95 (d,
.sup.3J.sub.H,H=7.1 Hz, 3H), 0.97 (d, .sup.3J.sub.H,H=7.1 Hz, 3H),
0.98 (d, .sup.3J.sub.H,H=6.8 Hz, 3H), 1.00 (d, .sup.3J.sub.H,H=6.9
Hz, 3H), 1.05 (d, .sup.3J.sub.H,H=6.9 Hz, 3H), 1.20 (d,
.sup.3J.sub.H,H=6.9 Hz, 3H), 1.21 (d, .sup.3J.sub.H,H=6.9 Hz, 3H),
2.17 (sept, .sup.3J.sub.H,H=6.8 Hz, 1H), 2.40 (sept,
.sup.3J.sub.H,H=6.9 Hz, 1H), 2.75-2.82 (m, 2H), 3.36 (s, 3H), 6.17
(bt, .sup.3J.sub.H,H=7.0 Hz, 2H), 6.43-6.50 (m, 3H), 6.62 (d, J=1.5
Hz, 1H), 6.66-6.82 (m, 6H), 6.88 (dd, .sup.3J.sub.H,H=7.1 Hz, J=1.3
Hz, 1H), 6.96 (dt, .sup.3J.sub.H,H=7.4 Hz, J=1.5 Hz, 1H), 7.08 (bd,
.sup.3J.sub.H,H=6.7 Hz, 1H), 7.31-7.37 (m, 4H), 7.51-7.59 (m, 6H),
7.69-7.72 (m, 2H).
[0352] Photoluminescence (in a film, 2% in PMMA):
X.sub.max=458, 488 nm, CIE: (0.19; 0.33)
Example 8
Complex Em-4-i
##STR00262##
[0354] A solution of 0.15 g of complex Em-4-s in 200 ml of
3-methoxypropionitrile is irradiated with a blacklight blue lamp at
room temperature for 2 h (Osram, L18W/73, .lamda..sub.max=370-380
nm). The solvent is removed under reduced pressure. The residue is
carefully washed with methanol. This gives 0.05 g Em-4-i as a
yellow powder (33%).
[0355] .sup.1H NMR (500 MHz, CD.sub.2Cl.sub.2):
[0356] .delta.=0.71 (d, .sup.3J.sub.H,H=6.9 Hz, 3H), 0.84 (d,
.sup.3J.sub.H,H=6.8 Hz, 3H), 0.88 (d, .sup.3J.sub.H,H=6.9 Hz, 3H),
1.03 (d, .sup.3J.sub.H,H=6.8 Hz, 3H), 1.06 (d, .sup.3J.sub.H,H=6.7
Hz, 3H), 1.07 (d, .sup.3J.sub.H,H=6.8 Hz, 3H), 1.18 (d,
.sup.3J.sub.H,H=6.9 Hz, 3H), 1.19 (d, .sup.3J.sub.H,H=6.9 Hz, 3H),
1.89 (sept, .sup.3J.sub.H,H=6.8 Hz, 1H), 2.50 (sept,
.sup.3J.sub.H,H=6.9 Hz, 1H), 2.58 (sept, .sup.3J.sub.H,H=6.9 Hz,
1H), 2.73 (sept, .sup.3J.sub.H,H=6.9 Hz, 1H), 6.17 (bd,
.sup.3J.sub.H,H=7.8 Hz, 2H), 6.42-6.52 (m, 3H), 6.60 (dt,
.sup.3J.sub.H,H=7.6 Hz, J=1.3 Hz, 1H), 6.64-6.70 (m, 4H), 6.76-6.78
(m, 2H), 6.81 (d, J=61.4 Hz, 1H), 6.91-6.94 (m, 2H), 7.27-7.38 (m,
4H), 7.50-7.56 (m, 6H), 7.75-7.77 (m, 2H).
[0357] Photoluminescence (in a film, 2% in PMMA):
.lamda..sub.max=456, 488 nm, CIE: (0.19; 0.33)
[0358] The photoluminescence quantum yield of the isomer Em-4-i has
1.40 times the quantum yield of the isomer Em-4-s.
Example 9
3,4-Diphenyl-1-o-tolyl-4H-[1,2,4]-triazolium iodide C5
##STR00263##
[0360] Stage 1: Aq. NaHCO.sub.3 solution (5%, 330 g, 190 mmol, 2.0
equiv.) is added at room temp. to a suspension of o-tolylhydrazine
hydrochloride (15 g, 97 mmol) in methyl chloride (450 ml). After
stirring for 30 minutes, the biphasic solution is phase-separated.
The organic phase is dried over Na.sub.2SO.sub.4, freed of the
solvent and dried under reduced pressure at 60.degree. C. to
isolate tolylhydrazine as a pale yellow solid (7.3 g, 62%).
[0361] Stage 2: Benzoyl chloride (8.4 g, 60 mmol, 1.0 equiv.) is
initially charged in toluene (anhydrous, 60 ml) and cooled to
5.degree. C. Then aniline (5.6 g, 60 mmol, 1.0 equiv.) is added,
and the reaction mixture is heated to reflux for 16 h and then
stirred at room temp. for a further 48 h. Then the mixture is
heated to 80.degree. C., thionyl chloride (21.4 g, 180 mmol, 3.0
equiv.) is added at this temperature and the mixture is stirred for
a further 2 h. Then the mixture is cooled to room temp. and the
excess thionyl chloride is drawn off under reduced pressure. The
reaction mixture is admixed with THF (anhydrous, 180 ml) and
triethylamine (9.1 g, 90 mmol, 1.5 equiv.) and cooled to 5.degree.
C., and then the tolylhydrazine of stage 1 (7.3 g, 60 mmol),
dissolved in THF (20 ml), is added. The mixture is stirred at room
temperature for 16 h. After the removal of the solvent, the residue
is recrystallized from acetic acid (2%, 150 ml), washed with iPrOH
(80 ml, 20 ml) and dried (10.3 g, 57%).
[0362] Stage 3: Triethyl orthoformate (9.0 ml, 8.1 g, 56 mmol, 5.6
equiv.) and 3 g of the hydrazone of stage 2 (10 mmol) are initially
charged, ammonium iodide (1.4 g, 10 mmol, 1.0 equiv.) is added and
the suspension is heated to reflux for 7 h. After cooling, the
solid is filtered off with suction and washed repeatedly with
n-hexane and ethyl acetate, from which the iodide salt is obtained
as a gray powder (3.2 g, 73%).
[0363] .sup.1H NMR (400 MHz, DMSO):
[0364] .delta.=2.55 (s, 3H), 7.47-7.90 (m, 14H), 11.07 (s, 1H).
Complex Mixture Em5-s:
##STR00264##
[0366] 1.12 g (2.5 mmol) of imidazolium iodide C5 are suspended in
100 ml of anhydrous toluene. At 0.degree. C., 8.2 ml (4.1 mmol) of
potassium bis(trimethylsilyl)amide (0.5M in toluene) are added
dropwise within 5 min. The solution formed is allowed to warm up to
10.degree. C. and admixed with a suspension of 1.42 g (0.85 mmol)
of chloro dimer D1 and 75 ml of anhydrous toluene. The reaction
mixture is heated to 90.degree. C. and stirred at this temperature
for 2 h. After cooling, the precipitate is removed. The filtrate is
washed successively with 3.times.30 ml of aqueous NaHCO.sub.3
solution and 1.times.30 ml of water, dried over MgSO.sub.4 and
freed of the solvent under reduced pressure. The residue is
purified by column chromatography (solvent:
cyclohexane/acetone=4/1). This gives 1.2 g (63%) Em5-s as a mixture
of two cyclometalation isomers.
[0367] Photoluminescence (in a film, 2% in PMMA):
[0368] .lamda..sub.max=461, 489 nm, CIE: (0.19; 0.33)
Example 10
Complex Mixture Em5-i
##STR00265##
[0370] A solution of 0.60 g of Em5-s complex mixture in 200 ml of
3-methoxypropionitril is irradiated with a blacklight blue lamp at
room temperature for 7 h (Osram, L18W/73, .lamda..sub.max=370-380
nm). The solvent is removed under reduced pressure. The residue is
carefully washed with methanol. This gives 0.10 g of Em5-i as a
pale yellow powder (17%, again mixture of two cyclometalation
isomers).
[0371] MS (Maldi):
m/e=1110 (M+H).sup.+
[0372] Photoluminescence (in a film, 2% in PMMA):
.lamda..sub.max=456, 487 nm, CIE: (0.20; 0.34)
[0373] The photoluminescence quantum yield of the isomerized Em5-i
complex mixture has 1.50 times the quantum yield of the Em5-s
complex mixture.
Example 11
1-Methyl-2-phenyl-1H-imidazole L2
##STR00266##
[0375] 13.0 g (90 mmol) of 2-phenylimidazole are dissolved in 600
ml of DMF, admixed slowly with 4.0 g (100 mmol) of sodium hydride
(60% in mineral oil) and stirred at room temperature for 30 min.
Then 14.0 g (99 mmol) of methyl iodide are added. The reaction
mixture is stirred at room temperature for 1.5 h and then admixed
cautiously with 350 ml of water. The mixture is extracted with
2.times.200 ml of ethyl acetate. The extract is dried over sodium
sulfate and concentrated. This gives 12.0 g (84%) L2.
[0376] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2):
[0377] .delta.=3.74 (s, 3H), 7.00 (s, 1H), 7.05 (s, 1H), 7.40-7.43
(m, 1H), 7.45-7.48 (m, 2H), 7.62-7.63 (m, 2H).
.mu.-Dichloro Dimer D2:
##STR00267##
[0379] The synthesis is performed analogously to D1. The
precipitate obtained is extracted with dichloromethane. After
removing the solvent, D2 is obtained from the extract in a yield of
36%.
[0380] .sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz):
[0381] .delta.=4.13 (s, 12H), 6.05 (d, .sup.3J.sub.H,H=7.7 Hz, 4H),
6.55 (t, .sup.3J.sub.H,H=7.5 Hz, 4H), 6.74 (t, .sup.3J.sub.H,H=7.5
Hz, 4H), 6.94 (s, 4H), 7.27 (s, 4H), 7.37 (d, .sup.3J.sub.H,H=7.7
Hz, 4H).
Complex Em6-s:
##STR00268##
[0383] 1.20 g (3.6 mmol) of
5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole Cl are
heated to 90.degree. C. under reduced pressure for 20 h. After
cooling to room temperature, first 1.21 of anhydrous toluene and
then 0.99 g (0.9 mmol) of chloro dimer D2 are added. The mixture is
heated to reflux for 8 h. The precipitate formed is filtered off.
The filtrate is concentrated to approx. 800 ml and washed
successively with 3.times.500 ml of saturated NaHCO.sub.3 solution
and 1.times.500 ml of distilled water, dried over Na.sub.2SO.sub.4
and freed of the solvent under reduced pressure. The residue is
purified by column chromatography (cyclohexane/acetone=5/1). This
gives 118 mg of the complex Em6-s (8%).
[0384] .sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz):
[0385] .delta.=3.95 (s, 3H), 4.03 (s, 3H), 6.00 (bd,
.sup.3J.sub.H,H=7.3 Hz, 1H), 6.23 (bt, .sup.3J.sub.H,H=7.3 Hz, 1H),
6.27 (d, J=1.5 Hz, 1H), 6.47 (bd, .sup.3J.sub.H,H=7.1 Hz, 1H), 6.51
(d, J=1.5 Hz, 1H), 6.60 (bt, .sup.3J.sub.H,H=7.5 Hz, 1H), 6.67-6.72
(m, 4H), 6.79-6.88 (m, 6H), 6.95 (dt, .sup.3J.sub.H,H=7.5 Hz, J=1.5
Hz, 1H), 7.05 (bt, .sup.3J.sub.H,H=7.5 Hz, 1H), 7.24-7.27 (m, 2H),
7.33-7.36 (m, 4H), 7.47 (bd, .sup.3J.sub.H,H=6.8 Hz, 1H), 7.61 (bd,
.sup.3J.sub.H,H=6.9 Hz, 1H).
[0386] Photoluminescence (in a film, 2% in PMMA):
.lamda..sub.max=456, 486 nm, CIE: (0.21; 0.33)
Example 12
Complex Em7-s
##STR00269##
[0388] 0.67 g (2.0 mmol) of
5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole Cl are
heated to 90.degree. C. under reduced pressure for 20 h. After
cooling to room temperature, the residue is dissolved in 50 ml of
anhydrous toluene and added to a suspension of 1.00 g (0.9 mmol) of
chloro dimer D2 and 0.36 g (1.9 mmol) of AgBF.sub.4 in 1.2 I of
anhydrous toluene. The mixture is stirred under reflux for 8 h. The
precipitate formed is filtered off. The filtrate is concentrated to
approx. 800 ml and washed successively with 3.times.500 ml of
saturated NaHCO.sub.3 solution and 1.times.500 ml of distilled
water, dried over Na.sub.2SO.sub.4 and freed of the solvent under
reduced pressure. The residue is purified by column chromatography
(cyclohexane/acetone=5/1). This gives 70 mg of the complex Em7-s
(5%).sub..
[0389] MS (Maldi):
m/e=943 (M+H).sup.+
[0390] .sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz):
[0391] .delta.=3.70 (s, 3H), 5.86 (d, J=1.3 Hz, 1H), 5.96 (bd,
.sup.3J.sub.H,H=8.1 Hz, 2H), 6.10 (d, J=1.3 Hz, 1H), 6.56 (bd,
.sup.3J.sub.H,H=7.2 Hz, 1H), 6.72-6.75 (m, 4H), 6.80 (bt,
.sup.3J.sub.H,H=7.3 Hz, 1H), 6.86-6.92 (m, 3H), 6.94 (bt,
.sup.3J.sub.H,H=7.5 Hz, 1H), 7.02-7.12 (m, 5H), 7.19-7.40 (m, 13H),
7.56 (bd, .sup.3J.sub.H,H=7.7 Hz, 1H), 7.70 (bd,
.sup.3J.sub.H,H=7.0 Hz, 1H).
[0392] Photoluminescence (in a film, 2% in PMMA):
.lamda..sub.max=476, 502 nm, CIE: (0.22; 0.37)
Example 13
Complex Em7-s*
##STR00270##
[0394] 0.90 g (2.7 mmol) of
5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole Cl are
heated to 90.degree. C. under reduced pressure for 20 h. After
cooling to room temperature, first 800 ml of anhydrous toluene and
then 0.99 g (0.9 mmol) of chloro dimer D2 are added. The mixture is
stirred under reflux for 3 h. The precipitate formed is filtered
off. The filtrate is washed successively with 3.times.50 ml of
saturated NaHCO.sub.3 solution and 1.times.50 ml of distilled
water, dried over MgSO.sub.4 and freed of the solvent under reduced
pressure. The residue is purified by column chromatography
(cyclohexane/acetone=2/1). As well as 50 mg of the complex Em6-s,
150 mg of the complex Em7-s* are obtained.
[0395] .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz):
[0396] .delta.=3.86 (s, 3H), 5.95 (bd, .sup.3J.sub.H,H=7.3 Hz, 2H),
6.23 (bd, J=1.4 Hz, 1H), 6.38 (bt, .sup.3J.sub.H,H=7.3 Hz, 1H),
6.44 (bd, .sup.3J.sub.H,H=7.3 Hz, 1H), 6.54 (bt,
.sup.3J.sub.H,H=7.5 Hz, 1H), 6.61-6.67 (m, 4H), 6.78-6.91 (m, 5H),
6.96 (bt, .sup.3J.sub.H,H=7.5 Hz, 1H), 7.07-7.13 (m, 4H), 7.19-7.36
(m, 12H), 7.53 (bd, .sup.3J.sub.H,H=7.0 Hz, 1H), 7.76 (bd,
.sup.3J.sub.H,H=7.3 Hz, 1H).
[0397] Photoluminescence (in a film, 2% in PMMA):
.lamda..sub.max=482, 508 nm, CIE: (0.24; 0.40)
Example 14
.mu.-Dichloro Dimer D3
##STR00271##
[0399] The synthesis is performed analogously to D1. Yield:
87%.
[0400] .sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz):
[0401] .delta.=2.21 (s, 12H), 2.28 (s, 12H), 2.44 (s, 12H), 6.38
(d, .sup.3J.sub.H,H=7.4 Hz, 4H), 7.09 (d, .sup.3J.sub.H,H=8.7 Hz,
4H), 7.19 (m, 4H), 7.30 (bd, .sup.3J.sub.H,H=8.7 Hz, 4H), 7.42 (m,
8H), 7.55 (m, 4H), 7.86 (s, 4H), 8.00 (d, .sup.3J.sub.H,H=8.4 Hz,
4H), 8.48 (bs, 4H).
Complex Em8-s:
##STR00272##
[0403] 0.37 g (1.1 mmol) of
5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole Cl are
heated to 90.degree. C. under reduced pressure for 18 h. After
cooling to room temperature, first 120 ml of anhydrous toluene and
then 0.50 g (0.28 mmol) of chloro dimer D3 are added. The mixture
is heated to 75.degree. C. for 3 h. The white precipitate formed is
filtered off. The filtrate is washed with 3.times.30 ml of
saturated NaHCO.sub.3 solution and 1.times.30 ml of distilled
water, dried over MgSO.sub.4 and freed of the solvent under reduced
pressure. The residue is purified by column chromatography (silica
gel, ethyl acetate:cyclohexane=1:5). This gives 0.19 g of the
complex Em8-s (28%).
[0404] .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz):
[0405] .delta.=2.03 (s, 3H), 2.10 (s, 3H), 2.20 (s, 3H), 2.28 (s,
3H), 2.44 (s, 3H), 2.48 (s, 3H), 6.21 (d, .sup.3J.sub.H,H=7.6 Hz,
1H), 6.63-7.39 (m, 28H), 7.45 (d, .sup.3J.sub.H,H=7.9 Hz, 1H), 7.67
(d, .sup.3J.sub.H,H=7.9 Hz, 1H), 7.70 (d, .sup.3J.sub.H,H=7.6 Hz,
1H), 8.21 (bs, 2H).
[0406] Photoluminescence (in a film, 2% in PMMA):
.lamda..sub.max=456 nm, CIE: (0.24; 0.29)
Example 15
Comparative Example, Noninventive
Complex CEm1
##STR00273##
[0408] CEm1 corresponds to compound (N-3) from WO 2006067074
[0409] The synthesis is analogous to WO 2006067074.
.lamda..sub.PL (PMMA): 472 nm, 491 nm, quantum yield.sub.PL: 2%
[0410] Owing to its very low phosphorescence quantum yield, complex
CEm1 is not suitable as an emitter in OLEDs.
Example 16
Comparative Example, Noninventive
Complex CEm2
##STR00274##
[0412] CEm2 corresponds to the compound "Compound 3" from WO
2006121811. The synthesis was analogous WO 2006121811.
Example 17
Production of an OLED
Comparison of Different Emitters
[0413] The ITO substrate used as the anode is cleaned first with
commercial detergents for LCD production (Deconex.RTM. 20NS, and
25ORGAN-ACID.RTM. neutralizing agent) and then in an
acetone/isopropanol mixture in an ultrasound bath. To eliminate
possible organic residues, the substrate is exposed to a continuous
ozone flow in an ozone oven for a further 25 minutes. This
treatment also improves the hole injection properties of the ITO.
Next, the hole injection layer AJ20-1000 from Plexcore respectively
PEDT: PSS (CLEVIOS P AR 4083) from H. C. Starck is spun on from
solution.
[0414] Thereafter, the organic materials specified below are
applied by vapor deposition to the cleaned substrate at about
10.sup.-7-10.sup.-9 mbar at a rate of approx. 0.5-5 nm/min. The
hole conductor and exciton blocker applied to the substrate is
Ir(DPBIC).sub.3 with a thickness of 45 nm, of which the first 35 nm
are doped with MoO.sub.x to improve the conductivity,
##STR00275##
(for preparation see Ir complex (7) in the application
PCT/EP/04/09269).
[0415] Subsequently, a mixture of emitter and of the compound Ma1
is applied by vapor deposition with a thickness of 40 nm, the
latter compound functioning as a matrix material. Subsequently, the
material Ma1 is applied by vapor deposition with a thickness of 10
nm as an exciton and hole blocker.
##STR00276##
[0416] Next, an electron transporter BCP
(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) is applied by vapor
deposition in a thickness of 20 nm, as are a 0.75 nm-thick lithium
fluoride layer and finally a 100 nm-thick Al electrode. All
components are adhesive-bonded to a glass lid in an inert nitrogen
atmosphere.
[0417] To characterize the OLED, electroluminescence spectra are
recorded at different currents and voltages. In addition, the
current-voltage characteristic is measured in combination with the
light output emitted. The light output can be converted to
photometric parameters by calibration with a photometer. The
lifetime t.sub.1/2 of the diode is defined by the time taken for
the luminance to fall to 50% of its initial value. The lifetime
measurement is carried out at a constant current.
[0418] For the different emitters in the above-described OLED
structure, the following electrooptical data are obtained:
TABLE-US-00004 Cd/A @ t.sub.1/2 @ 1000nits (normalized to the
Emitter CIE 300nits value of CEm2) Em1-i 0.22/0.37 23.2 cd/A 594%
Em3-i 0.18/0.28 19.5 cd/A 135% Em2-i 0.17/0.25 24.5 cd/A 245% CEm2
0.20/0.35 10.3 cd/A 100%
Example 18
Comparison of Different Isomers of One Emitter
[0419] By way of example, the influence of the different isomers on
the OLED performance is shown in two cases. For the different
emitters and isomers in the above-described OLED structure, the
following electrooptical data are obtained:
TABLE-US-00005 Cd/A @ t.sub.1/2 @ 1000nits (normalized to the
Emitter CIE 300nits value of Em1-s) Em1-s 0.19/0.31 18.2 cd/A 100%
Em1-i 0.22/0.37 23.2 cd/A 406% Cd/A @ t.sub.1/2 @ 1000nits
(normalized to the Emitter CIE 300nits value of Em2-s) Em2-s
0.21/0.35 15.4 cd/A 100% Em2-i 0.17/0.25 24.5 cd/A 178%
Example 19
Influence of a Mixed Electron Conductor Layer
[0420] The example which follows shows the influence of the doping
of the BCP electron conductor layer with Liq.
##STR00277##
[0421] The following OLED structure is used:
ITO-40 nm AJ20-1000-35 nm Ir(DPBIC).sub.3 mixed with MoO.sub.x-10
nm Ir(DPBIC).sub.3-40 nm Ma1 mixed with 20 wt % Em1-i-5 nm Ma1-40
nm electron conductor-1 nm Liq-100 nm Al. The preparation of the
OLED is carried out in analogy to Example 17.
TABLE-US-00006 Electron Cd/A @ t.sub.1/2 @ 1000nits (normalized to
the conductor CIE 300nits value of BCP) BCP 0.22/0.36 16.8 cd/A
100% BCP:Liq 50% 0.21/0.36 21.7 cd/A 170%
Example 20
Complex Em9-s
##STR00278##
[0423] Imidazoliumiodide C6 corresponds to a pre-intermediate of
the compound "example 1" in WO 2006056418. The synthesis is carried
out in analogy to the synthesis of the compound "example 1" in WO
2006056418.
[0424] 2.0 g (6.4 mmol) of imidazoliumiodide C6 and 0.75 g (3.2
mmol) Ag.sub.2O are stirred in 170 ml anhydrous acetonitrile for 4
h at 50.degree. C. The solvent is then removed in vacuo. To the
residue 170 ml anhydrous toluene is added and 3.6 g (2.1 mmol)
chlorodimer D1 are added. Subsequently it is heated under reflux
for 24 h. After cooling the reaction mixture is filtered. The
filtrate is freed from solvent in vacuo. To the residue methylene
chloride is added, washed with water, reduced after drying and
purified by chromatography (cyclohexane/acetic ester), where by
0.26 g Em9-s are isolated (6%) and 0.63 g of a mixed fraction of
complex Em9-s with not complexed phenylimidazol-ligand as well as
0.10 mg of a further complex with inverse ligand stoichiometry.
Further 1.3 g of chlorodimer D1 (36%) are reisolated.
[0425] .sup.1H-NMR (CD.sub.2Cl.sub.2, 400 MHz):
[0426] .delta.=0.83 (d, 3H), 0.89-0.96 (m, probably interpreted as
4.times.d, 12H), 1.00 (d, 3H), 1.13 (d, 3H), 1.15 (d, 3H), 1.98
(sept, 1H), 2.31 (sept, 1H), 2.70 (sept, 1H), 2.74 (sept, 1H), 3.21
(s, 3H), 6.10 (dd, 2H), 6.37-6.45 (m, 4H), 6.56-6.65 (m, 4H), 6.70
(dd, 1H), 6.83 (m.sub.c, 1H), 6.95 (d, 1H), 7.06 (m.sub.c, 1H),
7.19 (m.sub.c, 2H), 7.25-7.31 (m, 4H), 7.44-7.50 (m, 3H).
[0427] MS (Maldi):
m/e=979 (M+H).sup.+
[0428] photoluminescence (in film, 2% in PMMA):
.lamda..sub.max=456, 487 nm, CIE: (0.20; 0.30)
Example 21
Complex Em9-i
##STR00279##
[0430] A solution of 0.17 g of complex Em9-s in 2000 ml acetonitril
are irradiated at 15.degree. C. for 9.5 h with a
blacklight-blue-lamp (Osram, L18W/73, .lamda..sub.max=370-380 nm).
The solvent is removed in vacuo. The residue is purified by
chromatography (cyclohexane/acetic ester). 0.055 g of Em9-i (32%,
contaminated with traces of a further complex) are obtained as well
as 0.075 g of reisolated Em9-s (44%) are reisolated.
[0431] .sup.1H-NMR [CD.sub.2Cl.sub.2, 400 MHz, sample comprises
traces of a further complex observable for example at 0.77 (m),
0.83 (d), 1.04 (d), 1.21 (m), 1.92 (sept), 2.34 (sept), 7.20-7.23
(m), 7.31-7.34 (m)]:
[0432] .delta.=0.65 (d, 3H), 0.77 (d, 3H), 0.85 (d, 3H), 0.97 (d,
3H), 0.98 (d, 3H), 1.02 (d, 3H), 1.13 (d, 6H), 1.82 (sept, 1H),
2.33 (sept, 1H), 2.54 (sept, 1H), 2.67 (sept, 1H), 3.04 (s, 3H),
6.09 (dd, 2H), 6.37 (td, 1H), 6.40-6.44 (m, 3H), 6.50 (m, 1H), 6.59
(d, 1H), 6.61 (td, 1H), 6.68 (d, 1H), 6.70 (d, 1H), 6.72 (d, 1H),
6.86 (d, 1H), 6.96 (br.s, 1H), 7.14 (m.sub.c, 2H), 7.20-7.23 (m,
1H), 7.23-7.31 (m, 3H), 7.44-7.50 (m, 3H).
[0433] MS (Maldi):
m/e=979 (M+H).sup.+
[0434] photoluminescence (in film, 2% in PMMA):
.lamda..sub.max=457, 485 nm, CIE: (0.17; 0.26)
[0435] The photoluminescence quantum efficiency of the isomer Em9-i
has the 1.14-fold value of the quantum efficiency of the isomer
Em9-s.
Example 22
Complex Em10-s
1,3-Diphenyl-4,5-di-o-tolyl-imidazolium-tetrafluoroborate C7
##STR00280##
[0436] Step 1: Preparation of
2-anilino-1,2-di-o-toluene-ethanone
[0437] A solution of 18.00 g (74.91 mmol) o-toluoine are dissolved
in 100 ml anhydrous toluene and 21.00 g (224.9 mmol) of anilin and
0.2 g conc. HCl are added at room temperature. The reaction mixture
is heated for 10 hours to boiling under reflux, where by the water
formed is revolved out. After cooling to room temperature the
reaction mixture is diluted with 100 ml acetic ester and then
shaked two times with 70 ml 1 n HCl each. Subsequently the organic
phase is washed with 100 ml of water and 70 ml of brine, dryed over
magnesium sulfate and reduced to a yellow resin. The crude product
is purified chromatographically on silica gel with methylene
chloride as eluent. After removal of the solvent 19.6 g (83%) of a
yellow oil are obtained.
Step 2: Preparation of
N-(2-oxo-1,2-di-o-tolyl-ethyl)-N-phenyl-formamide
[0438] A solution of 19.50 g (58.7 mmol)
2-anilino-1,2-di-o-tolyl-ethanone in 80 ml of tetrahydrofuran is
meaned with 7.80 g (88.1 mmol) acetformylanhydride and stirred for
17 hours at room temperature. The reaction mixture is reduced at a
rotarap to a syrup and purified at silica gel with a petrol
ether-acetic ester solution as eluent at first in a ratio of 10:1
then 1:1. After removal of the solvent 18.4 g (91%) of a nearly
colorless syrup are obtained.
Step 3: Preparation of
3-phenyl-4,5-di-o-tolyl-oxazolium-tetrafluoroborate
[0439] To 9.80 g (55.9 mmol) of 50% tetrafluoroboric acid 63 g
trifluoroacetic anhydride are added by a syringe at 5-10.degree. C.
in 15 min (exothermic!). The cooled solution is subsequently added
dropwise to a suspension of 20.00 g (55.3 mmol)
N-(2-oxo-1,2-di-o-tolyl-ethyl)-N-phenyl-formamide in 60 g of
trifluoroacetic anhydride at room temperature in 10 min, whereby
the temperature rises to 28.degree. C. The reaction mixture is
stirred for 3 hours at 20-25.degree. C. and then reduced at a
rotarap to an oil. After addition of 100 ml diethylether 9.7 g
(55.3 mmol) 50% tetrafluoroboric acid are added dropwise by
stirring, whereby a precipitate is formed. After stirring for one
hour the precipitate is drawn off, washed three times with 10 ml
diethyl ether each and dried. 22.55 g (99%) of a colorless powder
are obtained.
Step 4: Preparation of
1,3-diphenyl-4,5-di-o-tolylimidazolium-tetrafluoroborate C7
[0440] To a suspension of 3.50 g (8.47 mmol)
3-phenyl-4,5-di-o-tolyl-oxazolium-tetrafluoroborate in 35 ml of
ethanol 1.58 g (16.9 mmol) of aniline are added. After stirring for
45 min at room temperature, the solution is reduced to an orange
colored resin and subsequently 15 mol sulfuric acid are added. The
solution is stirred for 2 hours at room temperature. The reaction
solution is stirred in 300 ml ice water where by a precipitate is
formed. The suspension is stirred for a further hour and then
filtered over a suction filter. The residue is washed with water
and sucked to dryness to a large extend. The residue is stirred in
an Erlenmeyer flask with 40 ml of diethyl ether, sucked and washed
with 10 ml of diethyl ether. The stirring in diethyl ether with
subsequent suction is repeated two times. After drying 3.10 g (71%
d.th.) of a colorless powder are obtained.
Complex Em10-s:
##STR00281##
[0442] A suspension of 1.61 g (3.30 mmol)
1,3-diphenyl-4,5-di-o-tolyl-imidazolium-tetrafluoroborate in 25 ml
of toluene are stirred for 15 min under argon at room temperature
and then cooled to 0.degree. C. 12.6 ml (6.29 mmol) 0.5 M
potassium-bis(trimethylsilyl)-amide in toluene are added with 1
min. The reaction solution is then stirred for 15 min at
0-12.degree. C., and subsequently, 2.50 g (1.50 mmol)
bis(iridium-p-chloro-complex) D1 are added. It is purged with 5 ml
of toluene. The orange-yellow suspension is heated under reflux to
boiling. After 75 min the reaction solution is cooled to room
temperature diluted with 20 ml acetic ester and then extracted two
times with 20 ml of phosphate buffer solution (ph 7). The organic
phase is separated, dryed over sodium sulfate and then reduced to
dryness. The solid is shortly heated in 150 ml of methanol under
reflux to boiling. After cooling of the suspension to 50.degree. C.
the solid is sucked, washed two times with 10 ml of methanol each
and dryed. 2.52 g of a yellow solid are obtained. The filtrate is
reduced to 40 ml and stirred overnight at room temperature. The
precipitate is sucked, washed with a small amount of methanol and
dried. 0.28 g of a yellow solid are obtained, which is combined
with the residue.
[0443] Therefore, alltogether 2.80 g (78% of th.) of a yellow solid
melting at 282-283.degree. C. are obtained.
[0444] MS (Maldi):
m/e=1197.4 (M+H).sup.+
[0445] Photoluminescence (in film, 2% in PMMA):
.lamda..sub.max=464, 493 nm, CIE: (0.19; 0.35)
Example 23
Complexes Em10-i and Em10-i*
##STR00282##
[0447] 0.50 g (0.42 mmol) of Em10-s are dissolved in 300 ml of
acetonitril and irradiated with a mercury pressure dipping lamp TQ
150 (365 nm, 150 W) for 5.5 hours. The solution is freed from the
solvent. The residue is dissolved in 30 ml of methanol by heating.
After cooling the precipitate is sucked, washed with methanol and
dried. The complex isomer Em10-i [0.19 g (38%)] is obtained as
yellow powder melting at 316-317.degree. C.
[0448] MS (Maldi):
m/e=1196.7 (M).sup.+
[0449] Photoluminescence (in film, 2% in PMMA):
.lamda..sub.max=460, 491 nm, CIE: (0.18; 0.32)
[0450] The filtrate is reduced to dryness, stirred with 10 ml of
n-pentane, sucked, washed with pentane and dried. The complex
isomer Em10-i* [0.16 g (32%)] is obtained as ocher yellow solid
melting at 207-209.degree. C.
[0451] MS (Maldi):
m/e=1197.8 (M+H).sup.+
[0452] Photoluminescence (in film, 2% in PMMA):
.lamda..sub.max=458, 490 nm, CIE: (0.19; 0.33)
I) Diode Examples concerning Em1-s
Example 24
Influence of the Matrix Materials on Em1-s
Diode Structure:
[0453] ITO-PEDT:PSS-35 nm Ir(DPBIC).sub.3 mixed with 10 wt.-%
MoO.sub.x-10 nm Ir(DPBIC).sub.3-40 nm Matrix MaX mixed with 15
wt.-% Em1-s-10 nm LB1-20 nm electron conductor BCP-0.70 nm LiF-100
nm Al.
[0454] The preparation of the diode is carried out in analogy to
Example 17.
[0455] Exciton and hole blocker LB1:
##STR00283##
TABLE-US-00007 EQE @ 300 nits and Matrix Voltage in Cd/A @
normalized to the value "MaX" CIE V@300 nits 300 nits of Ma2
Ma2.sup.1 0.20/0.36 8.8 10.1 100% Ma3 0.20/0.32 5.5 20.5 166%
Ma4.sup.2 0.19/0.32 6.5 16.3 134% Ma5 0.20/0.31 6.2 13.9 115%
Ma6.sup.3 0.19/0.30 6.2 22.8 195% .sup.1In this case 40 nm BCP were
used as electron conductor. .sup.2In this case 30 nm BCP were used
as electron conductor. .sup.3In this case AJ20 - 1000 of Plexcore
instead of PEDT: PSS were used as hole injection layer.
Structures of the Matrices "MaX" (=Ma2-Ma6) and Description of
their Synthesis in WO2010/079051:
TABLE-US-00008 Synthesis of MaX described in Matrix "MaX"
WO2010/079051 as Structure Ma2 BS 10 ##STR00284## Ma3 BS15
##STR00285## Ma4 BS18 ##STR00286## Ma5 BS20 ##STR00287## Ma6 BS 31
##STR00288##
II) Diode Examples concerning Em1-i
Example 25
Influence of the Matrix Materials on Em1-i
[0456] Structure A: ITO-AJ20-1000-35 nm Ir(DPBIC).sub.3 mixed with
50 wt.-% MoO.sub.3-10 nm Ir(DPBIC).sub.3-40 nm "MaX" mixed with 20
wt.-% Em1-i-5 nm "MaX"-40 nm electron conductor BCP:Liq 50 wt.-%-1
nm Liq-100 nm Al. The preparation of the diode is carried out in
analogy to Example 17.
[0457] Structure B: ITO-AJ20-1000-35 nm Ir(DPBIC).sub.3 mixed with
10 wt.-% MoO.sub.3-10 nm Ir(DPBIC).sub.3-40 nm "MaX" mixed with 15
wt.-% Em1-i-10 nm LB1-20 nm electron conductor BCP-0.70 nm LiF-100
nm Al. The preparation of the diode is carried out in analogy to
Example 17.
TABLE-US-00009 Voltage EQE@300 in nits nor- Matrix Diode V Cd/
malized to MaX structure CIE @300nits A@300nits the value of Ma7
Structure A 0.22/0.36 5.8 18.8 100% Ma8 Structure B 0.23/0.38 7.0
17.3 91% Ma9 Structure A.sup.1 0.23/0.38 4.3 17.9 95% .sup.1In this
case 5 nm Ma1 are used as excition and hole blocker.
Structures of the Matrices MaX and Description of their Synthesis
in WO2010/079051:
TABLE-US-00010 Matrix Compound in MaX WO2010/079051 Structure Ma7
BS26 ##STR00289## Ma8 BS29 ##STR00290## Ma9 BS28 ##STR00291##
Example 26
Influence of the Matrix Materials on Em1-i
[0458] ITO-AJ20-1000-10 nm Ma1 mixed with 10 wt.-% MoO.sub.x-10 nm
Ma10 mixed with 15 wt.-% Em1-i and 15 wt.-% Ma1-5 nm Ma1-20 nm
electron conductor BCP mixed with 20 wt.-% Ma1-1 nm
Cs.sub.2CO.sub.3-100 nm Al. The preparation of the diode is carried
out in analogy to Example 17.
[0459] The synthesis of matrix material Ma10 is described in
JP2009046408, compound B, [0039], p. 13.
Ma10
##STR00292##
TABLE-US-00011 [0460] Matrix Voltage MaX CIE in V @ 300 units Ma10
0.19/0.35 3.8
* * * * *