U.S. patent application number 16/872456 was filed with the patent office on 2020-08-27 for materials for organic electroluminescent devices.
The applicant listed for this patent is Merck Patent GmbH. Invention is credited to Tobias GROSSMANN, Dominik JOOSTEN, Jonas Valentin KROEBER, Aurelie LUDEMANN, Amir Hossain Parham.
Application Number | 20200270235 16/872456 |
Document ID | / |
Family ID | 1000004824569 |
Filed Date | 2020-08-27 |
![](/patent/app/20200270235/US20200270235A1-20200827-C00001.png)
![](/patent/app/20200270235/US20200270235A1-20200827-C00002.png)
![](/patent/app/20200270235/US20200270235A1-20200827-C00003.png)
![](/patent/app/20200270235/US20200270235A1-20200827-C00004.png)
![](/patent/app/20200270235/US20200270235A1-20200827-C00005.png)
![](/patent/app/20200270235/US20200270235A1-20200827-C00006.png)
![](/patent/app/20200270235/US20200270235A1-20200827-C00007.png)
![](/patent/app/20200270235/US20200270235A1-20200827-C00008.png)
![](/patent/app/20200270235/US20200270235A1-20200827-C00009.png)
![](/patent/app/20200270235/US20200270235A1-20200827-C00010.png)
![](/patent/app/20200270235/US20200270235A1-20200827-C00011.png)
View All Diagrams
United States Patent
Application |
20200270235 |
Kind Code |
A1 |
Parham; Amir Hossain ; et
al. |
August 27, 2020 |
MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES
Abstract
The present invention describes carbazolyl compounds substituted
by electron-deficient heteroaryl groups, especially for use as
triplet matrix materials in organic electroluminescent devices. The
invention further relates to a process for preparing the compounds
of the invention and to electronic devices comprising these.
Inventors: |
Parham; Amir Hossain;
(Frankfurt Am Main, DE) ; LUDEMANN; Aurelie;
(Frankfurt am Main, DE) ; JOOSTEN; Dominik;
(Ober-Ramstadt, DE) ; GROSSMANN; Tobias;
(Darmstadt, DE) ; KROEBER; Jonas Valentin;
(Frankfurt am Main, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Merck Patent GmbH |
Darmstadt |
|
DE |
|
|
Family ID: |
1000004824569 |
Appl. No.: |
16/872456 |
Filed: |
May 12, 2020 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
15772557 |
May 1, 2018 |
|
|
|
PCT/EP2016/001678 |
Oct 11, 2016 |
|
|
|
16872456 |
|
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 2251/5384 20130101;
H01L 51/0074 20130101; C09K 2211/185 20130101; Y02E 10/549
20130101; H01L 51/5096 20130101; C07D 487/04 20130101; C09K
2211/1088 20130101; C07D 405/14 20130101; C09K 2211/1007 20130101;
C09K 2211/1014 20130101; H01L 51/5072 20130101; C07D 495/04
20130101; C09K 2211/1044 20130101; H01L 51/0067 20130101; H01L
51/0073 20130101; C09K 11/06 20130101; C07D 409/14 20130101; H01L
51/0085 20130101; C09K 2211/1059 20130101; H01L 51/5016 20130101;
C07D 491/048 20130101; C09K 2211/1092 20130101; H01L 51/0072
20130101; Y02P 70/50 20151101; C09K 2211/1029 20130101 |
International
Class: |
C07D 405/14 20060101
C07D405/14; C07D 487/04 20060101 C07D487/04; C07D 495/04 20060101
C07D495/04; H01L 51/00 20060101 H01L051/00; H01L 51/50 20060101
H01L051/50; C09K 11/06 20060101 C09K011/06; C07D 409/14 20060101
C07D409/14; C07D 491/048 20060101 C07D491/048 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 2, 2015 |
EP |
15192535.1 |
Claims
1.-15. (canceled)
16. An electronic device comprising at least one compound according
to formula (1) ##STR00358## where A is CR; Y is O or S; W is the
same or different at each instance and is CR or N, where not more
than one W group per cycle is N and where W is C when an L.sup.1 or
L.sup.2 group is bonded to this position, or two adjacent W groups
together are a group of the following formula (2) or (3), where
each of the two carbazolyl derivative groups in the compound of the
formula (1) have not more than two groups of the formula (2) or
formula (3): ##STR00359## where the dotted bonds indicate the
linkage of this group, A has definitions given above and Z is NR,
CR.sub.2, O or S; Ar.sup.1, Ar.sup.2 is an aromatic ring system
having 5 to 30 aromatic ring atoms or a dibenzofuran or
dibenzothiophene group, where the aromatic ring system or the
dibenzofuran or dibenzothiophene group may be substituted in each
case by one or more nonaromatic R radicals, or is a group of one of
the following formulae (4) and (5): ##STR00360## where the dotted
bond represents the bond to the nitrogen atom; with the proviso
that exactly one of the Ar.sup.1 and Ar.sup.2 groups is a group of
one of the formulae (4) and (5); X is the same or different at each
instance and is CR or N, where X in formula (5) is C when the group
of the formula (5) in this position is joined to L.sup.3, with the
proviso that, in formula (4), two or three X groups are N and, in
formula (5), one, two or three X groups are N; L.sup.1, L.sup.2,
L.sup.3 is the same or different at each instance and is a single
bond or an aromatic or heteroaromatic ring system which has 5 to 30
aromatic ring atoms and may be substituted by one or more R
radicals; R is the same or different at each instance and is
selected from the group consisting of H, D, F, CN,
N(R.sup.1).sub.2, C(.dbd.O)R.sup.1, P(.dbd.O)(R.sup.1).sub.2,
Si(R.sup.1).sub.3, a straight-chain alkyl or alkoxy group having 1
to 20 carbon atoms or a branched or cyclic alkyl, or alkoxy group
having 3 to 20 carbon atoms, each of which may be substituted by
one or more R.sup.1 radicals, where one or more nonadjacent
CH.sub.2 groups may be replaced by 0, and where one or more
hydrogen atoms may be replaced by D or an aromatic or
heteroaromatic ring system which has 5 to 40 aromatic ring atoms
and may be substituted in each case by one or more R.sup.1
radicals; at the same time, it is optionally possible for two R
substituents bonded to the same carbon atom or to adjacent carbon
atoms to form a monocyclic or polycyclic, aliphatic, aromatic or
heteroaromatic ring system which may be substituted by one or more
R.sup.1 radicals; R.sup.1 is the same or different at each instance
and is selected from the group consisting of H, D, F, CN,
N(R.sup.2).sub.2, a straight-chain alkyl group having 1 to 10
carbon atoms or a branched or cyclic alkyl group having 3 to 10
carbon atoms, each of which may be substituted by one or more
R.sup.2 radicals, where one or more hydrogen atoms may be replaced
by D or F, or an aromatic or heteroaromatic ring system which has 5
to 40 aromatic ring atoms and may be substituted in each case by
one or more R.sup.2 radicals; at the same time, it is optionally
possible for two R.sup.1 substituents bonded to the same carbon
atom or to adjacent carbon atoms to form a monocyclic or
polycyclic, aliphatic, aromatic or heteroaromatic ring system which
may be substituted by one or more R.sup.2 radicals; R.sup.2 is the
same or different at each instance and is selected from the group
consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having
1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system
having 5 to 30 aromatic ring atoms in which one or more hydrogen
atoms may be replaced by D, F, CN and which may be substituted by
one or more alkyl groups each having 1 to 4 carbon atoms; at the
same time, it is possible for two or more adjacent R.sup.2
substituents together to form a mono- or polycyclic, aliphatic ring
system.
17. The electronic device according to claim 16, wherein the
electronic device is an organic electroluminescent device and the
least one compound according to formula (1) is used as matrix
material for fluorescent or phosphorescent emitters in an emitting
layer and/or as electron transport or hole blocker material in an
electron transport layer and/or in a hole-blocking layer.
18. The electronic device according to claim 16, wherein the least
one compound is selected from the compounds of the formulae (7a),
(7b), (7c), (7d) and (7e) ##STR00361## where: W two adjacent W
groups together are a group of the following formula (2a) or (3a)
and the two other W groups are CR, where W in formula (7d) is C
when an L.sup.1 group is bonded to this position, and in formula
(7e) is C when the dibenzofuran or dibenzothiophene is bonded to
this position: ##STR00362## where the dotted bonds indicate the
linkage of this group; n is the same or different at each instance
and is 0, 1, 2, 3 or 4; m is the same or different at each instance
and is 0, 1, 2 or 3; the further symbols used have the definitions
given in claim 16.
19. The electronic device according to claim 16, wherein L.sup.1
and L.sup.2 are single bonds.
20. The electronic device according to claim 16, wherein the at
least one compound is selected from the compounds of the formulae
(9a), (9b), (9c), (9d) and (9e) ##STR00363## where W, n and m have
the definitions given in claim 17 and the further symbols used
those given in claim 16.
21. The electronic device according to claim 16, wherein in the at
least one compound the group of the formula (4) is selected from
the structures of the formulae (4-1) to (4-3) and that the group of
the formula (5) is selected from the structures of the formulae
(5-1) to (5-18) ##STR00364## ##STR00365## ##STR00366## where the
dotted bond represents the bond to the nitrogen atom and in
addition: R is the same or different at each instance and is H, an
alkyl group which has 1 to 10 carbon atoms and may be substituted
by one or more R.sup.1 groups, or an aromatic or heteroaromatic
ring system which has 5 to 40 aromatic ring atoms and may be
substituted in each case by one or more R.sup.1 radicals.
22. The electronic device according to claim 16, wherein in the at
least one compound L.sup.3 is a single bond or an aromatic ring
system having 6 to 12 aromatic ring atoms.
23. The electronic device according to claim 16, wherein in the at
least one compound the Ar.sup.1 or Ar.sup.2 group which is not a
group of the formula (4) or (5) is selected from the group
consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl,
quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or
4-spirobifluorenyl, 1-, 2-, 3- or 4-dibenzofuranyl and 1-, 2-, 3-
or 4-dibenzothienyl, each of which may be substituted by one or
more nonaromatic R radicals.
24. The electronic device according to claim 18, wherein in the at
least one compound the index n is the same or different at each
instance and is 0, 1, 2 or 3, and in that the index m is the same
or different at each instance and is 0, 1 or 2.
25. The electronic device according to claim 16, wherein in the at
least one compound R is selected from the group consisting of H, D,
F, CN, N(R.sup.1).sub.2, C(.dbd.O)R.sup.1,
P(.dbd.O)(R.sup.1).sub.2, a straight-chain alkyl or alkoxy group
having 1 to 10 carbon atoms or a branched or cyclic alkyl or alkoxy
group having 3 to 10 carbon atoms or an alkenyl group having 2 to
10 carbon atoms, each of which may be substituted by one or more
R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may
be replaced by O and where one or more hydrogen atoms may be
replaced by D or F, an aromatic or heteroaromatic ring system which
has 5 to 24 aromatic ring atoms and may be substituted in each case
by one or more R.sup.1 radicals; at the same time, it is optionally
possible for two R substituents bonded to the same carbon atom or
to adjacent carbon atoms to form a monocyclic or polycyclic,
aliphatic, aromatic or heteroaromatic ring system which may be
substituted by one or more R.sup.1 radicals.
26. The electronic device according to claim 16, wherein the least
one compound is selected from the compounds of the formulae (10)
and (11) ##STR00367## where the symbols used have the definitions
given in claim 16 and Ar is the same or different at each instance
and is an aromatic or heteroaromatic ring system which has 5 to 40
aromatic ring atoms and may be substituted by one or more R.sup.1
radicals.
Description
[0001] The present invention describes carbazolyl compounds
substituted by electron-deficient heteroaryl groups, especially for
use as triplet matrix materials in organic electroluminescent
devices. The invention further relates to a process for preparing
the compounds of the invention and to electronic devices comprising
these.
[0002] Emitting materials used in organic electroluminescent
devices (OLEDs) are frequently organometallic complexes which
exhibit phosphorescence. For quantum-mechanical reasons, up to four
times the energy efficiency and power efficiency is possible using
organometallic compounds as phosphorescent emitters. In general
terms, there is still a need for improvement in OLEDs, especially
also in OLEDs which exhibit phosphorescence, for example with
regard to efficiency, operating voltage and lifetime.
[0003] The properties of phosphorescent OLEDs are not just
determined by the triplet emitters used. More particularly, the
other materials used, for example matrix materials, are also of
particular significance here. Improvements to these materials can
thus also lead to distinct improvements in the OLED properties.
[0004] According to the prior art, matrix materials used for
phosphorescent emitters in organic electroluminescent devices
include carbazole derivatives and dibenzofuran derivatives. JP
2012-049518, U.S. Pat. Nos. 7,935,434 and 8,221,908 disclose
dibenzofuran derivatives substituted by two N-phenylcarbazolyl
groups. WO 2014/081206 discloses compounds in which two carbazolyl
groups, one of which is substituted on the nitrogen atom by an
electron-deficient heteroaryl group, are joined to one another via
an arylene group.
[0005] There is generally still a need for improvement in these
materials for use as matrix materials, in aspects including the
external quantum efficiency (EQE). It is therefore an object of the
present invention to provide compounds suitable for use in a
phosphorescent or fluorescent OLED, especially as matrix material.
More particularly, it is an object of the present invention to
provide matrix materials which are suitable for red-, yellow- and
green-phosphorescing OLEDs and possibly also for
blue-phosphorescing OLEDs, and which lead to long lifetime, good
efficiency and low operating voltage. More particularly, it is an
object of the present invention to provide materials that lead to
an improved external quantum efficiency.
[0006] It has been found that, surprisingly, electroluminescent
devices containing compounds of the formula (1) below have
improvements over the prior art, especially when used as matrix
material for phosphorescent dopants.
[0007] The present invention therefore provides a compound of the
following formula (1):
##STR00001##
[0008] where the symbols used are as follows: [0009] A is the same
or different at each instance and is CR or N, where not more than
two A groups per cycle are N, preferably not more than one A group
per cycle is N; more preferably, all A groups are CR; [0010] Y is O
or S; [0011] W is the same or different at each instance and is CR
or N, where not more than two W groups per cycle are N and where W
is C when an L.sup.1 or L.sup.2 group is bonded to this position,
or two adjacent W groups together are a group of the following
formula (2) or (3), where each of the two carbazolyl derivative
groups in the compound of the formula (1) have not more than two
groups of the formula (2) or formula (3):
[0011] ##STR00002## [0012] where the dotted bonds indicate the
linkage of this group, A has definitions given above and Z is NR,
CR.sub.2, O or S; [0013] Ar.sup.1, Ar.sup.2 is an aromatic ring
system having 5 to 30 aromatic ring atoms or a dibenzofuran or
dibenzothiophene group, where the aromatic ring system or the
dibenzofuran or dibenzothiophene group may be substituted in each
case by one or more nonaromatic R radicals, or is a group of one of
the following formulae (4) and (5):
[0013] ##STR00003## [0014] where the dotted bond represents the
bond to the nitrogen atom; [0015] with the proviso that exactly one
of the Ar.sup.1 and Ar.sup.2 groups is a group of one of the
formulae (4) and (5); [0016] X is the same or different at each
instance and is CR or N, where X in formula (5) is C when the group
of the formula (5) in this position is joined to L.sup.3, with the
proviso that, in formula (4), two or three X groups are N and, in
formula (5), one, two or three X groups are N; [0017] L.sup.1,
L.sup.2, L.sup.3 is the same or different at each instance and is a
single bond or an aromatic or heteroaromatic ring system which has
5 to 30 aromatic ring atoms and may be substituted by one or more R
radicals; [0018] R is the same or different at each instance and is
selected from the group consisting of H, D, F, Cl, Br, I, CN,
NO.sub.2, N(R.sup.1).sub.2, C(.dbd.O)R.sup.1,
P(.dbd.O)(R.sup.1).sub.2 P(R.sup.1).sub.2, B(R.sup.1).sub.2,
Si(R.sup.1).sub.3, a straight-chain alkyl, alkoxy or thioalkyl
group having 1 to 20 carbon atoms or a branched or cyclic alkyl,
alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl
group having 2 to 20 carbon atoms, each of which may be substituted
by one or more R.sup.1 radicals, where one or more nonadjacent
CH.sub.2 groups may be replaced by R.sup.1C.dbd.CR.sup.1,
Si(R.sup.1).sub.2, C.dbd.O, C.dbd.S, C.dbd.NR.sup.1,
P(.dbd.O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and
where one or more hydrogen atoms may be replaced by D, F, Cl, Br,
I, CN or NO.sub.2, an aromatic or heteroaromatic ring system which
has 5 to 40 aromatic ring atoms and may be substituted in each case
by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy
group which has 5 to 40 aromatic ring atoms and may be substituted
by one or more R.sup.1 radicals; at the same time, it is optionally
possible for two R substituents bonded to the same carbon atom or
to adjacent carbon atoms to form a monocyclic or polycyclic,
aliphatic, aromatic or heteroaromatic ring system which may be
substituted by one or more R.sup.1 radicals; [0019] R.sup.1 is the
same or different at each instance and is selected from the group
consisting of H, D, F, Cl, Br, I, CN, N(R.sup.2).sub.2,
C(.dbd.O)R.sup.1, a straight-chain alkyl group having 1 to 10
carbon atoms or a branched or cyclic alkyl group having 3 to 10
carbon atoms or an alkenyl group having 2 to 10 carbon atoms, each
of which may be substituted by one or more R.sup.2 radicals, where
one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or
CN, or an aromatic or heteroaromatic ring system which has 5 to 40
aromatic ring atoms and may be substituted in each case by one or
more R.sup.2 radicals; at the same time, it is optionally possible
for two R.sup.1 substituents bonded to the same carbon atom or to
adjacent carbon atoms to form a monocyclic or polycyclic,
aliphatic, aromatic or heteroaromatic ring system which may be
substituted by one or more R.sup.2 radicals; [0020] R.sup.2 is the
same or different at each instance and is selected from the group
consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having
1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system
having 5 to 30 aromatic ring atoms in which one or more hydrogen
atoms may be replaced by D, F, CN and which may be substituted by
one or more alkyl groups each having 1 to 4 carbon atoms; at the
same time, it is possible for two or more adjacent R.sup.2
substituents together to form a mono- or polycyclic, aliphatic ring
system.
[0021] Adjacent carbon atoms in the context of the present
invention are carbon atoms bonded directly to one another.
[0022] The wording that two or more radicals together may form a
ring, in the context of the present description, shall be
understood to mean, inter alia, that the two radicals are joined to
one another by a chemical bond with formal elimination of two
hydrogen atoms. This is illustrated by the following scheme:
##STR00004##
[0023] In addition, however, the abovementioned wording shall also
be understood to mean that, if one of the two radicals is hydrogen,
the second radical binds to the position to which the hydrogen atom
was bonded, forming a ring. This shall be illustrated by the
following scheme:
##STR00005##
[0024] An aryl group in the context of this invention contains 6 to
40 carbon atoms; a heteroaryl group in the context of this
invention contains 2 to 40 carbon atoms and at least one
heteroatom, with the proviso that the sum total of carbon atoms and
heteroatoms is at least 5. The heteroatoms are preferably selected
from N, O and/or S, where the heteroaryl group preferably contains
not more than three heteroatoms. An aryl group or heteroaryl group
is understood here to mean either a simple aromatic cycle, i.e.
benzene, or a simple heteroaromatic cycle, for example pyridine,
pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group,
for example naphthalene, anthracene, phenanthrene, quinoline,
isoquinoline, etc.
[0025] A fused aryl group in the context of the present invention
is a group in which two or more aromatic groups are fused, i.e.
annelated, to one another along a common edge, as, for example, in
naphthalene. By contrast, for example, fluorene is not a fused aryl
group in the context of the present invention, since the two
aromatic groups in fluorene do not have a common edge.
[0026] An aromatic ring system in the context of this invention
contains 6 to 40 carbon atoms in the ring system. A heteroaromatic
ring system in the context of this invention contains 1 to 40
carbon atoms and at least one heteroatom in the ring system, with
the proviso that the sum total of carbon atoms and heteroatoms is
at least 5. The heteroatoms are preferably selected from N, O
and/or S, where the heteroaromatic ring system preferably contains
not more than four heteroatoms, more preferably not more than three
heteroatoms. An aromatic or heteroaromatic ring system in the
context of this invention shall be understood to mean a system
which does not necessarily contain only aryl or heteroaryl groups,
but in which it is also possible for two or more aryl or heteroaryl
groups to be interrupted by a nonaromatic unit (preferably less
than 10% of the atoms other than H), for example a carbon, nitrogen
or oxygen atom or a carbonyl group. For example, systems such as
9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl
ethers, stilbene, etc. shall also be regarded as aromatic ring
systems in the context of this invention, and likewise systems in
which two or more aryl groups are interrupted, for example, by a
linear or cyclic alkyl group. In addition, systems in which two or
more aryl or heteroaryl groups are bonded directly to one another,
for example biphenyl, terphenyl, quaterphenyl or bipyridine, shall
likewise be regarded as an aromatic or heteroaromatic ring
system.
[0027] A cyclic alkyl, alkoxy or thioalkoxy group in the context of
this invention is understood to mean a monocyclic, bicyclic or
polycyclic group.
[0028] In the context of the present invention, a C.sub.1- to
C.sub.20-alkyl group in which individual hydrogen atoms or CH.sub.2
groups may also be substituted by the abovementioned groups are
understood to mean, for example, the methyl, ethyl, n-propyl,
i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl,
cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl,
neopentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl,
3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl,
n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl,
1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl,
1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl,
2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl,
trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl,
1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl,
1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl-n-dec-1-yl,
1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl,
1,1-dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl,
1,1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hept-1-yl,
1,1-diethyl-n-oct-1-yl, 1,1-diethyl-n-dec-1-yl,
1,1-diethyl-n-dodec-1-yl, 1,1-diethyl-n-tetradec-1-yl,
1,1-diethyl-n-hexadec-1-yl, 1,1-diethyl-n-octadec-1-yl,
1-(n-propyl)cyclohex-1-yl, 1-(n-butyl)cyclohex-1-yl,
1-(n-hexyl)cyclohex-1-yl, 1-(n-octyl)cyclohex-1-yl and
1-(n-decyl)cyclohex-1-yl radicals. An alkenyl group is understood
to mean, for example, ethenyl, propenyl, butenyl, pentenyl,
cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl,
octenyl, cyclooctenyl or cyclooctadienyl. An alkynyl group is
understood to mean, for example, ethynyl, propynyl, butynyl,
pentynyl, hexynyl, heptynyl or octynyl. A C.sub.1- to
C.sub.40-alkoxy group is understood to mean, for example, methoxy,
trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,
s-butoxy, t-butoxy or 2-methylbutoxy.
[0029] An aromatic or heteroaromatic ring system which has 5-40
aromatic ring atoms and may also be substituted in each case by the
abovementioned radicals and which may be joined to the aromatic or
heteroaromatic system via any desired positions is understood to
mean, for example, groups derived from benzene, naphthalene,
anthracene, benzanthracene, phenanthrene, benzophenanthrene,
pyrene, chrysene, perylene, fluoranthene, benzofluoranthene,
naphthacene, pentacene, benzopyrene, biphenyl, biphenylene,
terphenyl, terphenylene, fluorene, spirobifluorene,
dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or
trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis-
or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene,
spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran,
thiophene, benzothiophene, isobenzothiophene, dibenzothiophene,
pyrrole, indole, isoindole, carbazole, indolocarbazole,
indenocarbazole, pyridine, quinoline, isoquinoline, acridine,
phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,
benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole,
indazole, imidazole, benzimidazole, naphthimidazole,
phenanthrimidazole, pyridimidazole, pyrazinimidazole,
quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole,
anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole,
1,3-thiazole, benzothiazole, pyridazine, benzopyridazine,
pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene,
2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene,
4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine,
phenoxazine, phenothiazine, fluorubine, naphthyridine,
azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole,
1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole,
1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole,
1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole,
1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole,
1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine,
pteridine, indolizine and benzothiadiazole.
[0030] Preference is given to the compounds of the following
formula (1a):
##STR00006##
[0031] where the symbols used have the definitions given above and
A is C when an L.sup.1 or L.sup.2 group is bonded to this
position.
[0032] In a preferred embodiment of the invention, the L.sup.2
group is a single bond. A preferred embodiment of the compound of
the formula (1) is thus a compound of the following formula (6),
and a preferred embodiment of the compound of the formula (1a) is a
compound of the formula (6a):
##STR00007##
[0033] where the symbols used have the definitions given above.
[0034] In a preferred embodiment of the invention, W is the same or
different at each instance and is CR, or two W are a group of the
formula (2a) or (3a) and the remaining W are CR, and A is the same
or different at each instance and is CR. Preference is thus given
to the compounds of the following formulae (7a), (7b), (7c), (7d)
and (7e):
##STR00008## ##STR00009##
[0035] where: [0036] W two adjacent W groups together are a group
of the following formula (2a) or (3a) and the two other W groups
are CR and preferably CH, where W in formula (7d) is C when an
L.sup.1 group is bonded to this position, and in formula (7e) is C
when the dibenzofuran or dibenzothiophene is bonded to this
position:
[0036] ##STR00010## [0037] where the dotted bonds indicate the
linkage of this group; [0038] n is the same or different at each
instance and is 0, 1, 2, 3 or 4; [0039] m is the same or different
at each instance and is 0, 1, 2 or 3; [0040] the further symbols
used have the definitions given above.
[0041] In a further preferred embodiment of the invention, L.sup.1
and L.sup.2 are each a single bond. Preference is thus given to the
compounds of the following formulae (8a), (8b), (8c), (8d) and
(8e):
##STR00011## ##STR00012##
[0042] where the symbols and indices used have the definitions
given above.
[0043] In a particularly preferred embodiment of the invention, the
two carbazole groups or carbazole derivatives are joined by the 3
position, i.e. via the position para to the nitrogen atoms.
Particular preference is thus given to the compounds of the
following formulae (9a), (9b), (9c), (9d) and (9e):
##STR00013##
[0044] where the symbols and indices used have the definitions
given above.
[0045] Very particular preference is given to compounds in which
all W groups are CR or C, i.e. the compounds of the formulae (7a),
(8a) and (9a).
[0046] Preference is further given to compounds of the
abovementioned formulae in which Y is O.
[0047] In a further preferred embodiment of the invention, Z, if
the compound contains a group of the formula (2), is O, NR where
the R radical bonded to the nitrogen is not H, or C(R).sub.2, more
preferably NR where the R radical bonded to the nitrogen is not H,
or C(R).sub.2, and most preferably C(R).sub.2.
[0048] In a preferred embodiment of the invention, each of the
carbazolyl derivative groups contains not more than one group of
the formula (2) or formula (3).
[0049] When the compound of the invention contains a group of the
formula (2), this may be bonded in various positions. This is shown
hereinafter in schematic form with reference to preferred
embodiments in which the A groups and the other W groups are CR, by
the formulae (A) to (F):
##STR00014##
[0050] where the symbols and indices used have the definitions
given above and the dotted bond represents the linkage in the
compound of the invention. The same applies to the other carbazole
derivatives which, rather than the Ar.sup.1 group, contains an
Ar.sup.2 group bonded to the nitrogen.
[0051] When the compound of the invention contains a group of the
formula (3), this may be bonded in various positions. This is shown
hereinafter in schematic form with reference to preferred
embodiments in which the A groups and the other W groups are CR, by
the formulae (G) to (K):
##STR00015##
[0052] where the symbols and indices used have the definitions
given above and the dotted bond represents the linkage in the
compound of the invention.
[0053] The same applies to the other carbazole derivative
containing an Ar.sup.2 group.
[0054] There follows a description of preferred embodiments of the
Ar.sup.1 and Ar.sup.2 groups. As described above, one of the
Ar.sup.1 and Ar.sup.2 groups is an aromatic ring system having 5 to
30 aromatic ring atoms or is a dibenzofuran or dibenzothiophene
group, each of which may be substituted by one or more nonaromatic
R radicals, and the other of the Ar.sup.1 and Ar.sup.2 groups is a
heteroaryl group of one of the formulae (4) and (5).
[0055] In one embodiment of the compounds of formula (1) or (1a) or
the compounds of formula (6), (7a) to (7e), (8a) to (8e) and (9a)
to (9e), Ar.sup.1 is an aromatic ring system having 5 to 30
aromatic ring atoms or a dibenzofuran or dibenzothiophene group,
where the aromatic ring system or the dibenzofuran or
dibenzothiophene group may be substituted in each case by one or
more nonaromatic R radicals, and Ar.sup.2 is a heteroaryl group of
one of the formulae (4) and (5).
[0056] In a further embodiment of the compounds of formula (1) or
(1a) or the compounds of formula (6), (7a) to (7e), (8a) to (8e)
and (9a) to (9e), Ar.sup.2 is an aromatic ring system having 5 to
30 aromatic ring atoms or a dibenzofuran or dibenzothiophene group,
where the aromatic ring system or the dibenzofuran or
dibenzothiophene group may be substituted in each case by one or
more nonaromatic R radicals, and Ar.sup.1 is a heteroaryl group of
one of the formulae (4) and (5).
[0057] In a preferred embodiment of the invention, the group of the
formula (4) is selected from the structures of the following
formulae (4-1) to (4-3):
##STR00016##
[0058] where the dotted bond represents the bond to the nitrogen
atom and in addition: [0059] R is the same or different at each
instance and is H, an alkyl group which has 1 to 10 carbon atoms
and may be substituted by one or more R.sup.1 radicals, but is
preferably unsubstituted, or an aromatic or heteroaromatic ring
system which has 5 to 40 aromatic ring atoms and may be substituted
in each case by one or more R.sup.1 radicals, but is preferably
unsubstituted; preferably, R is not H.
[0060] In a particularly preferred embodiment of the invention, the
group of the formula (4) is selected from the structures of the
following formulae (4-1a) to (4-3a):
##STR00017##
[0061] where the dotted bond represents the bond to the nitrogen
atom and in addition: [0062] Ar is the same or different at each
instance and is an aromatic or heteroaromatic ring system which has
5 to 40 aromatic ring atoms and may be substituted in each case by
one or more R.sup.1 radicals, but is preferably unsubstituted.
[0063] In a preferred embodiment of the group of the formula (5),
one or two symbols X are N, more preferably two symbols X.
Preferably, the group of the formula (5) is selected from the
structures of the following formulae (5-1) to (5-18):
##STR00018## ##STR00019## ##STR00020##
[0064] where the dotted bond represents the bond to the nitrogen
atom and in addition: [0065] R is the same or different at each
instance and is H, an alkyl group which has 1 to 10 carbon atoms
and may be substituted by one or more R.sup.1 radicals, but is
preferably unsubstituted, or an aromatic or heteroaromatic ring
system which has 5 to 40 aromatic ring atoms and may be substituted
in each case by one or more R.sup.1 radicals, but is preferably
unsubstituted; preferably, R is not H.
[0066] More preferably, the group of the formula (5) is selected
from the structures of the following formulae (5-1a) to
(5-18a):
##STR00021## ##STR00022##
[0067] where the dotted bond represents the bond to the nitrogen
atom and Ar has the definitions given above.
[0068] In a preferred embodiment of the invention, L.sup.3 is the
same or different at each instance and is a single bond or an
aromatic ring system having 6 to 12 aromatic ring atoms, more
preferably a single bond or para- or meta-phenylene and most
preferably a single bond.
[0069] In a further preferred embodiment of the invention, Ar in
the groups of the formulae (4-1a) to (4-3a) and (5-1a) to (5-18a)
is the same or different at each instance and is an aromatic or
heteroaromatic ring system having 6 to 24 aromatic ring atoms,
preferably having 6 to 18 aromatic ring atoms, more preferably an
aromatic ring system having 6 to 12 aromatic ring atoms or a
heteroaromatic ring system having 6 to 13 aromatic ring atoms, each
of which may be substituted by one or more R.sup.1 radicals, but is
preferably unsubstituted. Examples of suitable Ar groups are
selected from the group consisting of phenyl, ortho-, meta- or
para-biphenyl, terphenyl, especially branched terphenyl,
quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or
4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl,
pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or
4-dibenzothienyl and 1-, 2-, 3- or 4-carbazolyl, each of which may
be substituted by one or more R.sup.1 radicals, but are preferably
unsubstituted.
[0070] Examples of suitable Ar groups are the structures Ar-1 to
Ar-19 groups listed below:
##STR00023## ##STR00024## ##STR00025## ##STR00026##
[0071] where R.sup.1 has the definitions given above and is
preferably H, the dotted bond represents the linkage of this group
and V is NR.sup.1, O, S or C(R.sup.1).sub.2.
[0072] In a further preferred embodiment of the invention, the
Ar.sup.1 or Ar.sup.2 group which is not a group of the formula (4)
or (5) is an aromatic ring system having 6 to 24 aromatic ring
atoms, preferably having 6 to 18 aromatic ring atoms, more
preferably having 6 to 12 aromatic ring atoms, or is a dibenzofuran
or dibenzothiophene group, where these groups may each be
substituted by one or more nonaromatic R radicals, but are
preferably unsubstituted. Examples of suitable Ar.sup.1 or Ar.sup.2
groups which are not a group of the formula (4) or (5) are selected
from the group consisting of phenyl, ortho-, meta- or
para-biphenyl, terphenyl, especially branched terphenyl,
quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or
4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1-, 2-, 3- or
4-dibenzofuranyl and 1-, 2-, 3- or 4-dibenzothienyl, each of which
may be substituted by one or more nonaromatic R radicals, but are
preferably unsubstituted.
[0073] Examples of suitable Ar.sup.1 or Ar.sup.2 groups are the
structures Ar.sup.1-1 to Ar.sup.1-19 or Ar.sup.2-1 to Ar.sup.2-19
listed below:
##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031##
##STR00032##
[0074] where R has the definitions given above and is preferably H,
the dotted bond represents the bond to the nitrogen atom and
Y.sup.3 is the same or different at each instance and is CR.sub.2,
O or S.
[0075] In a further preferred embodiment of the invention, in
compounds of the formulae (7a) to (7e), (8a) to (8e) and (9a) to
(9e), the index n is the same or different at each instance and is
0, 1, 2 or 3, more preferably 0, 1 or 2 and even more preferably 0
or 1 and especially 0.
[0076] In yet a further preferred embodiment of the invention, in
compounds of the formulae (7a) to (7e), (8a) to (8e) and (9a) to
(9e), the index m is the same or different at each instance and is
0, 1 or 2, more preferably 0 or 1 and even more preferably 0.
[0077] There follows a description of preferred substituents R. R
is preferably selected from the group consisting of H, D, F, CN,
N(R.sup.1).sub.2, C(.dbd.O)R.sup.1, P(.dbd.O)(R.sup.1).sub.2, a
straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms or
a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon
atoms or an alkenyl group having 2 to 10 carbon atoms, where the
alkyl, alkoxy or alkenyl group may be substituted in each case by
one or more R.sup.1 radicals, where one or more nonadjacent
CH.sub.2 groups may be replaced by O and where one or more hydrogen
atoms may be replaced by D or F, an aromatic or heteroaromatic ring
system which has 5 to 24 aromatic ring atoms and may be substituted
in each case by one or more R.sup.1 radicals, but is preferably
unsubstituted; at the same time, it is optionally possible for two
R substituents bonded to the same carbon atom or to adjacent carbon
atoms to form a monocyclic or polycyclic, aliphatic, aromatic or
heteroaromatic ring system which may be substituted by one or more
R.sup.1 radicals.
[0078] More preferably, these R substituents are selected from the
group consisting of H, D, F, CN, a straight-chain alkyl group
having 1 to 8 carbon atoms, preferably having 1, 2, 3 or 4 carbon
atoms, or a branched or cyclic alkyl group having 3 to 8 carbon
atoms, preferably having 3 or 4 carbon atoms, or an alkenyl group
having 2 to 8 carbon atoms, preferably having 2, 3 or 4 carbon
atoms, where the alkyl or alkenyl group may be substituted in each
case by one or more R.sup.1 radicals, but is preferably
unsubstituted, or an aromatic or heteroaromatic ring system having
6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic
ring atoms, more preferably having 6 to 13 aromatic ring atoms,
each of which may be substituted by one or more nonaromatic R.sup.1
radicals, but is preferably unsubstituted; at the same time, it is
optionally possible for two R substituents bonded to the same
carbon atom or to adjacent carbon atoms to form a monocyclic or
polycyclic aliphatic ring system which may be substituted by one or
more R.sup.1 radicals, but is preferably unsubstituted.
[0079] Most preferably, the R substituents are selected from the
group consisting of H and an aromatic or heteroaromatic ring system
having 6 to 18 aromatic ring atoms, preferably having 6 to 13
aromatic ring atoms, each of which may be substituted by one or
more nonaromatic R.sup.1 radicals, but is preferably unsubstituted.
Examples of suitable R substituents are selected from the group
consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl,
especially branched terphenyl, quaterphenyl, especially branched
quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or
4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or
4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl and 1-, 2-, 3- or
4-carbazolyl, each of which may be substituted by one or more
R.sup.1 radicals, but are preferably unsubstituted. Suitable
structures R are the same structures as depicted above for Ar-1 to
Ar-19.
[0080] When Z in the structure of the formula (2) is NR, it is
preferable when the R radical bonded to this nitrogen atom is the
same or different at each instance and is an aromatic or
heteroaromatic ring system which has 5 to 24 aromatic ring atoms
and may be substituted in each case by one or more R.sup.1
radicals, more preferably an aromatic or heteroaromatic ring system
which has 6 to 18 aromatic ring atoms and may be substituted by one
or more R.sup.1 radicals. Examples of suitable R substituents are
selected from the group consisting of phenyl, ortho-, meta- or
para-biphenyl, terphenyl, especially branched terphenyl,
quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or
4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl,
pyrimidinyl, 1,3,5-triazinyl, 4,6-diphenyl-1,3,5-triazinyl, 1-, 2-,
3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl and 1-, 2-,
3- or 4-carbazolyl, where the carbazolyl group is substituted on
the nitrogen atom by an R.sup.1 radical other than H or D. These
groups may each be substituted by one or more R.sup.1 radicals, but
are preferably unsubstituted. Suitable structures R are the same
structures as depicted above for Ar-1 to Ar-19.
[0081] In a further preferred embodiment of the invention, R.sup.1
is the same or different at each instance and is selected from the
group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical
having 1 to 6 carbon atoms, preferably having 1, 2, 3 or 4 carbon
atoms, or an aromatic or heteroaromatic ring system having 5 to 30
aromatic ring atoms, preferably having 5 to 24 aromatic ring atoms,
more preferably having 5 to 13 aromatic ring atoms, which may be
substituted by one or more alkyl groups each having 1 to 4 carbon
atoms, but is preferably unsubstituted.
[0082] It is further preferable when the aromatic or heteroaromatic
R or R.sup.1 or R.sup.2 or Ar.sup.1 or Ar.sup.2 groups in the
compound of the invention do not have any aryl or heteroaryl groups
having more than two aromatic six-membered rings fused directly to
one another. Fused aryl groups which have more than two aromatic
six-membered rings are fused directly to one another but are
nevertheless also suitable in accordance with the invention are
phenanthrene and triphenylene, since these also have a high triplet
level.
[0083] The abovementioned preferences can occur individually or
together. It is preferable when the abovementioned preferences
occur together.
[0084] Very particular preference is given to the compounds of the
following formulae (10) and (11):
##STR00033##
[0085] where the symbols used have the definitions given above and
especially the preferred definitions given above.
[0086] Examples of suitable compounds of the invention are the
structures depicted below:
##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038##
##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043##
##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048##
##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053##
##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058##
##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063##
##STR00064## ##STR00065## ##STR00066##
[0087] The compounds of the invention can be prepared by synthesis
steps known to those skilled in the art, for example bromination,
Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc.
A suitable synthesis method is shown in general terms in Scheme 2
below: Scheme 1 shows the synthesis of the 1-bromo-substituted
dibenzofuran which is used as reactant. Scheme 2 shows the
functionalization of the dibenzofuran in the 8 position and the
conversion to the compounds of the invention.
##STR00067##
##STR00068##
[0088] The present invention therefore further provides a process
for preparing the compounds of the invention by reacting an
optionally substituted 1,8-dihalodibenzofuran or
1,8-dihalodibenzothiophene or a corresponding derivative having one
or more nitrogen atoms in the base skeleton with a carbazole
derivative, followed by reaction with the other carbazole
derivative, where the reactions with the carbazole derivatives are
each C--C couplings, especially Suzuki couplings.
[0089] For the processing of the compounds of the invention from a
liquid phase, for example by spin-coating or by printing methods,
formulations of the compounds of the invention are required. These
formulations may, for example, be solutions, dispersions or
emulsions. For this purpose, it may be preferable to use mixtures
of two or more solvents. Suitable and preferred solvents are, for
example, toluene, anisole, o-, m- or p-xylene, methyl benzoate,
mesitylene, tetralin, veratrole, THF, methyl-THF, THP,
chlorobenzene, dioxane, phenoxytoluene, especially
3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene,
1,2,4,5-tetramethylbenzene, 1-methylnaphthalene,
2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone,
3-methylanisole, 4-methylanisole, 3,4-dimethylanisole,
3,5-dimethylanisole, acetophenone, .alpha.-terpineol,
benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone,
cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane,
methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene,
dibenzyl ether, diethylene glycol butyl methyl ether, triethylene
glycol butyl methyl ether, diethylene glycol dibutyl ether,
triethylene glycol dimethyl ether, diethylene glycol monobutyl
ether, tripropylene glycol dimethyl ether, tetraethylene glycol
dimethyl ether, 2-isopropylnaphthalene, pentylbenzene,
hexylbenzene, heptylbenzene, octylbenzene,
1,1-bis(3,4-dimethylphenyl)ethane, hexamethylindane or mixtures of
these solvents.
[0090] The present invention therefore further provides a
formulation comprising a compound of the invention and at least one
further compound. The further compound may, for example, be a
solvent, especially one of the abovementioned solvents or a mixture
of these solvents. The further compound may alternatively be at
least one further organic or inorganic compound which is likewise
used in the electronic device, for example an emitting compound,
especially a phosphorescent dopant, and/or a further matrix
material. Suitable emitting compounds and further matrix materials
are listed at the back in connection with the organic
electroluminescent device. This further compound may also be
polymeric.
[0091] The compounds of the invention and mixtures are suitable for
use in an electronic device. An electronic device is understood to
mean a device containing at least one layer containing at least one
organic compound. This component may also comprise inorganic
materials or else layers formed entirely from inorganic
materials.
[0092] The present invention therefore further provides for the use
of the compounds or mixtures of the invention in an electronic
device, especially in an organic electroluminescent device.
[0093] The present invention still further provides an electronic
device comprising at least one of the above-detailed compounds or
mixtures of the invention.
[0094] In this case, the preferences detailed above for the
compound also apply to the electronic devices.
[0095] The electronic device is preferably selected from the group
consisting of organic electroluminescent devices (OLEDs, PLEDs),
organic integrated circuits (O-ICs), organic field-effect
transistors (O-FETs), organic thin-film transistors (O-TFTs),
organic light-emitting transistors (O-LETs), organic solar cells
(O-SCs), organic dye-sensitized solar cells, organic optical
detectors, organic photoreceptors, organic field-quench devices
(O-FQDs), light-emitting electrochemical cells (LECs), organic
laser diodes (O-lasers) andorganic plasmon emitting devices (D. M.
Koller et al., Nature Photonics 2008, 1-4), preferably organic
electroluminescent devices (OLEDs, PLEDs), especially
phosphorescent OLEDs.
[0096] The organic electroluminescent device comprises cathode,
anode and at least one emitting layer. Apart from these layers, it
may also comprise further layers, for example in each case one or
more hole injection layers, hole transport layers, hole blocker
layers, electron transport layers, electron injection layers,
exciton blocker layers, electron blocker layers and/or charge
generation layers. It is likewise possible for interlayers having
an exciton-blocking function, for example, to be introduced between
two emitting layers. However, it should be pointed out that not
necessarily every one of these layers need be present. In this
case, it is possible for the organic electroluminescent device to
contain an emitting layer, or for it to contain a plurality of
emitting layers. If a plurality of emission layers are present,
these preferably have several emission maxima between 380 nm and
750 nm overall, such that the overall result is white emission; in
other words, various emitting compounds which may fluoresce or
phosphoresce are used in the emitting layers. Especially preferred
are systems having three emitting layers, where the three layers
show blue, green and orange or red emission (for the basic
construction, see, for example, WO 2005/011013). These may be
fluorescent or phosphorescent emission layers or else hybrid
systems in which fluorescent and phosphorescent emission layers are
combined with one another. A white-emitting electroluminescent
device can be used, for example, for lighting applications, but
also in combination with a colour filter for full-colour
displays.
[0097] The compound of the invention according to the
above-detailed embodiments may be used in different layers,
according to the exact structure. Preference is given to an organic
electroluminescent device containing a compound of formula (1) or
according to the preferred embodiments as matrix material for
fluorescent or phosphorescent emitters, especially for
phosphorescent emitters, and/or as electron transport or hole
blocker material in an electron transport layer and/or in a
hole-blocking layer, according to the exact substitution. In this
context, the above-detailed preferred embodiments also apply to the
use of the materials in organic electronic devices.
[0098] In a preferred embodiment of the invention, the compound of
formula (1) or according to the preferred embodiments is used as
matrix material for a phosphorescent compound in an emitting layer.
In this case, the organic electroluminescent device may contain an
emitting layer, or it may contain a plurality of emitting layers,
where at least one emitting layer contains at least one compound of
the invention as matrix material.
[0099] When the compound of formula (1) or according to the
preferred embodiments is used as matrix material for an emitting
compound in an emitting layer, it is preferably used in combination
with one or more phosphorescent materials (triplet emitters).
Phosphorescence in the context of this invention is understood to
mean luminescence from an excited state having spin multiplicity
>1, especially from an excited triplet state. In the context of
this application, all luminescent transition metal complexes and
luminescent lanthanide complexes, especially all iridium, platinum
and copper complexes, shall be regarded as phosphorescent
compounds.
[0100] The mixture of the compound of formula (1) or according to
the preferred embodiments and the emitting compound contains
between 99% and 1% by volume, preferably between 98% and 10% by
volume, more preferably between 97% and 60% by volume and
especially between 95% and 80% by volume of the compound of formula
(1) or according to the preferred embodiments, based on the overall
mixture of emitter and matrix material. Correspondingly, the
mixture contains between 1% and 99% by volume, preferably between
2% and 90% by volume, more preferably between 3% and 40% by volume
and especially between 5% and 20% by volume of the emitter, based
on the overall mixture of emitter and matrix material. If the
compounds are processed from solution, preference is given to using
the corresponding amounts in % by weight rather than the
above-specified amounts in % by volume.
[0101] Suitable phosphorescent compounds (=triplet emitters) are
especially compounds which, when suitably excited, emit light,
preferably in the visible region, and also contain at least one
atom of atomic number greater than 20, preferably greater than 38
and less than 84, more preferably greater than 56 and less than 80,
especially a metal having this atomic number. Preferred
phosphorescence emitters used are compounds containing copper,
molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium,
palladium, platinum, silver, gold or europium, especially compounds
containing iridium or platinum. In the context of the present
invention, all luminescent compounds containing the abovementioned
metals are regarded as phosphorescent compounds.
[0102] Examples of the above-described emitters can be found in
applications WO 00/70655, WO 2001/41512, WO 2002/02714, WO
2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO
05/019373, US 2005/0258742, WO 2009/146770, WO 2010/015307, WO
2010/031485, WO 2010/054731, WO 2010/054728, WO 2010/086089, WO
2010/099852, WO 2010/102709, WO 2011/032626, WO 2011/066898, WO
2011/157339, WO 2012/007086, WO 2014/008982, WO 2014/023377, WO
2014/094961, WO 2014/094960, WO 2015/036074, WO 2015/104045, WO
2015/117718, WO 2016/015815 and the as yet unpublished applications
EP 15000307.7, EP 15182264.0 and EP 16179378.1. In general, all
phosphorescent complexes as used for phosphorescent OLEDs according
to the prior art and as known to those skilled in the art in the
field of organic electroluminescence are suitable, and the person
skilled in the art will be able to use further phosphorescent
complexes without exercising inventive skill.
[0103] A further preferred embodiment of the present invention is
the use of the compound of formula (1) or according to the
preferred embodiments as matrix material for a phosphorescent
emitter in combination with a further matrix material. In a
preferred embodiment of the invention, the further matrix material
is a hole-transporting compound. In a further preferred embodiment
of the invention, the further matrix material is an
electron-transporting compound. In yet a further preferred
embodiment, the further matrix material is a compound having a
large band gap which is not involved to a significant degree, if at
all, in the hole and electron transport in the layer.
[0104] Suitable matrix materials for the compounds of the invention
are ketones, phosphine oxides, sulphoxides and sulphones, for
example according to WO 2004/013080, WO 2004/093207, WO 2006/005627
or WO 2010/006680, triarylamines, carbazole derivatives, e.g. CBP
(N,N-biscarbazolylbiphenyl), m-CBP or the carbazole derivatives
disclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP
1205527, WO 2008/086851 or US 2009/0134784, combinations of
triazines and carbazoles, for example according to WO 2011/057706
or WO 2014/015931, indolocarbazole derivatives, for example
according to WO 2007/063754 or WO 2008/056746, indenocarbazole
derivatives, for example according to WO 2010/136109, WO
2011/000455, WO 2013/041176 or WO 2013/056776, spiroindenocarbazole
derivatives, for example according to WO 2014/094963 or WO
2015/124255, azacarbazoles, for example according to EP 1617710, EP
1617711, EP 1731584, JP 2005/347160, bipolar matrix materials, for
example according to WO 2007/137725, lactams, for example according
to WO 2011/116865, WO 2011/137951, WO 2013/064206 or WO
2014/056567, silanes, for example according to WO 2005/111172,
azaboroles or boronic esters, for example according to WO
2006/117052 or WO 2013/091762, diazasilole derivatives, for example
according to WO 2010/054729, diazaphosphole derivatives, for
example according to WO 2010/054730, triazine derivatives, for
example according to WO 2010/015306, WO 2007/063754, WO 2008/056746
or WO 2014/023388, zinc complexes, for example according to EP
652273 or WO 2009/062578, dibenzofuran derivatives, for example
according to WO 2009/148015, WO 2015/169412, WO 2016/015810 or WO
2016/023608, bridged carbazole derivatives, for example according
to US 2009/0136779, WO 2010/050778, WO 2011/042107 or WO
2011/088877, or triphenylene derivatives, for example according to
WO 2012/048781. It is likewise possible for a further
phosphorescent emitter which emits at a shorter wavelength than the
actual emitter to be present as co-host in the mixture.
[0105] Preferred co-host materials are triarylamine derivatives,
especially monoamines, indenocarbazole derivatives,
4-spirocarbazole derivatives, lactams, triazine derivatives and
carbazole derivatives.
[0106] Preferred triarylamine derivatives which are used as co-host
materials together with the compounds of the invention are selected
from the compounds of the following formula (12):
##STR00069##
[0107] where Ar is the same or different at each instance and has
the definitions given above. Preferably, the Ar groups are the same
or different at each instance and are selected from the
abovementioned Ar-1 to Ar-19 groups.
[0108] In a preferred embodiment of the compounds of the formula
(12), at least one Ar group is selected from a biphenyl group,
which may be an ortho-, meta- or para-biphenyl group. In a further
preferred embodiment of the compounds of the formula (12), at least
one Ar group is selected from a fluorene group or spirobifluorene
group, where these groups may each be bonded to the nitrogen atom
in the 1, 2, 3 or 4 position. In yet a further preferred embodiment
of the compounds of the formula (12), at least one Ar group is
selected from a phenylene or biphenyl group, where the group is an
ortho-, meta- or para-bonded group, substituted by a dibenzofuran
group, a dibenzothiophene group or a carbazole group, especially a
dibenzofuran group, where the dibenzofuran or dibenzothiophene
group is bonded to the phenylene or biphenyl group via the 1, 2, 3
or 4 position and where the carbazole group is bonded to the
phenylene or biphenyl group via the 1, 2, 3 or 4 position or via
the nitrogen atom.
[0109] In a particularly preferred embodiment of the compounds of
the formula (12), one Ar group is selected from a fluorene or
spirobifluorene group, especially a 4-fluorene or 4-spirobifluorene
group, and one Ar group is selected from a biphenyl group,
especially a para-biphenyl group, or a fluorene group, especially a
2-fluorene group, and the third Ar group is selected from a
para-phenylene group or a para-biphenyl group, substituted by a
dibenzofuran group, especially a 4-dibenzofuran group, or a
carbazole group, especially an N-carbazole group or a 3-carbazole
group.
[0110] Preferred indenocarbazole derivatives which are used as
co-host materials together with the compounds of the invention are
selected from the compounds of the following formula (13):
##STR00070##
[0111] where Ar and R have the definitions listed above. Preferred
embodiments of the Ar group are the structures Ar-1 to Ar-19 listed
above.
[0112] A preferred embodiment of the compounds of the formula (13)
is the compounds of the following formula (13a):
##STR00071##
[0113] where Ar and R have the definitions given above. The two R
groups bonded to the indeno carbon atom here are preferably the
same or different and are each an alkyl group having 1 to 4 carbon
atoms, especially methyl groups, or an aromatic ring system having
6 to 12 carbon atoms, especially phenyl groups. More preferably,
the two R groups are bonded to the indeno carbon atom are methyl
groups. Further preferably, the R substituent bonded to the
indenocarbazole base skeleton in formula (13a) is H or a carbazole
group which may be bonded to the indenocarbazole base skeleton via
the 1, 2, 3 or 4 position or via the nitrogen atom, especially via
the 3 position.
[0114] Preferred 4-spirocarbazole derivatives which are used as
co-host materials together with the compounds of the invention are
selected from the compounds of the following formula (14):
##STR00072##
[0115] where Ar and R have the definitions listed above. Preferred
embodiments of the Ar group are the structures Ar-1 to Ar-19 listed
above.
[0116] A preferred embodiment of the compounds of the formula (14)
is the compounds of the following formula (14a):
##STR00073##
[0117] where Ar and R have the definitions given above.
[0118] Preferred lactams which are used as co-host materials
together with the compounds of the invention are selected from the
compounds of the following formula (15):
##STR00074##
[0119] where R has the definitions listed above.
[0120] A preferred embodiment of the compounds of the formula (15)
is the compounds of the following formula (15a):
##STR00075##
[0121] where R has the definitions given above. Preferably, R here
is the same or different at each instance and is H or an aromatic
or heteroaromatic ring system which has 5 to 40 aromatic ring atoms
and which may be substituted by one or more R.sup.1 radicals. Most
preferably, the R substituents are selected from the group
consisting of H and an aromatic or heteroaromatic ring system
having 6 to 18 aromatic ring atoms, preferably having 6 to 13
aromatic ring atoms, each of which may be substituted by one or
more nonaromatic R.sup.1 radicals, but is preferably unsubstituted.
Examples of suitable R substituents are selected from the group
consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl,
especially branched terphenyl, quaterphenyl, especially branched
quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or
4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or
4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl and 1-, 2-, 3- or
4-carbazolyl, each of which may be substituted by one or more
R.sup.1 radicals, but are preferably unsubstituted. Suitable
structures R are the same structures as depicted above for Ar-1 to
Ar-19, where these structures are substituted by R.sup.1 rather
than R.
[0122] In a further embodiment of the invention, the organic
electroluminescent device of the invention does not contain any
separate hole injection layer and/or hole transport layer and/or
hole blocker layer and/or electron transport layer, meaning that
the emitting layer directly adjoins the hole injection layer or the
anode, and/or the emitting layer directly adjoins the electron
transport layer or the electron injection layer or the cathode, as
described, for example, in WO 2005/053051. It is additionally
possible to use a metal complex identical or similar to the metal
complex in the emitting layer as hole transport or hole injection
material directly adjoining the emitting layer, as described, for
example, in WO 2009/030981.
[0123] In addition, it is possible to use the compounds of the
invention in a hole blocker or electron transport layer.
[0124] In the further layers of the organic electroluminescent
device of the invention, it is possible to use any materials as
typically used according to the prior art. The person skilled in
the art is therefore able, without exercising inventive skill, to
use any materials known for organic electroluminescent devices in
combination with the inventive compounds of formula (1) or
according to the preferred embodiments.
[0125] Additionally preferred is an organic electroluminescent
device, characterized in that one or more layers are coated by a
sublimation process. In this case, the materials are applied by
vapour deposition in vacuum sublimation systems at an initial
pressure of less than 10.sup.-5 mbar, preferably less than
10.sup.-6 mbar. It is also possible that the initial pressure is
even lower or higher, for example less than 10.sup.-7 mbar.
[0126] Preference is likewise given to an organic
electroluminescent device, characterized in that one or more layers
are coated by the OVPD (organic vapour phase deposition) method or
with the aid of a carrier gas sublimation. In this case, the
materials are applied at a pressure between 10.sup.-5 mbar and 1
bar. A special case of this method is the OVJP (organic vapour jet
printing) method, in which the materials are applied directly by a
nozzle and thus structured (for example, M. S. Arnold et al., Appl.
Phys. Lett. 2008, 92, 053301).
[0127] Preference is additionally given to an organic
electroluminescent device, characterized in that one or more layers
are produced from solution, for example by spin-coating, or by any
printing method, for example inkjet printing, LITI (light-induced
thermal imaging, thermal transfer printing), screen printing,
flexographic printing, offset printing or nozzle printing. For this
purpose, soluble compounds are needed, which are obtained, for
example, through suitable substitution.
[0128] In addition, hybrid methods are possible, in which, for
example, one or more layers are applied from solution and one or
more further layers are applied by vapour deposition. For example,
it is possible to apply the emitting layer from solution and to
apply the electron transport layer by vapour deposition.
[0129] These methods are known in general terms to those skilled in
the art and can be applied by those skilled in the art without
exercising inventive skill to organic electroluminescent devices
comprising the compounds of the invention.
[0130] The compounds of the invention generally have very good
properties on use in organic electroluminescent devices. Especially
in the case of use of the compounds of the invention in organic
electroluminescent devices, the lifetime is significantly better
compared to similar compounds according to the prior art. At the
same time, the further properties of the organic electroluminescent
device, especially the efficiency and voltage, are likewise better
or at least comparable.
[0131] The invention is now illustrated in detail by the examples
which follow, without any intention of restricting it thereby.
EXAMPLES
[0132] The syntheses which follow, unless stated otherwise, are
conducted under a protective gas atmosphere in dried solvents. The
solvents and reagents can be purchased, for example, from
Sigma-ALDRICH or ABCR. For the compounds known from the literature,
the corresponding CAS numbers are also reported in each case.
a) 6-Bromo-2-fluoro-2'-methoxybiphenyl
##STR00076##
[0134] 200 g (664 mmol) of 1-bromo-3-fluoro-2-iodobenzene, 101 g
(664 mmol) of 2-methoxyphenylboronic acid and 137.5 g (997 mmol) of
sodium tetraborate are dissolved in 1000 ml of THF and 600 ml of
water, and degassed. 9.3 g (13.3 mmol) of
bis(triphenylphosphine)palladium(II) chloride and 1 g (20 mmol) of
hydrazinium hydroxide are added. The reaction mixture is stirred
under a protective gas atmosphere at 70.degree. C. for 48 h. The
cooled solution is supplemented with toluene, washed repeatedly
with water, dried and concentrated. The product is purified via
column chromatography on silica gel with toluene/heptane (1:2).
Yield: 155 g (553 mmol), 83% of theory.
[0135] The following compound is prepared in an analogous
manner:
TABLE-US-00001 Reactant 1 Reactant 2 Product Yield a1 ##STR00077##
##STR00078## ##STR00079## 92%
b) 6'-Bromo-2'-fluorobiphenyl-2-ol
##STR00080##
[0137] 112 g (418 mmol) of 6-bromo-2-fluoro-2'-methoxybiphenyl are
dissolved in 2 l of dichloromethane and cooled to 5.degree. C.
41.01 ml (431 mmol) of boron tribromide are added dropwise to this
solution within 90 min, and stirring of the mixture continues
overnight. The mixture is subsequently admixed gradually with
water, and the organic phase is washed three times with water,
dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation
and purified by chromatography. Yield: 104 g (397 mmol), 98% of
theory.
[0138] The following compound is prepared in an analogous
manner:
TABLE-US-00002 Reactant 1 Product Yield b1 ##STR00081##
##STR00082## 92%
c) 1-Bromodibenzofuran
##STR00083##
[0140] 111 g (416 mmol) of 6'-bromo-2'-fluorobiphenyl-2-ol are
dissolved in 2 l of DMF (max. 0.003% H.sub.2O) SeccoSolv.RTM. and
cooled to 5.degree. C. 20 g (449 mmol) of sodium hydride (60%
suspension in paraffin oil) are added to this solution in portions,
once the addition has ended the mixture is stirred for 20 min, and
then the mixture is heated to 100.degree. C. for 45 min. After
cooling, 500 ml of ethanol are added gradually to the mixture,
which is concentrated by rotary evaporation and then purified by
chromatography. Yield: 90 g (367 mmol), 88.5% of theory.
[0141] The following compound is prepared in an analogous
manner:
TABLE-US-00003 Reactant 1 Product Yield c1 ##STR00084##
##STR00085## 81%
d) 1-Bromo-8-iododibenzofuran
##STR00086##
[0143] 20 g (80 mmol) of 1-bromodibenzofuran, 2.06 g (40.1 mmol) of
iodine, 3.13 g (17.8 mmol) of iodic acid, 80 ml of acetic acid and
5 ml of sulphuric acid and 5 ml of water and 2 ml of chloroform are
stirred at 65.degree. C. for 3 h. After cooling, the mixture is
admixed with water, and the precipitated solids are filtered off
with suction and washed three times with water. The residue is
recrystallized from toluene and from dichloromethane/heptane. The
yield is 25.6 g (68 mmol), corresponding to 85% of theory.
[0144] The following compounds are prepared in an analogous
manner:
TABLE-US-00004 Reactant 1 Product 1 Yield d1 ##STR00087##
##STR00088## 81% d2 ##STR00089## ##STR00090## 67%
e) 3-(9-Bromodibenzofuran-2-yl)-9-phenyl-9H-carbazole
##STR00091##
[0146] 58 g (156 mmol) of 1-bromo-8-iododibenzofuran, 50 g (172
mmol) of N-phenylcarbazole-3-boronic acid and 36 g (340 mmol) of
sodium carbonate are suspended in 1000 ml of ethylene glycol
dimethyl ether and 280 ml of water. 1.8 g (1.5 mmol) of
tetrakis(triphenylphosphine)palladium(0) are added to this
suspension, and the reaction mixture is heated under reflux for 16
h. After cooling, the organic phase is removed, filtered through
silica gel, washed three times with 200 ml of water and then
concentrated to dryness. The yield is 48 g (89 mmol), corresponding
to 64% of theory.
[0147] The following compounds are prepared in an analogous
manner:
TABLE-US-00005 Reactant 1 Reactant 2 Product Yield e1 ##STR00092##
##STR00093## ##STR00094## 67% e2 ##STR00095## ##STR00096##
##STR00097## 65% e3 ##STR00098## ##STR00099## ##STR00100## 62% e4
##STR00101## ##STR00102## ##STR00103## 63% e5 ##STR00104##
##STR00105## ##STR00106## 61% e6 ##STR00107## ##STR00108##
##STR00109## 60% e7 ##STR00110## ##STR00111## ##STR00112## 56% e8
##STR00113## ##STR00114## ##STR00115## 54% e9 ##STR00116##
##STR00117## ##STR00118## 68% e10 ##STR00119## ##STR00120##
##STR00121## 67% e11 ##STR00122## ##STR00123## ##STR00124## 57% e12
##STR00125## ##STR00126## ##STR00127## 60% e13 ##STR00128##
##STR00129## ##STR00130## 63% e14 ##STR00131## ##STR00132##
##STR00133## 68% e15 ##STR00134## ##STR00135## ##STR00136## 63% e16
##STR00137## ##STR00138## ##STR00139## 65% e17 ##STR00140##
##STR00141## ##STR00142## 60% e18 ##STR00143## ##STR00144##
##STR00145## 58% e19 ##STR00146## ##STR00147## ##STR00148## 59% e20
##STR00149## ##STR00150## ##STR00151## 56% e21 ##STR00152##
##STR00153## ##STR00154## 52% e22 ##STR00155## ##STR00156##
##STR00157## 55% e23 ##STR00158## ##STR00159## ##STR00160## 57% e24
##STR00161## ##STR00162## ##STR00163## 56% e25 ##STR00164##
##STR00165## ##STR00166## 70% e26 ##STR00167## ##STR00168##
##STR00169## 75% e27 ##STR00170## ##STR00171## ##STR00172## 72% e28
##STR00173## ##STR00174## ##STR00175## 56% e29 ##STR00176##
##STR00177## ##STR00178## 57% e30 ##STR00179## ##STR00180##
##STR00181## 62% e31 ##STR00182## ##STR00183## ##STR00184## 61% e32
##STR00185## ##STR00186## ##STR00187## 48% e33 ##STR00188##
##STR00189## ##STR00190## 46% e34 ##STR00191## ##STR00192##
##STR00193## 50% e35 ##STR00194## ##STR00195## ##STR00196## 66%
f)
3-[1-[9-[(4,6-Diphenyl-1,3,5-triazin-2-yl)-9H-carbazol-3-yl]-8-dibenzof-
uranyl]-9-phenyl-9H-carbazole
##STR00197##
[0149] 76 g (156 mmol) of
3-(9-bromodibenzofuran-2-yl)-9-phenyl-9H-carbazole, 90 g (172 mmol)
of
9-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-(4,4,5,5-tetramethyl-[1,3,2]dioxab-
orolan-2-yl)-9H-carbazole and 36 g (340 mmol) of sodium carbonate
are suspended in 1000 ml of ethylene glycol dimethyl ether and 280
ml of water. 1.8 g (1.5 mmol) of
tetrakis(triphenylphosphine)palladium(0) are added to this
suspension, and the reaction mixture is heated under reflux for 16
h. After cooling, the organic phase is removed, filtered through
silica gel, washed three times with 200 ml of water and then
concentrated to dryness. The residue is recrystallized five times
from DMF and finally fractionally sublimed twice (p about 10.sup.-6
mbar, T=350-370.degree. C.). Yield: 81 g (110 mmol), 65% of theory:
99.9% by HPLC.
[0150] The following compounds are prepared in an analogous
manner:
TABLE-US-00006 Reactant Reactant Product Yield f1 ##STR00198##
##STR00199## ##STR00200## 61% f2 ##STR00201## ##STR00202##
##STR00203## 53% f3 ##STR00204## ##STR00205## ##STR00206## 54% f4
##STR00207## ##STR00208## ##STR00209## 65% f5 ##STR00210##
##STR00211## ##STR00212## 67% f6 ##STR00213## ##STR00214##
##STR00215## 57% f7 ##STR00216## ##STR00217## ##STR00218## 63% f8
##STR00219## ##STR00220## ##STR00221## 63% f9 ##STR00222##
##STR00223## ##STR00224## 68% f10 ##STR00225## ##STR00226##
##STR00227## 64% f11 ##STR00228## ##STR00229## ##STR00230## 66% f12
##STR00231## ##STR00232## ##STR00233## 68% f13 ##STR00234##
##STR00235## ##STR00236## 60% f14 ##STR00237## ##STR00238##
##STR00239## 58% f15 ##STR00240## ##STR00241## ##STR00242## 61% f16
##STR00243## ##STR00244## ##STR00245## 63% f17 ##STR00246##
##STR00247## ##STR00248## 63% f18 ##STR00249## ##STR00250##
##STR00251## 65% f19 ##STR00252## ##STR00253## ##STR00254## 60% f20
##STR00255## ##STR00256## ##STR00257## 58% f21 ##STR00258##
##STR00259## ##STR00260## 57% f22 ##STR00261## ##STR00262##
##STR00263## 56% f23 ##STR00264## ##STR00265## ##STR00266## 51% f24
##STR00267## ##STR00268## ##STR00269## 53% f25 ##STR00270##
##STR00271## ##STR00272## 56% f26 ##STR00273## ##STR00274##
##STR00275## 56% f27 ##STR00276## ##STR00277## ##STR00278## 70% f28
##STR00279## ##STR00280## ##STR00281## 73% f29 ##STR00282##
##STR00283## ##STR00284## 72% f30 ##STR00285## ##STR00286##
##STR00287## 73% f31 ##STR00288## ##STR00289## ##STR00290## 56% f32
##STR00291## ##STR00292## ##STR00293## 55% f33 ##STR00294##
##STR00295## ##STR00296## 62% f34 ##STR00297## ##STR00298##
##STR00299## 60% f35 ##STR00300## ##STR00301## ##STR00302## 45% f36
##STR00303## ##STR00304## ##STR00305## 57% f37 ##STR00306##
##STR00307## ##STR00308## 62% f38 ##STR00309## ##STR00310##
##STR00311## 65% f39 ##STR00312## ##STR00313## ##STR00314## 67% f40
##STR00315## ##STR00316## ##STR00317## 72%
[0151] Production of the OLEDs
[0152] In examples C1 to I26 which follow (see Tables 1 and 2), the
data of various OLEDs are presented.
[0153] Pretreatment for Examples C1-I26:
[0154] Glass plaques coated with structured ITO (indium tin oxide)
of thickness 50 nm are treated prior to coating with an oxygen
plasma, followed by an argon plasma. These plasma-treated glass
plaques form the substrates to which the OLEDs are applied.
[0155] The OLEDs basically have the following layer structure:
substrate/hole injection layer (HIL)/hole transport layer
(HTL)/electron blocker layer (EBL)/emission layer (EML)/optional
hole blocker layer (HBL)/electron transport layer (ETL)/optional
electron injection layer (EIL) and finally a cathode. The cathode
is formed by an aluminium layer of thickness 100 nm. The exact
structure of the OLEDs can be found in Table 1. The materials used
for production of the OLEDs are shown in Table 3.
[0156] All materials are applied by thermal vapour deposition in a
vacuum chamber. In this case, the emission layer always consists of
at least one matrix material (host material) and an emitting dopant
(emitter) which is added to the matrix material(s) in a particular
proportion by volume by co-evaporation. Details given in such a
form as IC5:PA1:TEG2 (30%:55%:15%) mean here that the material 105
is present in the layer in a proportion by volume of 30%, PA1 in a
proportion by volume of 55% and TEG2 in a proportion by volume of
15%. Analogously, the electron transport layer may also consist of
a mixture of two materials.
[0157] The OLEDs are characterized in a standard manner. For this
purpose, the electroluminescence spectra, the current efficiency
(measured in cd/A) and the external quantum efficiency (EQE,
measured in percent) are determined as a function of luminance,
calculated from current-voltage-luminance characteristics (IUL
characteristics) assuming Lambertian emission characteristics. The
electroluminescence spectra are determined at a luminance of 1000
cd/m.sup.2, and the CIE 1931 x and y colour coordinates are
calculated therefrom. The parameter U1000 in Table 2 refers to the
voltage which is required for a luminance of 1000 cd/m.sup.2.
CE1000 denotes the current efficiency which is achieved at 1000
cd/m.sup.2. Finally, EQE1000 refers to the external quantum
efficiency at an operating luminance of 1000 cd/m.sup.2.
[0158] The data for the various OLEDs are collated in Table 2.
Examples C1-C6 are comparative examples according to the prior art;
examples 11-126 show data of OLEDs of the invention.
[0159] Some of the examples are elucidated in detail hereinafter,
in order to illustrate the advantages of the OLED of the
invention.
[0160] Use of Compounds of the Invention as Matrix Material in
Phosphorescent OLEDs
[0161] The materials of the invention, when used as matrix material
in combination with an electron-conducting compound (for example
compound 105 in the examples adduced below) in the emission layer
(EML) in phosphorescent OLEDs, result in significant improvements
over the prior art, particularly in relation to the external
quantum efficiency of the OLEDs. By use of the inventive compounds
f40, f, f30, f16 and f21 (according to the examples cited above),
it is possible to achieve an improvement in the EQE by about 10% to
50% compared to the compounds from the prior art PA1, PA2, PA3,
PA4, PA5 and PA6 (comparison of examples C1, C2, C3, C4, C5 and C6
with examples I1, I2, I3, I15 and I16).
TABLE-US-00007 TABLE 1 Structure of the OLEDs HIL HTL EBL HBL EIL
thick- thick- thick- EML thick- ETL thick- Ex. ness ness ness
thickness ness thickness ness C1 HATCN SpMA1 SpMA3 IC5:SdT1:TEG2 --
ST2:LiQ -- 5 nm 230 nm 20 nm (30%:55%:15%) 30 nm (50%:50%) 40 nm C2
HATCN SpMA1 SpMA3 IC5:SdT2:TEG2 -- ST2:LiQ -- 5 nm 230 nm 20 nm
(30%:55%:15%) 30 nm (50%:50%) 40 nm C3 HATCN SpMA1 SpMA3
IC5:SdT3:TEG2 -- ST2:LiQ -- 5 nm 230 nm 20 nm (30%:55%:15%) 30 nm
(50%:50%) 40 nm C4 HATCN SpMA1 SpMA3 IC5:SdT4:TEG2 -- ST2:LiQ -- 5
nm 230 nm 20 nm (30%:55%:15%) 30 nm (50%:50%) 40 nm C5 HATCN SpMA1
SpMA3 IC5:SdT5:TEG2 -- ST2:LiQ -- 5 nm 230 nm 20 nm (30%:55%:15%)
30 nm (50%:50%) 40 nm C6 HATCN SpMA1 SpMA3 IC5:SdT6:TEG2 -- ST2:LiQ
-- 5 nm 230 nm 20 nm (30%:55%:15%) 30 nm (50%:50%) 40 nm I1 HATCN
SpMA1 SpMA3 IC5:f40:TEG2 -- ST2:LiQ -- 5 nm 230 nm 20 nm
(30%:55%:15%) 30 nm (50%:50%) 40 nm I2 HATCN SpMA1 SpMA3 IC5:f:TEG2
-- ST2:LiQ -- 5 nm 230 nm 20 nm (30%:55%:15%) 30 nm (50%:50%) 40 nm
I3 HATCN SpMA1 SpMA3 IC5:f30:TEG2 -- ST2:LiQ -- 5 nm 230 nm 20 nm
(30%:55%:15%) 30 nm (50%:50%) 40 nm I4 HATCN SpMA1 SpMA3 f1:TER5 --
ST2:LiQ -- 5 nm 125 nm 10 nm (95%:5%) 40 nm (50%:50%) 35 nm I5
HATCN SpMA1 SpMA3 f2:TER5 -- ST2:LiQ -- 5 nm 125 nm 10 nm (95%:5%)
40 nm (50%:50%) 35 nm I6 HATCN SpMA1 SpMA3 f4:TEG2 -- ST2:LiQ -- 5
nm 230 nm 20 nm (90%:10%0) 30 nm (50%:50%) 40 nm I7 HATCN SpMA1
SpMA3 f5:TER5 -- ST2:LiQ -- 5 nm 125 nm 10 nm (95%:5%) 40 nm
(50%:50%) 35 nm I8 HATCN SpMA1 SpMA3 f7:TEG2 -- ST2:LiQ -- 5 nm 230
nm 20 nm (90%:10%) 30 nm (50%:50%) 40 nm I9 HATCN SpMA1 SpMA3
f8:TEG2 -- ST2:LiQ -- 5 nm 230 nm 20 nm (90%:10%) 30 nm (50%:50%)
40 nm I10 HATCN SpMA1 SpMA3 f9:TER5 -- ST2:LiQ -- 5 nm 125 nm 10 nm
(95%:5%) 40 nm (50%:50%) 35 nm I11 HATCN SpMA1 SpMA3 f10:TEG 2 --
ST2:LiQ -- 5 nm 230 nm 20 nm (90%:10%) 30 nm (50%:50%) 40 nm I12
HATCN SpMA1 SpMA3 f11:TEG2 -- ST2:LiQ -- 5 nm 230 nm 20 nm
(90%:10%) 30 nm (50%:50%) 40 nm I13 HATCN SpMA1 SpMA3 f12:TER5 --
ST2:LiQ -- 5 nm 125 nm 10 nm (95%:5%) 40 nm (50%:50%) 35 nm I14
HATCN SpMA1 SpMA3 f13:TER5 -- ST2:LiQ -- 5 nm 125 nm 10 nm (95%:5%)
40 nm (50%:50%) 35 nm I15 HATCN SpMA1 SpMA3 IC5:f16:TEG2 -- ST2:LiQ
-- 5 nm 230 nm 20 nm (30%:55%:15%) 30 nm (50%:50%) 40 nm I16 HATCN
SpMA1 SpMA3 f17:TER5 -- ST2:LiQ -- 5 nm 125 nm 10 nm (95%:5%) 40 nm
(50%:50%) 35 nm I17 HATCN SpMA1 SpMA3 f19:TER5 -- ST2:LiQ -- 5 nm
125 nm 10 nm (95%:5%) 40 nm (50%:50%) 35 nm I18 HATCN SpMA1 SpMA3
IC5:f21:TEG2 -- ST2:LiQ -- 5 nm 230 nm 20 nm (30%:55%:15%) 30 nm
(50%:50%) 40 nm I19 HATCN SpMA1 SpMA3 f24:TER5 -- ST2:LiQ -- 5 nm
125 nm 10 nm (95%:5%) 40 nm (50%:50%) 35 nm I20 HATCN SpMA1 SpMA3
f25:TEG2 -- ST2:LiQ -- 5 nm 230 nm 20 nm (90%:10%) 30 nm (50%:50%)
40 nm I21 HATCN SpMA1 SpMA3 f26:TEG2 -- ST2:LiQ -- 5 nm 230 nm 20
nm (90%:10%) 30 nm (50%:50%) 40 nm I22 HATCN SpMA1 SpMA3 f27:TER5
-- ST2:LiQ -- 5 nm 125 nm 10 nm (95%:5%) 40 nm (50%:50%) 35 nm I23
HATCN SpMA1 SpMA3 f28:TER5 -- ST2:LiQ -- 5 nm 125 nm 10 nm (95%:5%)
40 nm (50%:50%) 35 nm I24 HATCN SpMA1 SpMA3 f31:TER5 -- ST2:LiQ --
5 nm 125 nm 10 nm (95%:5%) 40 nm (50%:50%) 35 nm I25 HATCN SpMA1
SpMA3 f33:TER5 -- ST2:LiQ -- 5 nm 125 nm 10 nm (95%:5%) 40 nm
(50%:50%) 35 nm I26 HATCN SpMA1 SpMA3 f39:TER5 -- ST2:LiQ -- 5 nm
125 nm 10 nm (95%:5%) 40 nm (50%:50%) 35 nm
TABLE-US-00008 TABLE 2 Data of the OLEDs U1000 CE 1000 EQE CIE x/y
at Ex. (V) (cd/A) 1000 1000 cd/m.sup.2 C1 3.6 44 12.2% 0.34/0.62 C2
3.7 44 12.1% 0.34/0.62 C3 3.5 45 12.5% 0.34/0.62 C4 3.6 44 12.3%
0.34/0.62 C5 3.5 63 16.9% 0.32/0.64 C6 3.6 60 16.7% 0.33/0.63 I1
3.5 68 18.3% 0.34/0.62 I2 3.5 67 18.2% 0.33/0.63 I3 3.6 69 18.5%
0.33/0.63 I4 3.6 23 22.4% 0.67/0.33 I5 3.5 24 22.7% 0.67/0.33 I6
3.5 69 18.5% 0.34/0.63 I7 3.5 23 22.5% 0.67/0.33 I8 3.4 66 17.9%
0.32/0.64 I9 3.6 66 18.0% 0.33/0.63 I10 3.3 25 22.9% 0.67/0.33 I11
3.6 69 18.7% 0.33/0.63 I12 3.5 68 18.6% 0.32/0.63 I13 3.6 24 22.7%
0.67/0.33 I14 3.7 27 23.0% 0.67/0.33 I15 3.6 67 18.4% 0.32/0.63 I16
3.5 23 22.5% 0.67/0.33 I17 3.6 22 22.2% 0.67/0.33 I18 3.6 67 18.2%
0.31/0.64 I19 3.6 27 23.1% 0.67/0.33 I20 3.4 68 18.7% 0.31/0.64 I21
3.5 65 18.1% 0.31/0.64 I22 3.3 22 21.9% 0.67/0.33 I23 3.4 23 22.5%
0.67/0.33 I24 3.5 23 22.4% 0.67/0.33 I25 3.4 24 22.8% 0.67/0.33 I26
3.5 28 23.1% 0.67/0.33
TABLE-US-00009 TABLE 3 Structural formulae of the materials for the
OLEDs ##STR00318## ##STR00319## ##STR00320## ##STR00321##
##STR00322## ##STR00323## ##STR00324## ##STR00325## ##STR00326##
##STR00327## ##STR00328## ##STR00329## ##STR00330## ##STR00331##
##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336##
##STR00337## ##STR00338## ##STR00339## ##STR00340## ##STR00341##
##STR00342## ##STR00343## ##STR00344## ##STR00345## ##STR00346##
##STR00347## ##STR00348## ##STR00349## ##STR00350## ##STR00351##
##STR00352## ##STR00353## ##STR00354## ##STR00355## ##STR00356##
##STR00357##
* * * * *