U.S. patent application number 15/121108 was filed with the patent office on 2017-01-12 for materials for organic light-emitting devices.
This patent application is currently assigned to MERCK PATENT GMBH. The applicant listed for this patent is MERCK PATENT GMBH. Invention is credited to Thomas EBERLE, Tobias GROSSMANN, Anja JATSCH, Jonas Valentin KROEBER, Rouven LINGE, Amir Hossain PARHAM.
Application Number | 20170012219 15/121108 |
Document ID | / |
Family ID | 50190161 |
Filed Date | 2017-01-12 |
United States Patent
Application |
20170012219 |
Kind Code |
A1 |
PARHAM; Amir Hossain ; et
al. |
January 12, 2017 |
MATERIALS FOR ORGANIC LIGHT-EMITTING DEVICES
Abstract
The invention relates to compounds which are suitable for use in
electronic devices, and electronic devices, in particular organic
electroluminescent devices, containing said compounds.
Inventors: |
PARHAM; Amir Hossain;
(Frankfurt Am Main, DE) ; JATSCH; Anja; (Frankfurt
Am Main, DE) ; GROSSMANN; Tobias; (Darmstadt, DE)
; EBERLE; Thomas; (Landau, DE) ; KROEBER; Jonas
Valentin; (Frankfurt Am Main, DE) ; LINGE;
Rouven; (Darmstadt, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MERCK PATENT GMBH |
Darmstadt |
|
DE |
|
|
Assignee: |
MERCK PATENT GMBH
Darmstadt
DE
|
Family ID: |
50190161 |
Appl. No.: |
15/121108 |
Filed: |
January 27, 2015 |
PCT Filed: |
January 27, 2015 |
PCT NO: |
PCT/EP2015/000147 |
371 Date: |
August 24, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07D 495/20 20130101;
C07D 495/14 20130101; C07D 519/00 20130101; H01L 51/0071 20130101;
C07D 487/10 20130101; C07D 513/04 20130101; C07D 403/10 20130101;
C07D 513/10 20130101; C07D 409/04 20130101; C07D 471/14 20130101;
C07D 487/04 20130101; C07D 333/76 20130101; C07D 498/10 20130101;
H01L 51/0073 20130101; C07D 471/20 20130101; C07D 471/22 20130101;
C09K 2211/1029 20130101; C07D 471/10 20130101; H01L 51/0067
20130101; C07D 471/16 20130101; C07D 209/96 20130101; C09K
2211/1011 20130101; C07D 491/147 20130101; C09K 11/025 20130101;
H01L 51/5012 20130101; C07D 498/04 20130101; H01L 51/0061 20130101;
C07D 471/04 20130101; C07D 491/20 20130101; H01L 51/0072 20130101;
C09K 11/06 20130101; C09K 2211/185 20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00; C07D 471/10 20060101 C07D471/10; C07D 498/10 20060101
C07D498/10; C07D 513/10 20060101 C07D513/10; C09K 11/06 20060101
C09K011/06; C07D 471/20 20060101 C07D471/20; C07D 495/20 20060101
C07D495/20; C07D 519/00 20060101 C07D519/00; C07D 471/22 20060101
C07D471/22; C09K 11/02 20060101 C09K011/02; C07D 491/20 20060101
C07D491/20 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 28, 2014 |
EP |
14000729.5 |
Claims
1.-17. (canceled)
18. A compound of formula (1) ##STR00215## wherein X is the same or
different at each instance and is CR or N or two adjacent X groups
together are O, S or NR, so as to give a five-membered ring, or two
adjacent X groups together are a group of the formula (2), (3) or
(4) with the proviso that the compound of the formula (1) contains
at least one group of the formula (2) ##STR00216## where indicates
the positions to which the group of the formula (2) or (3) or (4)
is fused to the compound of the formula (1); A.sup.1, A.sup.2 is
the same or different at each instance and is a single bond,
CR.sub.2, NR, O, S or C.dbd.O; Z is the same or different at each
instance and is C.dbd.O, C.dbd.S, CR.sub.2, BR, SiR.sub.2,
P(.dbd.O)R, SO or SO.sub.2; Y is C when Ar.sup.1 is a 6-membered
aryl or heteroaryl group, or is C or N when Ar.sup.1 is a
5-membered heteroaryl group; E is the same or different at each
instance and is a single bond, CR.sub.2, NR, O, S or C.dbd.O, with
the proviso that E in formula (4) is not a single bond; Ar.sup.1 is
the same or different at each instance and, together with the Y
group and the carbon atom shown explicitly, is an aromatic or
heteroaromatic ring system which has 5 to 24 aromatic ring atoms
and may be substituted by one or more R radicals; Ar.sup.2 is the
same or different at each instance and, together with the three
carbon atoms shown explicitly, is an aromatic or heteroaromatic
ring system which has 5 to 24 aromatic ring atoms and may be
substituted by one or more R radicals; G is the same or different
at each instance and is CR or N; 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(Ar.sup.3).sub.2, N(R.sup.1).sub.2,
C(.dbd.O)Ar.sup.3, C(.dbd.O)R.sup.1, P(.dbd.O)(Ar.sup.3).sub.2, a
straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40
carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl
group having 3 to 40 carbon atoms or an alkenyl or alkynyl group
having 2 to 40 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,
C.ident.C, Si(R.sup.1).sub.2, C.dbd.O, 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, 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, or an aralkyl or heteroaralkyl group
which has 5 to 40 aromatic ring atoms and may be substituted by one
or more R.sup.1 radicals, where it is optionally possible for two
or more adjacent R substituents to form a monocyclic or polycyclic,
aliphatic, aromatic or heteroaromatic ring system which may be
substituted by one or more R.sup.1 radicals; Ar.sup.3 is the same
or different at each instance and is an aromatic or heteroaromatic
ring system which has 5-30 aromatic ring atoms and may be
substituted by one or more nonaromatic R.sup.1 radicals; at the
same time, two Ar.sup.3 radicals bonded to the same nitrogen atom
or phosphorus atom may also be bridged to one another by a single
bond or a bridge selected from N(R.sup.1), C(R.sup.1).sub.2 and O;
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, NO.sub.2,
N(R.sup.2).sub.2, C(.dbd.O)R.sup.2, P(.dbd.O)(R.sup.2).sub.2, a
straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40
carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl
group having 3 to 40 carbon atoms or an alkenyl or alkynyl group
having 2 to 40 carbon atoms, each of which may be substituted by
one or more R.sup.2 radicals, where one or more nonadjacent
CH.sub.2 groups may be replaced by R.sup.2C.dbd.CR.sup.2,
C.ident.C, Si(R.sup.2).sub.2, C.dbd.O, C.dbd.NR.sup.2,
P(.dbd.O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or CONR.sup.2 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.2 radicals, an aryloxy or heteroaryloxy group
which has 5 to 40 aromatic ring atoms and may be substituted by one
or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group
which has 5 to 40 aromatic ring atoms and may be substituted by one
or more R.sup.2 radicals, where it is optionally possible for two
or more adjacent R.sup.1 substituents 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
selected from the group consisting of H, D, F, CN, an aliphatic
hydrocarbyl radical having 1 to 20 carbon atoms, an aromatic or
heteroaromatic ring system having 5 to 30 aromatic ring atoms,
where two or more adjacent R.sup.2 substituents together may form a
mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring
system.
19. The compound as claimed in claim 18, wherein A.sup.1 and
A.sup.2 are single bonds.
20. The compound as claimed in claim 18 comprising exactly one or
two groups of the formula (2).
21. The compound as claimed in claim 18, selected from the
compounds of the formula (5) to (10) ##STR00217## where
.smallcircle. represents the linkage to the nitrogen atom in the
group of the formula (2), and # represents the linkage to the E
group in the group of the formula (2).
22. The compound as claimed in claim 18, selected from the
compounds of the formulae (5a) to (10a) ##STR00218## where the
symbols used have the definitions given in claim 18.
23. The compound as claimed in claim 18, selected from compounds of
the formulae (5b) to (10b) ##STR00219## ##STR00220## where the
symbols used have the definitions given in claim 18.
24. The compound as claimed in claim 18, wherein in the group of
the formula (2), Z is the same or different and is C.dbd.O or
C.dbd.S, and in that E is a single bond, CR.sub.2, C.dbd.O or
NR.
25. The compound as claimed in claim 18, wherein Ar.sup.1 is a
group of the formula (13), (14), (15), (16) or (17) ##STR00221##
where the dotted bond indicates the linkage to Z and * indicates
the position of the linkage to Ar.sup.2; and in that Ar.sup.2 is a
group of the formula (20), (21) or (22) ##STR00222## where the
dotted bond indicates the linkage to N, # indicates the position of
the linkage to E and * indicates the linkage to Ar.sup.1; and in
addition: W is the same or different at each instance and is CR or
N, or two adjacent W groups are a group of the following formula
(18) or (19) ##STR00223## where E is as defined in claim 18, but is
not a single bond, G is the same or different at each instance and
is CR or N and indicate the corresponding adjacent W groups in the
formula (13) to (17); V is NR, O or S.
26. The compound as claimed in claim 18, wherein the group of the
formula (2) is selected from the groups of the formulae (23) to
(29): ##STR00224## where identifies the position of the linkage in
formula (1) and the further symbols used are as defined in claim
18.
27. The compound as claimed in claim 18, wherein the group of the
formula (2) is selected from the groups of the formulae (23a) to
(29a): ##STR00225## where the symbols used have the definitions
given in claim 18.
28. The compound as claimed in claim 18, selected from the
compounds of the formulae (5c) to (10c) ##STR00226## ##STR00227##
where the symbols used are as defined in claim 18.
29. The compound as claimed in claim 18, wherein all R radicals are
H or in that one or two R radicals are an aromatic or
heteroaromatic ring system which has 6 to 24 aromatic ring atoms
and may be substituted in each case by one or more R.sup.1
radicals, and the other R radicals are H.
30. An oligomer, polymer or dendrimer containing one or more of the
compounds as claimed in claim 18, wherein one or more bonds of the
compound to the polymer, oligomer or dendrimer are present in place
of one or more R radicals.
31. A formulation comprising at least one compound as claimed in
claim 18 and at least one further compound, especially a solvent or
a mixture of two or more solvents.
32. A method comprising incorporating the compound as claimed in
claim 18 in an electronic device.
33. An electronic device comprising at least one compound as
claimed in claim 18.
34. The electronic device as claimed in claim 33, wherein the
device is an organic electroluminescent device and the compound as
claimed in claim 18 is used in an emitting layer as matrix material
for fluorescent or phosphorescent emitters and/or in a hole blocker
layer and/or in an electron transport layer.
Description
[0001] The present invention relates to materials for use in
electronic devices, especially as host material for phosphorescent
emitters in organic electroluminescent devices, and to electronic
devices, especially organic electroluminescent devices, comprising
these materials.
[0002] Emitting materials used in organic electroluminescent
devices (OLEDs) are increasingly organometallic complexes which
exhibit phosphorescence rather than fluorescence, especially
iridium or platinum complexes. For quantum-mechanical reasons, up
to four times the energy efficiency and power efficiency is
possible using phosphorescent organometallic compounds as
phosphorescent emitters. In general terms, however, there is still
a need for improvement in OLEDs, especially also in OLEDs which
exhibit triplet emission (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. Also of particular
significance here are especially the other materials used, such as
matrix materials, hole blocker materials, electron transport
materials, hole transport materials and electron or exciton blocker
materials. Improvements to these materials can thus also lead to
distinct improvements in the OLED properties. For fluorescent OLEDs
too, there is still a need for improvement in these materials.
[0004] According to the prior art, lactams, for example according
to WO 2011/137951 or WO 2013/064206, are one kind of matrix
materials used for phosphorescent emitters. However, there is still
a need for improvement in the case of use of these matrix
materials, and likewise of other matrix materials, especially in
relation to the efficiency and lifetime of the device.
[0005] It is an object of the present invention to provide
compounds suitable for use in a fluorescent or, more particularly,
in a phosphorescent OLED, for example as matrix material or as
electron transport or hole blocker material, according to the exact
substitution pattern. More particularly, it is an object of the
present invention to provide matrix materials suitable for green-,
yellow- and red-phosphorescing OLEDs.
[0006] It has been found that, surprisingly, this object is
achieved by the compounds described in detail below, and these lead
to distinct improvements in the organic electroluminescent device,
especially with regard to lifetime, efficiency and operating
voltage. This is especially true of red-, yellow- and
green-phosphorescing electroluminescent devices, particularly when
the compounds are used as matrix material. The materials
additionally feature high thermal stability. The present invention
therefore provides these compounds and electronic devices,
especially organic electroluminescent devices, comprising these
compounds.
[0007] The present invention provides a compound of the following
formula (1)
##STR00001##
[0008] where the symbols used are as follows: [0009] X is the same
or different at each instance and is CR or N or two adjacent X
groups together are O, S or NR, so as to give a five-membered ring,
or two adjacent X groups together are a group of the formula (2),
(3) or (4) [0010] with the proviso that the compound of the formula
(1) contains at least one group of the formula (2)
[0010] ##STR00002## [0011] where identifies the corresponding
adjacent X groups in formula (1), i.e. the group of the formula (2)
or (3) or (4) is fused to the compound of the formula (1) at these
positions; [0012] A.sup.1, A.sup.2 is the same or different at each
instance and is a single bond, CR.sub.2, NR, O, S or C.dbd.O;
[0013] Z is the same or different at each instance and is C.dbd.O,
C.dbd.S, CR.sub.2, BR, SiR.sub.2, P(.dbd.O)R, SO or SO.sub.2;
[0014] Y is C when Ar.sup.1 is a 6-membered aryl or heteroaryl
group, or is C or N when Ar.sup.1 is a 5-membered heteroaryl group:
[0015] E is the same or different at each instance and is a single
bond, CR.sub.2, NR, O, S or C.dbd.O, with the proviso that E in
formula (4) is not a single bond; [0016] Ar.sup.1 is the same or
different at each instance and, together with the Y group and the
carbon atom shown explicitly, is an aromatic or heteroaromatic ring
system which has 5 to 24 aromatic ring atoms and may be substituted
by one or more R radicals; [0017] Ar.sup.2 is the same or different
at each instance and, together with the three carbon atoms shown
explicitly, is an aromatic or heteroaromatic ring system which has
5 to 24 aromatic ring atoms and may be substituted by one or more R
radicals; [0018] G is the same or different at each instance and is
CR or N: [0019] 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(Ar.sup.3).sub.2, N(R.sup.1).sub.2, C(.dbd.O)Ar.sup.3,
C(.dbd.O)R.sup.1, P(.dbd.O)(Ar.sup.3).sub.2, a straight-chain
alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a
branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40
carbon atoms or an alkenyl or alkynyl group having 2 to 40 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, C.ident.C, Si(R.sup.1).sub.2,
C.dbd.O, 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, 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, or an aralkyl or heteroaralkyl group which has 5 to 40
aromatic ring atoms and may be substituted by one or more R.sup.1
radicals, where it is optionally possible for two or more adjacent
R substituents to form a monocyclic or polycyclic, aliphatic,
aromatic or heteroaromatic ring system which may be substituted by
one or more R.sup.1 radicals; [0020] Ar.sup.3 is the same or
different at each instance and is an aromatic or heteroaromatic
ring system which has 5-30 aromatic ring atoms and may be
substituted by one or more nonaromatic R.sup.1 radicals; at the
same time, two Ar.sup.3 radicals bonded to the same nitrogen atom
or phosphorus atom may also be bridged to one another by a single
bond or a bridge selected from N(R.sup.1), C(R.sup.1).sub.2 and O;
[0021] 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,
NO.sub.2, N(R.sup.2).sub.2, C(.dbd.O)R.sup.2,
P(.dbd.O)(R.sup.2).sub.2, a straight-chain alkyl, alkoxy or
thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic
alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an
alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which
may be substituted by one or more R.sup.2 radicals, where one or
more nonadjacent CH.sub.2 groups may be replaced by
R.sup.2C.dbd.CR.sup.2, C.ident.C, Si(R.sup.2).sub.2, C.dbd.O,
C.dbd.NR.sup.2. P(.dbd.O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or
CONR.sup.2 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.2 radicals, an aryloxy or
heteroaryloxy group which has 5 to 40 aromatic ring atoms and may
be substituted by one or more R.sup.2 radicals, or an aralkyl or
heteroaralkyl group which has 5 to 40 aromatic ring atoms and may
be substituted by one or more R.sup.2 radicals, where it is
optionally possible for two or more adjacent R.sup.1 substituents
to form a monocyclic or polycyclic, aliphatic, aromatic or
heteroaromatic ring system which may be substituted by one or more
R.sup.2 radicals; [0022] R.sup.2 is selected from the group
consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having
1 to 20 carbon atoms, an aromatic or heteroaromatic ring system
having 5 to 30 aromatic ring atoms, where two or more adjacent
R.sup.2 substituents together may form a mono- or polycyclic,
aliphatic, aromatic or heteroaromatic ring system.
[0023] Adjacent X groups in the context of the present invention
are X groups bonded directly to one another. Adjacent substituents
in the context of the present invention are substituents bonded to
atoms that are in turn bonded directly to one another, or bonded to
the same atom.
[0024] An aryl group in the context of this invention contains 6 to
60 carbon atoms; a heteroaryl group in the context of this
invention contains 2 to 60 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. 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 (annelated) aryl or heteroaryl group,
for example naphthalene, anthracene, phenanthrene, quinoline,
isoquinoline, etc. Aromatic systems joined to one another by a
single bond, for example biphenyl, by contrast, are not referred to
as an aryl or heteroaryl group but as an aromatic ring system.
[0025] An aromatic ring system in the context of this invention
contains 6 to 80 carbon atoms in the ring system. A heteroaromatic
ring system in the context of this invention contains 2 to 60
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. 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 joined by a nonaromatic unit, for example a carbon, nitrogen
or oxygen atom. For example, systems such as fluorene,
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 joined, for example, by a short
alkyl group.
[0026] In the context of the present invention, an aliphatic
hydrocarbyl radical or an alkyl group or an alkenyl or alkynyl
group which may contain 1 to 40 carbon atoms and in which
individual hydrogen atoms or CH.sub.2 groups may also be replaced
by the abovementioned groups are preferably understood to mean the
methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl,
t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neopentyl, cyclopentyl,
n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl,
cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl,
2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl,
cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl,
octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl,
hexynyl, heptynyl or octynyl radicals. An alkoxy group having 1 to
40 carbon atoms is preferably understood to mean methoxy,
trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,
s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy,
cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy,
cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and
2,2,2-trifluoroethoxy. A thioalkyl group having 1 to 40 carbon
atoms is understood to mean especially methylthio, ethylthio,
n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio,
t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio,
cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio,
cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio,
pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio,
propenylthio, butenylthio, pentenylthio, cyclopentenylthio,
hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio,
octenylthio, cyclooctenylthio, ethynylthio, propynylthio,
butynylthio, pentynylthio, hexynylthio, heptynylthio or
octynylthio. In general, alkyl, alkoxy or thioalkyl groups
according to the present invention may be straight-chain, branched
or cyclic, where one or more nonadjacent CH.sub.2 groups may be
replaced by the abovementioned groups; in addition, it is also
possible for one or more hydrogen atoms to be replaced by D, F, Cl,
Br, I, CN or NO.sub.2, preferably F, Cl or CN, further preferably F
or CN, especially preferably CN.
[0027] An aromatic or heteroaromatic ring system which has 5-80
aromatic ring atoms and may also be substituted in each case by the
abovementioned R.sup.1 radicals or a hydrocarbyl radical and which
may be joined to the aromatic or heteroaromatic system via any
desired positions is especially understood to mean groups derived
from benzene, naphthalene, anthracene, benzanthracene,
phenanthrene, pyrene, chrysene, perylene, fluoranthene,
naphthacene, pentacene, benzopyrene, biphenyl, biphenylene,
terphenyl, triphenylene, fluorene, spirobifluorene,
dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or
trans-indenofluorene, cis- or trans-indenocarbazole, cis- or
trans-indolocarbazole, truxene, isotruxene, spirotruxene,
spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran,
thiophene, benzothiophene, isobenzothiophene, dibenzothiophene,
pyrrole, indole, isoindole, carbazole, 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,
hexaazatriphenylene, 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 or groups derived from a
combination of these systems.
[0028] Each cycle having X groups in the structure of the formula
(1) is a five- or six-membered ring, where ring formation between
the R radicals can also give rise to fused structures. Even when
adjacent X groups are a group of the formula (2), (3) or (4),
larger fused structures arise. This means that not more than one
X--X moiety per cycle is O, S or NR. It is preferable here when the
group of the formula (2) is bonded within a six-membered ring. It
is further preferable when each cycle contains not more than one
group of the formula (2), (3) or (4). Thus, when a cycle in formula
(1) contains a group of the formula (2), it is preferable when the
other X groups in this cycle are the same or different and are each
CR or N, especially CR.
[0029] It is further preferable when not more than one X group per
cycle is N. More preferably, no X group is N, meaning that all the
X groups that are not a group of the formula (2), (3) or (4) or O,
S or NR are more preferably CR.
[0030] When groups of the formula (3) or (4) are present, it is
preferable when not more than one G group in these formulae is N.
More preferably, all the G groups in the groups of the formula (3)
and (4) are CR.
[0031] There follows a schematic illustration of what is meant by
the term "cycle" or "cycle having the X groups" in formula (1) and
in the definition of X:
##STR00003##
[0032] In a preferred embodiment of the invention, at least one of
the A.sup.1 and A.sup.2 groups is a single bond. In this case, it
is preferable when a group of the formula (2) is bonded to the same
half of the spiro compound on which this A.sup.1 or A.sup.2 group
which is a single bond is also present. In a particularly preferred
embodiment of the invention, A.sup.1 and A.sup.2 are a single
bond.
[0033] According to the invention, in at least one of the cycles,
two adjacent X groups are a group of the formula (2). In a
preferred embodiment of the invention, the compound of the formula
(1) contains one or two groups of the formula (2), more preferably
exactly one group of the formula (2).
[0034] It is possible here for the groups of the formula (2) to be
bonded in any position and in any orientation. Suitable embodiments
of the formula (1) having exactly one group of the formula (2) are
therefore the compounds of the formula (5) to (10)
##STR00004##
[0035] where .smallcircle. represents the linkage to the nitrogen
atom in the group of the formula (2), # represents the linkage to
the E group in the group of the formula (2), and the further
symbols used are as defined above. In this case, it is preferable
that the two X groups in the cycle to which the group of the
formula (2) is bonded are CR or N, especially CR.
[0036] When the compound of the formula (1) has two groups of the
formula (2), these groups may either be bonded to the same half of
the spiro compound, as indicated schematically in the following
formula (11), or they may be bonded to the two different halves of
the spiro compound, as indicated schematically in the following
formula (12):
##STR00005##
[0037] It is possible here for the groups of the formula (2) again
to be bonded in all positions and in all possible orientations. A
preferred embodiment of compounds having two groups of the formula
(2) is the compound of the following formula (12a):
##STR00006##
[0038] where the symbols used have the definitions given above.
[0039] Preference is given to compounds of the formula (5) to (10)
in which at least one of the A.sup.1 and A.sup.2 groups is a single
bond. Particular preference is given to compounds in which A.sup.1
and A.sup.2 are each a single bond.
[0040] Preference is further given to compounds of the formula (5)
to (10) in which all X groups are the same or different at each
instance and are CR.
[0041] Very particular preference is given to compounds in which
A.sup.1 and A.sup.2 are each a single bond and in which all X
groups are the same or different at each instance and are CR,
according to the following formulae (5a) to (10a):
##STR00007## ##STR00008##
[0042] where the symbols used have the definitions given above.
Particular preference is given to the structures of the formulae
(5a) and (8a).
[0043] Preferred compounds of the formulae (5a) to (35a) are the
compounds of the formulae (5b) to (10b):
##STR00009## ##STR00010##
[0044] where the symbols used have the definitions given above.
[0045] There follows a description of the groups of the formula
(2).
[0046] In a preferred embodiment of the invention, Z is the same or
different and is C.dbd.O or C.dbd.S, more preferably C.dbd.O.
[0047] In a further preferred embodiment of the invention, E is a
single bond. CR.sub.2, C.dbd.O or NR, more preferably a single
bond, CR.sub.2 or C.dbd.O and most preferably a single bond.
[0048] In a further preferred embodiment of the invention, the
Ar.sup.1 group is a group of the following formula (13), (14),
(15), (16) and (17)
##STR00011##
[0049] where the dotted bond indicates the linkage to Z, *
indicates the position of the linkage to Ar.sup.2 and, in addition:
[0050] W is the same or different at each instance and is CR or N,
or two adjacent W groups are a group of the following formula (18)
or (19)
[0050] ##STR00012## [0051] where E is as defined above, but is
preferably not a single bond. G is the same or different at each
instance and is CR or N and indicate the corresponding adjacent W
groups in the formula (13) to (17); [0052] V is NR, O or S.
[0053] In a further preferred embodiment of the invention, the
Ar.sup.2 group is a group of one of the following formulae (20),
(21) and (22)
##STR00013##
[0054] where the dotted bond indicates the linkage to N, #
indicates the position of the linkage to E, * indicates the linkage
to Ar.sup.1 and W and V are each as defined above.
[0055] In a particularly preferred embodiment of the invention, the
abovementioned preferences occur simultaneously. Particular
preference is therefore given to groups of formula (2) for which:
[0056] Z is C.dbd.O or C.dbd.S; [0057] E is the same or different
at each instance and is a single bond, CR.sub.2, C.dbd.O or NR;
[0058] Ar.sup.1 is selected from the groups of the abovementioned
formulae (13), (14), (15), (16) and (17); [0059] Ar.sup.2 is
selected from the groups of the abovementioned formulae (20), (21)
and (22).
[0060] In a very particularly preferred embodiment of the
invention, for groups of the formula (2): [0061] Z is C.dbd.O;
[0062] E is a single bond; [0063] Ar.sup.1 is selected from the
groups of the abovementioned formulae (13), (14), (15), (16) and
(17); [0064] Ar.sup.2 is selected from the groups of the
abovementioned formulae (20), (21) and (22).
[0065] At the same time, the abovementioned preferred Ar.sup.1 and
Ar.sup.2 groups may be combined with one another as desired.
Suitable combinations are thus as follows:
TABLE-US-00001 Ar.sup.1 Ar.sup.2 Formula (13) Formula (20) Formula
(13) Formula (21) Formula (13) Formula (22) Formula (14) Formula
(20) Formula (14) Formula (21) Formula (14) Formula (22) Formula
(15) Formula (20) Formula (15) Formula (21) Formula (15) Formula
(22) Formula (16) Formula (20) Formula (16) Formula (21) Formula
(16) Formula (22) Formula (17) Formula (20) Formula (17) Formula
(21) Formula (17) Formula (22)
[0066] More preferably, at least one of the Ar.sup.1 and Ar.sup.2
groups is a 6-membered aryl or a 6-membered heteroaryl group. More
preferably, both Ar.sup.1 and Ar.sup.2 groups are a 6-membered aryl
or a 6-membered heteroaryl group. More preferably, thus, Ar.sup.1
is a group of the formula (13) and, at the same time, Ar.sup.2 is a
group of the formula (20).
[0067] Preferred embodiments of the group of the formula (2) are
therefore the compounds of the following formulae (23) to (29):
##STR00014##
[0068] where identifies the position of the linkage in formula (1)
and the further symbols used are as defined above.
[0069] As already stated above, it is also possible for two
adjacent W groups to be a group of the abovementioned formula (18)
or (19).
[0070] In a further preferred embodiment of the groups of the
formulae (13) to (17), (20) to (22) and (23) to (29), not more than
one W symbol in total per cycle is N, and the remaining W symbols
that are not a group of the formula (18) or (19) are CR. In a
particularly preferred embodiment of the invention, all W symbols
that are not a group of the formula (18) or (19) are CR.
Particularly preferred groups of the formula (2) are therefore the
groups of the following formulae (23a) to (29a):
##STR00015## ##STR00016##
[0071] where the symbols used have the definitions given above.
[0072] Very particular preference is therefore given to the
compounds of the following formulae (23b) to (29b):
##STR00017## ##STR00018##
[0073] where the symbols used have the definitions given above.
[0074] Very particularly preferred groups of the formula (2) are
the groups of the formula (23) or (23a) or (23b)
[0075] In this case, in the formulae (23) to (29), (23a) to (29a)
and (23b) to (29b), Z is preferably C.dbd.O.
[0076] In addition, in the formulae (23) to (29), (23a) to (29a)
and (23b) to (29b), E is preferably a single bond.
[0077] More preferably, in the formulae (23) to (29), (23a) to
(29a) and (23b) to (29b), Z is C.dbd.O and, at the same time, E is
a single bond.
[0078] It is additionally preferable, if two adjacent W groups are
a group of the formula (18) or (19), that not more than one G group
is N. More preferably, all G groups are CR. It is additionally
preferable, when two adjacent W groups are a group of the formula
(19), that E in the group of the formula (19) is CR.sub.2, C.dbd.O
or NR, especially CR.sub.2 or NR.
[0079] The compounds of the abovementioned formulae (5) to (10) or
the preferred embodiments may be combined as desired with the
groups of the abovementioned formulae (23) to (29) or the preferred
embodiments.
[0080] Suitable compounds are therefore the compounds listed in the
following table:
TABLE-US-00002 Group of the Compound formula (2) Formula (5)
Formula (23) Formula (5) Formula (24) Formula (5) Formula (25)
Formula (5) Formula (26) Formula (5) Formula (27) Formula (5)
Formula (28) Formula (5) Formula (29) Formula (6) Formula (23)
Formula (6) Formula (24) Formula (6) Formula (25) Formula (6)
Formula (26) Formula (6) Formula (27) Formula (6) Formula (28)
Formula (6) Formula (29) Formula (7) Formula (23) Formula (7)
Formula (24) Formula (7) Formula (25) Formula (7) Formula (26)
Formula (7) Formula (27) Formula (7) Formula (28) Formula (7)
Formula (29) Formula (8) Formula (23) Formula (8) Formula (24)
Formula (8) Formula (25) Formula (8) Formula (26) Formula (8)
Formula (27) Formula (8) Formula (28) Formula (8) Formula (29)
Formula (9) Formula (23) Formula (9) Formula (24) Formula (9)
Formula (25) Formula (9) Formula (26) Formula (9) Formula (27)
Formula (9) Formula (28) Formula (9) Formula (29) Formula (10)
Formula (23) Formula (10) Formula (24) Formula (10) Formula (25)
Formula (10) Formula (26) Formula (10) Formula (27) Formula (10)
Formula (28) Formula (10) Formula (29)
[0081] Preferred compounds are the compounds listed in the
following table:
TABLE-US-00003 Group of the Compound formula (2) Formula (5a)
Formula (23a) Formula (5a) Formula (24a) Formula (5a) Formula (25a)
Formula (5a) Formula (26a) Formula (5a) Formula (27a) Formula (5a)
Formula (28a) Formula (5a) Formula (29a) Formula (6a) Formula (23a)
Formula (6a) Formula (24a) Formula (6a) Formula (25a) Formula (6a)
Formula (26a) Formula (6a) Formula (27a) Formula (6a) Formula (28a)
Formula (6a) Formula (29a) Formula (7a) Formula (23a) Formula (7a)
Formula (24a) Formula (7a) Formula (25a) Formula (7a) Formula (26a)
Formula (7a) Formula (27a) Formula (7a) Formula (28a) Formula (7a)
Formula (29a) Formula (8a) Formula (23a) Formula (8a) Formula (24a)
Formula (8a) Formula (25a) Formula (8a) Formula (26a) Formula (8a)
Formula (27a) Formula (8a) Formula (28a) Formula (8a) Formula (29a)
Formula (9a) Formula (23a) Formula (9a) Formula (24a) Formula (9a)
Formula (25a) Formula (9a) Formula (26a) Formula (9a) Formula (27a)
Formula (9a) Formula (28a) Formula (9a) Formula (29a) Formula (10a)
Formula (23a) Formula (10a) Formula (24a) Formula (10a) Formula
(25a) Formula (10a) Formula (26a) Formula (10a) Formula (27a)
Formula (10a) Formula (28a) Formula (10a) Formula (29a)
[0082] Particularly preferred compounds are the compounds listed in
the following table:
TABLE-US-00004 Group of the Compound formula (2) Formula (5b)
Formula (23b) Formula (5b) Formula (24b) Formula (5b) Formula (25b)
Formula (5b) Formula (26b) Formula (5b) Formula (27b) Formula (5b)
Formula (28b) Formula (5b) Formula (29b) Formula (6b) Formula (23b)
Formula (6b) Formula (24b) Formula (6b) Formula (25b) Formula (6b)
Formula (26b) Formula (6b) Formula (27b) Formula (6b) Formula (28b)
Formula (6b) Formula (29b) Formula (7b) Formula (23b) Formula (7b)
Formula (24b) Formula (7b) Formula (25b) Formula (7b) Formula (26b)
Formula (7b) Formula (27b) Formula (7b) Formula (28b) Formula (7b)
Formula (29b) Formula (8b) Formula (23b) Formula (8b) Formula (24b)
Formula (8b) Formula (25b) Formula (8b) Formula (26b) Formula (8b)
Formula (27b) Formula (8b) Formula (28b) Formula (8b) Formula (29b)
Formula (9b) Formula (23b) Formula (9b) Formula (24b) Formula (9b)
Formula (25b) Formula (9b) Formula (26b) Formula (9b) Formula (27b)
Formula (9b) Formula (28b) Formula (9b) Formula (29b) Formula (10b)
Formula (23b) Formula (10b) Formula (24b) Formula (10b) Formula
(25b) Formula (10b) Formula (26b) Formula (10b) Formula (27b)
Formula (10b) Formula (28b) Formula (10b) Formula (29b)
[0083] Among these compounds, preference is given to compounds of
the formula (5) to (10) which contain a group of the formula (23)
as group of the formula (2), particular preference to compounds of
the formula (5a) to (10a) which contain a group of the formula
(23a) as group of the formula (2), and very particular preference
to compounds of the formula (5b) to (10b) which contain a group of
the formula (23b) as group of the formula (2).
[0084] Very particularly preferred compounds are thus the compounds
of the following formulae (5c) to (10c):
##STR00019## ##STR00020##
[0085] where the symbols used have the definitions given above.
[0086] Very particular preference is given to the compounds of the
following formulae (5d) to (10d):
##STR00021## ##STR00022##
[0087] where the symbols used have the definitions given above.
[0088] In a preferred embodiment of the invention, R in the
abovementioned formulae is the same or different at each instance
and is selected from the group consisting of H, D, F, Cl, Br, CN,
N(Ar.sup.3).sub.2, C(.dbd.O)Ar.sup.3, 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 or
alkynyl 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, or an aromatic or
heteroaromatic ring system which has 5 to 30 aromatic ring atoms
and may be substituted in each case by one or more R.sup.1
radicals.
[0089] In a particularly preferred embodiment of the invention, R
in the abovementioned formulae is the same or different at each
instance and is selected from the group consisting of H, D, F, CN,
N(Ar.sup.3).sub.2, a straight-chain alkyl group having 1 to 4
carbon atoms or a branched alkyl group having 3 or 4 carbon atoms
or a cyclic alkyl group having 5 or 6 carbon atoms, each of which
may be substituted by one or more R.sup.1 radicals, where one or
more hydrogen atoms may be replaced by D or F, or an aromatic or
heteroaromatic ring system which has 6 to 24 aromatic ring atoms
and may be substituted in each case by one or more R.sup.1
radicals.
[0090] In a very particularly preferred embodiment of the
invention, R in the abovementioned formulae is the same or
different at each instance and is selected from the group
consisting of H and an aromatic or heteroaromatic ring system which
has 6 to 24, preferably 6 to 18, aromatic ring atoms and may be
substituted in each case by one or more R.sup.1 radicals.
[0091] When the compounds of the formula (1) or the preferred
embodiments are used as electron transport material, it is
preferable when the Z group is C.dbd.O and/or when at least one of
the R radicals is an aromatic ring system or an electron-deficient
heteroaromatic ring system. According to the invention,
electron-deficient heteroaromatic groups are five-membered
heteroaromatic rings having at least two heteroatoms or
six-membered heteroaromatic rings having at least one heteroatom,
to each of which may be fused another one or more aromatic or
heteroaromatic groups.
[0092] When the compounds of the formula (1) or the preferred
embodiments are used as matrix material for a phosphorescent
emitter, it is preferable when the Z group is C.dbd.O and/or when
at least one of the R radicals is a substituted or unsubstituted
carbazole, indenocarbazole or indolocarbazole, each of which may be
bonded via a carbon atom or a nitrogen atom. In addition, it is
preferable in this case when the compounds of the invention do not
have any aryl or heteroaryl groups in which two or more
six-membered aryl or heteroaryl groups are fused directly to one
another. More preferably, in this case, the compound of the
invention does not contain any aryl or heteroaryl groups having
six-membered rings fused directly to one another at all.
[0093] In a preferred embodiment of the invention, either all R
radicals are H or exactly one or two R radical(s) is/are an
aromatic or heteroaromatic ring system which has 6 to 18 aromatic
ring atoms and may be substituted in each case by one or more
R.sup.1 radicals, and the other R radicals are H.
[0094] When one or more R radicals are an aromatic or
heteroaromatic ring system, preferred R radicals are the same or
different at each instance and are selected from the group
consisting of phenyl, ortho-, meta- or para-biphenyl,
ortho-terphenyl, meta-terphenyl, para-terphenyl or branched
terphenyl, ortho-quaterphenyl, meta-quaterphenyl, para-quaterphenyl
or branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or
4-spirobifluorenyl, 1- or 2-naphthyl, anthracene, phenanthrene,
triphenylene, pyrene, benzanthracene, pyrrole, furan, thiophene,
indole, benzofuran, benzothiophene, 1-, 2- or 3-carbazole, 1-, 2-
or 3-dibenzofuran, 1-, 2- or 3-dibenzothiophene, indenocarbazole,
indolocarbazole, pyrazole, imidazole, benzimidazole, pyridine,
pyrimidine, pyrazine, pyridazine, triazine or quinoline or
combinations of two or three of these groups, each of which may be
substituted by one or more R.sup.1 radicals.
[0095] Preferred aromatic or heteroaromatic ring systems R are
selected from the groups of the following formulae R-1 to R-53:
##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027##
##STR00028## ##STR00029##
[0096] where R.sup.1 is as defined above, the dotted bond
represents the bond to the group of the formula (1) and, in
addition: [0097] A is the same or different at each instance and is
CR.sup.1 or N, where not more than 3 X symbols per cycle are N;
[0098] Y.sup.1 is the same or different at each instance and is
C(R.sup.1).sub.2, NR.sup.1, O or S; [0099] n is 0 or 1, where n=0
means that no Y.sup.1 group is bonded at this position and R.sup.1
radicals thereof are bonded to the corresponding carbon atoms
instead.
[0100] The expression "per cycle" mentioned above and also used
hereinafter relates in the context of the present application to
each individual ring present in the compound, i.e. to each
individual 5- or 6-membered ring.
[0101] In a preferred embodiment of the R-1 group, no, one, two or
three A symbols are N. Particular preference is given to phenyl of
the formula R-1a, pyrimidine of the formula R-1b or triazine of the
formula R-1c
##STR00030##
[0102] where R.sup.1 is as defined above and, in formula R-1a, is
especially H or an aromatic or heteroaromatic ring system which has
6 to 18 aromatic ring atoms and may be substituted by one or more
R.sup.2 radicals, and, in formula R-1b and R-1c, is in each case
especially an aromatic or heteroaromatic ring system which has 6 to
18 aromatic ring atoms and may be substituted by one or more
R.sup.2 radicals.
[0103] In preferred groups of the abovementioned formulae R-2 to
R-53, not more than one A symbol per cycle is N. More preferably,
the symbol A is the same or different at each instance and is
CR.sup.1, especially CH.
[0104] When the abovementioned groups for R-1 to R-53 have two or
more Y.sup.1 groups, possible options for these include all
combinations from the definition of Y.sup.1. Preference is given to
groups in which one Y.sup.1 group is NR.sup.1 and the other Y.sup.1
group is C(R.sup.1).sub.2 or in which both Y.sup.1 groups are
NR.sup.1 or in which both Y.sup.1 groups are O.
[0105] In a further preferred embodiment of the invention, at least
one Y.sup.1 group is C(R.sup.1).sub.2 or NR.sup.1.
[0106] When Y.sup.1 is NR.sup.1, the substituent R.sup.1 bonded to
the nitrogen atom is preferably an aromatic or heteroaromatic ring
system which has 5 to 24 aromatic ring atoms and may also be
substituted by one or more R.sup.2 radicals. In a particularly
preferred embodiment, this substituent R.sup.1 is the same or
different at each instance and is an aromatic or heteroaromatic
ring system which has 6 to 24 aromatic ring atoms, which does not
have any fused aryl groups and which does not have any fused
heteroaryl groups in which two or more aromatic or heteroaromatic
6-membered ring groups are fused directly to one another, and which
may also be substituted in each case by one or more R.sup.2
radicals. Particular preference is given to phenyl, biphenyl,
terphenyl and quaterphenyl.
[0107] When Y.sup.1 is C(R.sup.1).sub.2, R.sup.1 is preferably the
same or different at each instance and is a linear alkyl group
having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, or a
branched alkyl group having 3 to 10 carbon atoms, preferably 3 or 4
carbon atoms, or an aromatic or heteroaromatic ring system having 5
to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms,
which may also be substituted by one or more R.sup.2 radicals. Most
preferably, R.sup.1 is a methyl group or a phenyl group. In this
case, the R.sup.1 radicals together may also form a ring system,
which leads to a spiro system.
[0108] In a further preferred embodiment of the invention. R is a
triarylamine group which may be substituted by one or more R.sup.1
radicals. The latter is preferably selected from the structures of
the following formula R-54:
##STR00031##
[0109] where the dotted bond indicates the linkage to the base
skeleton and Ar.sup.4 is the same or different at each instance and
is an aromatic or heteroaromatic ring system which has 5 to 18
aromatic ring atoms in each case, preferably 6 to 12 aromatic ring
atoms in each case, and may be substituted in each case by one or
more R.sup.1 radicals.
[0110] At the same time, in compounds which are processed by vacuum
evaporation, the alkyl groups preferably have not more than five
carbon atoms, more preferably not more than 4 carbon atoms, most
preferably not more than 1 carbon atom. For compounds which are
processed from solution, suitable compounds are also those
substituted by alkyl groups, especially branched alkyl groups,
having up to 10 carbon atoms or those substituted by oligoarylene
groups, for example ortho-, meta-, para- or branched terphenyl or
quaterphenyl groups.
[0111] The abovementioned preferred embodiments may be combined
with one another as desired. In a particularly preferred embodiment
of the invention, the abovementioned preferences occur
simultaneously.
[0112] Examples of preferred compounds according to the
above-detailed embodiments are the compounds of the following
structures:
##STR00032## ##STR00033## ##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##
[0113] The compounds of the formula (1) or the preferred
embodiments can be prepared by synthesis steps known to those
skilled in the art, as shown in schematic form in scheme 1.
##STR00060##
[0114] The synthesis proceeds from a halogen-functionalized,
especially bromine-functionalized, spirobifluorene derivative. When
the compounds contain A.sup.1 or A.sup.2 groups that are not single
bonds, the starting materials are the corresponding functionalized
spiro compounds having A.sup.1 and A.sup.2 groups. The latter is
converted in a C--N coupling reaction, for example a
Hartwig-Buchwald coupling, with an ortho-haloamino-substituted
aromatic or heteroaromatic, for example an ortho-chloroaminobenzene
derivative, followed by a palladium-catalyzed ring closure reaction
to give the corresponding spirocarbazole derivative. Reaction with
an ortho-halocarbonyl chloride to give the corresponding amide,
followed by a palladium-catalyzed ring closure reaction, leads to
the compounds of the invention. Alternatively, the reaction can
also be effected with an ortho-halobenzyl bromide or a
corresponding heteroaromatic compound, followed by a
palladium-catalyzed ring closure reaction and oxidation of the
cyclic amine to the lactam. Substituted compounds are obtainable by
using correspondingly substituted reactants.
[0115] The above-described inventive compounds, especially
compounds substituted by reactive leaving groups, such as bromine,
iodine, chlorine, boronic acid or boronic ester, or by reactive
polymerizable groups such as olefins or oxetanes, may find use as
monomers for production of corresponding oligomers, dendrimers or
polymers. The oligomerization or polymerization is preferably
effected via the halogen functionality or the boronic acid
functionality or via the polymerizable group. It is additionally
possible to crosslink the polymers via groups of this kind. The
compounds of the invention and polymers may be used in the form of
a crosslinked or uncrosslinked layer.
[0116] The invention therefore further provides oligomers, polymers
or dendrimers containing one or more of the above-detailed
inventive compounds, wherein one or more bonds of the inventive
compound to the polymer, oligomer or dendrimer are present.
According to the linkage of the compound of the invention, it
therefore forms a side chain of the oligomer or polymer or is
incorporated in the main chain. The polymers, oligomers or
dendrimers may be conjugated, partly conjugated or nonconjugated.
The oligomers or polymers may be linear, branched or dendritic. For
the repeat units of the compounds of the invention in oligomers,
dendrimers and polymers, the same preferences apply as described
above.
[0117] For preparation of the oligomers or polymers, the monomers
of the invention are homopolymerized or copolymerized with further
monomers. Preference is given to homopolymers or copolymers wherein
the units of formula (1) or the above-recited preferred embodiments
are present to an extent of 0.01 to 99.9 mol %, preferably 5 to 90
mol %, more preferably 20 to 80 mol %. Suitable and preferred
comonomers which form the polymer base skeleton are chosen from
fluorenes (for example according to EP 842208 or WO 2000/22026),
spirobifluorenes (for example according to EP 707020, EP 894107 or
WO 2006/061181), paraphenylenes (for example according to WO
92/18552), carbazoles (for example according to WO 2004/070772 or
WO 2004/113468), thiophenes (for example according to EP 1028136),
dihydrophenanthrenes (for example according to WO 2005/014689),
cis- and trans-indenofluorenes (for example according to WO
2004/041901 or WO 2004/113412), ketones (for example according to
WO 2005/040302), phenanthrenes (for example according to WO
2005/104264 or WO 2007/017066) or else a plurality of these units.
The polymers, oligomers and dendrimers may contain still further
units, for example hole transport units, especially those based on
triarylamines, and/or electron transport units. In addition, the
polymers may contain triplet emitters either in copolymerized form
or mixed in as a blend. Specifically the combination of units of
formula (1') or the above-recited preferred embodiments with
triplet emitters leads to particularly good results.
[0118] In addition, the compounds of formula (1) or the
above-recited preferred embodiments may also be further
functionalized and thus be converted to extended structures.
Examples here include the Suzuki reaction with arylboronic acids or
the Hartwig-Buchwald reaction with primary or secondary amines.
Thus, the compounds of formula (1) or the above-recited preferred
embodiments may also be bonded directly to phosphorescent metal
complexes or else to other metal complexes.
[0119] For the processing of the compounds of the invention from
the 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 or mixtures of these
solvents.
[0120] 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
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.
[0121] The compounds of the invention are suitable for use in an
electronic device, especially in an organic electroluminescent
device.
[0122] The present invention further provides for the use of the
above-recited inventive compounds of formula (1) or of the
preferred embodiments in an electronic device, especially in an
organic electroluminescent device.
[0123] An electronic device in the context of the present invention
is a device comprising at least one layer comprising at least one
organic compound. This component may also comprise inorganic
materials or else layers formed entirely from inorganic
materials.
[0124] The electronic device is preferably selected from the group
consisting of organic electroluminescent devices (OLEDs), 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 (O-DSSCs), organic optical
detectors, organic photoreceptors, organic field-quench devices
(O-FQDs), light-emitting electrochemical cells (LECs), organic
laser diodes (O-lasers) and organic plasmon emitting devices (D. M.
Koller et al., Nature Photonics 2008, 1-4), but preferably organic
electroluminescent devices (OLEDs), more preferably phosphorescent
OLEDs.
[0125] The organic electroluminescent device comprises cathode,
anode and at least one emitting layer. Apart from these layers, it
may 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).
[0126] 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 comprising a compound of formula (1) or
the above-recited preferred embodiments as matrix material for
fluorescent or phosphorescent emitters, especially for
phosphorescent emitters, and/or in a hole blocker layer and/or in
an electron transport layer and/or in an electron-blocking or
exciton-blocking layer and/or in a hole transport layer, according
to the exact substitution.
[0127] In a preferred embodiment of the invention, the compound of
formula (1) or the above-recited preferred embodiments is used as
matrix material for a fluorescent or phosphorescent compound,
especially 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.
[0128] When the compound of formula (1) or the above-recited
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 higher spin
multiplicity, i.e. a spin state >1, especially from an excited
triplet state. In the context of this application, all luminescent
complexes with transition metals or lanthanides, especially all
iridium, platinum and copper complexes, shall be regarded as
phosphorescent compounds.
[0129] The mixture of the compound of formula (1) or the
above-recited 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 the above-recited 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.
[0130] A further preferred embodiment of the present invention is
the use of the compound of formula (1) or the above-recited
preferred embodiments as matrix material for a phosphorescent
emitter in combination with a further matrix material. Particularly
suitable matrix materials which can be used in combination with the
inventive compounds are aromatic ketones, aromatic phosphine oxides
or aromatic sulfoxides or sulfones, 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) or the carbazole derivatives disclosed
in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527, WO
2008/086851 or WO 2013/041176, 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,
azacarbazole derivatives, for example according to EP 1617710, EP
1617711, EP 1731584, JP 2005/347160, bipolar matrix materials, for
example according to WO 2007/137725, silanes, for example according
to WO 2005/111172, azaboroles or boronic esters, for example
according to WO 2006/117052, triazine derivatives, for example
according to WO 2007/063754, WO 2008/056746, WO 2010/015306, WO
2011/057706, WO 2011/060859 or WO 2011/060877, zinc complexes, for
example according to EP 652273 or WO 2009/062578, diazasilole or
tetraazasilole derivatives, for example according to WO
2010/054729, diazaphosphole derivatives, for example according to
WO 2010/054730, bridged carbazole derivatives, for example
according to WO 2011/042107, WO 2011/060867, WO 2011/088877 and WO
2012/143080, or triphenylene derivatives, for example according to
WO 2012/048781. It is likewise possible for a further
phosphorescent emitter having shorter-wavelength emission than the
actual emitter to be present as co-host in the mixture, or a
compound not involved in charge transport to a significant extent,
if at all, as described, for example, in WO 2010/108579.
[0131] 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.
[0132] 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 2005/033244, WO
2005/019373. US 2005/0258742, WO 2010/086089. WO 2011/157339, WO
2012/007086, WO 2012/163471, WO 2013/000531, WO 2013/020631. WO
2014/008982 and WO 2014/023377. 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.
[0133] 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.
[0134] In a further preferred embodiment of the invention, the
compound of formula (1) or the above-recited preferred embodiments
is used as electron transport material in an electron transport or
electron injection layer. In this case, the emitting layer may be
fluorescent or phosphorescent. When the compound is used as
electron transport material, it may be preferable for it to be
doped, for example with alkali metal complexes, for example LiQ
(lithium hydroxyquinolinate).
[0135] In yet a further preferred embodiment of the invention, the
compound of formula (1) or the above-recited preferred embodiments
is used in a hole blocker layer. A hole blocker layer is understood
to be a layer which directly adjoins an emitting layer on the
cathode side.
[0136] It is additionally possible to use the compound of formula
(1) or the above-recited preferred embodiments both in a hole
blocker layer or electron transport layer and as matrix in an
emitting layer.
[0137] In yet a further embodiment of the invention, the compound
of formula (1) or the above-recited preferred embodiments is used
in a hole transport layer or in an electron blocker layer or
exciton blocker layer.
[0138] 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 will therefore be able, without exercising inventive skill,
to use any materials known for organic electroluminescent devices
in combination with the inventive compounds of formula (1) or the
above-recited preferred embodiments.
[0139] 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
vapor 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, for example less than 10.sup.-7 mbar.
[0140] Preference is likewise given to an organic
electroluminescent device, characterized in that one or more layers
are coated by the OVPD (organic vapor 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 vapor 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).
[0141] 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 screen printing, flexographic
printing, offset printing. LITI (light-induced thermal imaging,
thermal transfer printing), inkjet printing or nozzle printing. For
this purpose, soluble compounds are needed, which are obtained, for
example, through suitable substitution. These methods are
especially also suitable for oligomers, dendrimers and
polymers.
[0142] 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 vapor deposition.
[0143] 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.
[0144] The inventive compounds and the inventive organic
electroluminescent devices are notable for the following surprising
advantages over the prior art: [0145] 1. The inventive compounds or
compounds of formula (1) or the above-recited preferred
embodiments, especially used as matrix material for phosphorescent
emitters, lead to high efficiencies and to long lifetimes. This is
especially true when the compounds are used as matrix material for
a red-, yellow- or green-phosphorescing emitter. [0146] 2. Organic
electroluminescent devices containing the inventive compounds have
a low operating voltage. This leads to high power efficiencies.
[0147] 3. The inventive compounds have high thermal stability and
high glass transition temperatures. [0148] 4. When used as electron
transport material, the inventive compounds also lead to very good
properties in relation to efficiency, lifetime and operating
voltage of organic electroluminescent devices.
[0149] These abovementioned advantages are not accompanied by a
deterioration in the further electronic properties.
[0150] The invention is illustrated in detail by the examples which
follow, without any intention of restricting it thereby. The person
skilled in the art will be able to use the information given to
execute the invention over the entire scope disclosed and to
prepare further compounds of the invention without exercising
inventive skill and to use them in electronic devices or to employ
the process of the invention.
EXAMPLES
[0151] The syntheses which follow, unless stated otherwise, are
conducted under a protective gas atmosphere. The reactants can be
sourced from ALDRICH or ABCR. The numbers given in square brackets
for the compounds known from the literature indicate the CAS
numbers of these compounds.
Synthesis Examples
Example A
Synthesis of 1-bromospiro-9,9'-bifluorene,
3-bromospiro-9,9'-bifluorene, 4-bromospiro-9,9'-bifluorene,
4,4'-dibromospiro-9,9'-bifluorene,
3,6-dibromospiro-9,9'-bifluorene
a) 1-Bromospiro-9,9'-bifluorene
##STR00061##
[0153] 2.7 g (110 mmol) of iodine-activated magnesium turnings and
a mixture of 25.6 g (110 mmol) of 2-bromobiphenyl, 0.8 mL of
1,2-dichloroethane, 50 mL of 1,2-dimethoxyethane, 400 mL of THF and
200 mL of toluene are used to prepare the corresponding Grignard
reagent by trace heating with an oil bath at 70.degree. C. Once the
magnesium has reacted fully, the mixture is cooled to room
temperature and then a solution of 25.9 g (100 mmol) of
1-bromofluorenone [36804-63-4] in 500 mL of THF is added dropwise,
and the reaction mixture is heated to 50.degree. C. for 4 h and
then stirred at room temperature for a further 12 h. 100 mL of
water are added, the mixture is stirred briefly, the organic phase
is removed and the solvent is removed under reduced pressure. The
residue is suspended in 500 mL of glacial acetic acid heated to
40.degree. C., 0.5 mL of conc. sulfuric acid is added to the
suspension and the mixture is then stirred at 100.degree. C. for 2
h. After cooling, the precipitated solid is filtered off with
suction and washed once with 100 mL of glacial acetic acid and
three times with 100 mL each time of ethanol, and finally
recrystallized from dioxane. Yield: 26.9 g (68 mmol), 68%: purity
about 98% by .sup.1H NMR.
TABLE-US-00005 Br-biphenyl Br-fluorenone Product: Br-spiro Yield
##STR00062## 2052-07-5 ##STR00063## 2041-19-2 ##STR00064## 85%
##STR00065## 13029-09-9 ##STR00066## 486-25-9 ##STR00067## 90%
1161009-88-6 ##STR00068## 2052-07-5 ##STR00069## 216312-73-1
##STR00070## 85% ##STR00071## 13029-09-9 ##STR00072## 4269-17-4
##STR00073## 90% 1257321-41-7
Example 1a
(2-Chlorophenyl)-4-spiro-9,9'-bifluorenylamine
##STR00074##
[0155] 54 g (137 mmol) of 4-bromospiro-9,9'-bifluorene, 17.9 g (140
mmol) of 2-chloroaniline, 68.2 g (710 mmol) of sodium
tert-butoxide, 613 mg (3 mmol) of palladium(II) acetate and 3.03 g
(5 mmol) of dppf are dissolved in 1.3 L of toluene and stirred
under reflux for 5 h. The reaction mixture is cooled down to room
temperature, extended with toluene and filtered through Celite. The
filtrate is concentrated under reduced pressure and the residue is
crystallized from toluene/heptane. The product is isolated as a
colorless solid. Yield: 52.2 g (118 mmol), 86% of theory.
[0156] In an analogous manner, it is possible to prepare the
following compounds:
TABLE-US-00006 Reactant 1 Reactant 2 Product Yield 1b ##STR00075##
##STR00076## 7285-66-7 ##STR00077## 83% 1c ##STR00078##
##STR00079## 858426-71-8 ##STR00080## 78% 1d ##STR00081##
171408-76-7 ##STR00082## 7285-66-7 ##STR00083## 72% 1e ##STR00084##
171408-76-7 ##STR00085## 95-51-2 ##STR00086## 74% 1f ##STR00087##
##STR00088## 95-51-2 ##STR00089## 68% 1g ##STR00090## ##STR00091##
95-51-2 ##STR00092## 79% 1h ##STR00093## ##STR00094## 95-51-2
##STR00095## 63% 1i ##STR00096## ##STR00097## 95-51-2 ##STR00098##
61%
Example 2a
Spiro[9H-fluoren-9,7'(1'H)-indeno[1,2-a]carbazole]
##STR00099##
[0158] 45 g (102 mmol) of
(2-chlorophenyl)-4-spiro-9,9'-bifluorenylamine, 56 g (409 mmol) of
potassium carbonate, 4.5 g (12 mmol) of tricyclohexylphosphine
tetrafluoroborate and 1.38 g (6 mmol) of palladium(II) acetate are
suspended in 500 mL of dimethylacetamide and stirred under reflux
for 6 h. After cooling, the reaction mixture is with 300 mL of
water and 600 mL of dichloromethane. The mixture is stirred for a
further 30 min, the organic phase is separated off and filtered
through a short Celite bed, and then the solvent is removed under
reduced pressure. The crude product is subjected to hot extraction
with toluene and recrystallized from toluene. The product is
isolated as a beige solid. Yield: 32.5 g (80 mmol correspond to 78%
of theory).
[0159] In an analogous manner, it is possible to prepare the
following compounds:
TABLE-US-00007 Reactant Product Yield 2b ##STR00100## ##STR00101##
72% 2c ##STR00102## ##STR00103## 73% 2d ##STR00104## ##STR00105##
56% 2e ##STR00106## ##STR00107## 71% 2f ##STR00108## ##STR00109##
67% 2g ##STR00110## ##STR00111## 51% 2h ##STR00112## ##STR00113##
43% 2i ##STR00114## ##STR00115## 47%
Example 3a
Nucleophilic Substitution
##STR00116##
[0161] In a 500 mL four-neck flask, 760 mg (19 mmol) of sodium
hydride are initially charged in 50 mL of THF. By means of a
dropping funnel, 7.0 g (17 mmol) of spirocarbazole 2a, dissolved in
200 mL of THF, are added dropwise and the mixture is stirred for a
further 1 h. Subsequently, 4.3 g (17 mmol) of 2-bromobenzyl
bromide, dissolved in 100 mL of THF, are added dropwise and the
mixture is stirred at room temperature for 5 h until conversion is
complete. The reaction mixture is added to ice and warmed to room
temperature. The precipitated solid is filtered and washed with
n-heptane and dried under reduced pressure. The product is obtained
as a colorless solid. Yield: 9.3 g (16 mmol, corresponding to 94%
of theory).
[0162] In an analogous manner, it is possible to obtain the
following compounds:
TABLE-US-00008 Ex. Reactant 1 Reactant 2 Product Yield 3b
##STR00117## ##STR00118## 172976-02-2 ##STR00119## 79% 3c
##STR00120## ##STR00121## 3433-80-5 ##STR00122## 87% 3d
##STR00123## ##STR00124## 3433-80-5 ##STR00125## 92% 3e
##STR00126## ##STR00127## 1214372-35-6 ##STR00128## 90% 3f
##STR00129## ##STR00130## 172976-02-2 2eq ##STR00131## 90% 3g
##STR00132## ##STR00133## 202805-71-8 ##STR00134## 82% 3h
##STR00135## ##STR00136## 3433-80-5 2 eq ##STR00137## 88% 3i
##STR00138## ##STR00139## 3433-80-5 ##STR00140## 79%
Example 4a
Cyclization
##STR00141##
[0164] A 1 L four-neck flask is initially charged with 29 g (50
mmol) of 3a and 9.90 g (101 mmol) of potassium acetate in 500 mL of
DMF, and argon is passed through for 30 minutes. Subsequently, 1.75
g (1.51 mmol) of Pd(PPh.sub.3).sub.4 are added and the mixture is
heated under reflux for 16 h until conversion is complete. The
reaction mixture is cooled down to room temperature and hydrolyzed
with 400 mL of water. The precipitated solid is filtered and washed
with water. After drying under reduced pressure, the product is
obtained as a gray solid. Yield: 4.7 g (50.0 mmol, corresponding to
99% of theory).
[0165] In an analogous manner, it is possible to obtain the
following compounds:
TABLE-US-00009 Ex. Reactant 1 Product Yied 4b ##STR00142##
##STR00143## 80% 4c ##STR00144## ##STR00145## 84% 4d ##STR00146##
##STR00147## 85% 4e ##STR00148## ##STR00149## 81% 4f ##STR00150##
##STR00151## 88% 4g ##STR00152## ##STR00153## 79% 4h ##STR00154##
##STR00155## 78% 4i ##STR00156## ##STR00157## 76%
Example 5a
Oxidation
##STR00158##
[0167] In a 1 L four-neck flask, 23.5 g (47.6 mmol) of 4a are
dissolved in 500 mL of dichloromethane/water (1:1). Subsequently,
17.5 g (47.6 mmol) of dibenzo-18-crown-6 and, in portions, 91.0 g
(576 mmol) of potassium permanganate are added and the mixture is
stirred at room temperature for 24 h and under reflux for 4 days.
After cooling to room temperature, the solvents are removed under
reduced pressure. The solid obtained is subjected to hot extraction
with toluene. The precipitated solid is filtered off and washed
four times with 200 mL of cold acetonitrile. This is followed by
hot extraction with toluene up to an HPLC purity of >99.9% and
recrystallization. After subliming twice (340.degree. C. at
<10.sup.-4 bar), the product is obtained in an HPLC purity of
>99.9% as a white solid. Yield: 3 g (7 mmol, corresponding to
15%).
[0168] In an analogous manner, it is possible to obtain the
following compounds:
TABLE-US-00010 Ex. Reactant 1 Product Yield 5b ##STR00159##
##STR00160## 23% 5c ##STR00161## ##STR00162## 24% 5d ##STR00163##
##STR00164## 26% 5e ##STR00165## ##STR00166## 21% 5f ##STR00167##
##STR00168## 23% 5g ##STR00169## ##STR00170## 18% 5h ##STR00171##
##STR00172## 31% 5i ##STR00173## ##STR00174## 23%
Method 2
Example 6a
Nucleophilic Substitution
##STR00175##
[0170] 2.1 g (52.5 mmol) of 60% NaH in mineral oil are dissolved in
500 mL of THF under a protective atmosphere. 33.8 g (50 mmol) of
compound 2a and 11.5 g (52.5 mmol) of 15-crown-5 dissolved in 200
mL of THF are added. After 1 h at room temperature, a solution of
12 g (55 mmol) of 2-bromobenzoyl chloride in 250 mL of THF is added
dropwise. The reaction mixture is stirred at room temperature for
18 h. After this time, the reaction mixture is poured onto ice and
extracted three times with dichloromethane. The combined organic
phases are dried over Na.sub.2SO.sub.4 and concentrated. The
residue is subjected to hot extraction with toluene and
recrystallized from toluene/n-heptane. Yield: 17 g (29 mmol), 60%;
purity: about 98% by .sup.1H NMR.
[0171] In an analogous manner, it is possible to obtain the
following compounds:
TABLE-US-00011 Ex. Reactant 1 Reactant 2 Product Yield 6b
##STR00176## ##STR00177## 7154-66-7 ##STR00178## 68% 6c
##STR00179## ##STR00180## 7154-66-7 ##STR00181## 64% 6d
##STR00182## ##STR00183## 72899-51-5 ##STR00184## 63%
Example 7a
Cyclization
##STR00185##
[0173] Under protective gas, 43 mL of tributyltin hydride (16 mmol)
and 30 g (12-5 mmol) of 1,1'-azobis(cyclohexane-1-carbonitrile) in
600 mL of toluene are added dropwise over the course of 4 h to a
boiling solution of 7.4 g (12.5 mmol) of compound 5a in 600 mL of
toluene. This is followed by heating under reflux for 3 h. After
this time, the reaction mixture is poured onto ice and extracted
three times with dichloromethane. The combined organic phases are
dried over Na.sub.2SO.sub.4 and concentrated. The residue is
recrystallized from toluene and from dichloromethane/iso-propanol
and finally sublimed under high vacuum: purity is 99.9%. Yield: 4.2
g (8.2 mmol), 66%.
[0174] In an analogous manner, it is possible to obtain the
following compounds:
TABLE-US-00012 Ex. Reactant 1 Product Yield 7b ##STR00186##
##STR00187## 68% 7c ##STR00188## ##STR00189## 64% 7d ##STR00190##
##STR00191## 63%
[0175] Production of the OLEDs
[0176] In examples C1 to I11 which follow (see tables 1 and 2), the
data of various OLEDs are presented.
Pretreatment for Examples C1-I11
[0177] Glass plaques coated with structured ITO (indium tin oxide)
of thickness 50 nm, for improved processing, are coated with 20 nm
of PEDOT:PSS (poly(3,4-ethylenedioxythiophene)
poly(styrenesulfonate), purchased as CLEVIOS.TM. P VP Al 4083 from
Heraeus Precious Metals GmbH Deutschland, spun on from aqueous
solution). These coated glass plates form the substrates to which
the OLEDs are applied.
[0178] The OLEDs basically have the following layer structure:
substrate/hole transport layer (HTL)/optional interlayer
(IL)/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 aluminum 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.
[0179] All materials are applied by thermal vapor 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 5e:IC2:TEG1 (45%:45%:10%) mean here that the material from
example 5e is present in the layer in a proportion by volume of
45%, the material IC2 in a proportion by volume of 45% and TEG1 in
a proportion by volume of 10%. Analogously, the electron transport
layer may also consist of a mixture of two materials.
[0180] The OLEDs are characterized in a standard manner. For this
purpose, the electroluminescence spectra, the current efficiency
(measured in cd/A), the power efficiency (measured in lm/W) and the
external quantum efficiency (EQE, measured in percent) are as a
function of luminance, calculated from current-voltage-luminance
characteristics (IUL characteristics) assuming Lambertian radiation
characteristics. The electroluminescence spectra are determined at
a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color
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 and PE1000 respectively refer to the current and
power efficiencies which are 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.
[0181] The data for the various OLEDs are collated in Table 2.
Examples C1-C2 are comparative examples according to the prior art;
examples I1-I11 show data of OLEDs of the invention.
[0182] Some of the examples are elucidated in detail hereinafter,
in order to illustrate the advantages of the OLEDs of the
invention.
[0183] Use of Mixtures of the Invention in the Emission Layer of
Phosphorescent OLEDs
[0184] The materials of the invention, when used as matrix
materials in phosphorescent OLEDs, give significant improvements in
voltage and power efficiency over the prior art. By using the
compound 5d of the invention in combination with the green-emitting
dopant TEG1, it is possible to observe a significant improvement in
voltage and power efficiency over the prior art (C1, C2) (example
I1).
TABLE-US-00013 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL
ETL EIL Ex. thickness thickness thickness thickness thickness
thickness thickness C1 SpA1 HATCN SpMA1 SdT1:TEG1 -- ST2:LiQ
(50%:50%) -- 70 nm 5 nm 90 nm (90%:10%) 40 nm 30 nm C2 SpA1 HATCN
SpMA1 SdT2:TEG1 -- ST2:LiQ (50%:50%) -- 70 nm 5 nm 90 nm (90%:10%)
40 nm 30 nm I1 SpA1 HATCN SpMA1 5d:TEG1 -- ST2:LiQ (50%:50%) -- 70
nm 5 nm 90 nm (90%:10%) 40 nm 30 nm I2 SpA1 HATCN SpMA1 5a:TER1 --
ST2:LiQ (50%:50%) -- 90 nm 5 nm 130 nm (92%:8%) 40 nm 40 nm I3 SpA1
HATCN SpMA1 5b:TER1 -- ST2:LiQ (50%:50%) -- 90 nm 5 nm 130 nm
(92%:8%) 40 nm 40 nm I4 SpA1 HATCN SpMA1 IC1:TEG1 -- 5c:ST2
(50%:50%) LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 40 nm 3 nm I5 SpA1
HATCN SpMA1 5e:IC2:TEG1 -- ST2:LiQ (50%:50%) -- 70 nm 5 nm 90 nm
(45%:45%:10%) 40 nm 30 nm I6 SpA1 HATCN SpMA1 5f:TEG1 (90%:10%) --
ST2:LiQ (50%:50%) -- 70 nm 5 nm 90 nm 40 nm 30 nm I7 SpA1 HATCN
SpMA1 5d:TEG1 -- ST2:LiQ (50%:50%) -- 70 nm 5 nm 90 nm (90%:10%) 40
nm 30 nm I8 SpA1 HATCN SpMA1 IC1:TEG1 -- 5h:ST1 (50%:50%) LiQ 70 nm
5 nm 90 nm (90%:10%) 30 nm 40 nm 3 nm I9 SpA1 HATCN SpMA1 IC1:TEG1
5i ST2:LiQ (50%:50%) -- 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm 30
nm I10 SpA1 HATCN SpMA1 IC1:TEG1 -- 7c:ST2 (50%:50%) LiQ 70 nm 5 nm
90 nm (90%:10%) 30 nm 40 nm 3 nm I11 SpA1 HATCN SpMA1 7d:IC2:TEG1
-- ST2:LiQ (50%:50%) -- 70 nm 5 nm 90 nm (45%:45%:10%) 40 nm 30
nm
TABLE-US-00014 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE
CIE x/y at Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 C1 5.3 46 27
12.9% 0.33/0.62 C2 3.8 52 43 14.5% 0.33/0.62 I1 3.4 54 50 14.7%
0.34/0.63 I2 5.4 13 8 13.1% 0.66/0.34 I3 4.6 13 9 12.7% 0.67/0.33
I4 3.5 59 53 16.2% 0.34/0.63 I5 3.4 60 55 16.6% 0.33/0.62 I6 4.2 47
35 13.2% 0.37/0.60 I7 3.3 57 54 15.2% 0.33/0.63 I8 3.4 60 55 16.4%
0.34/0.63 I9 3.8 60 50 16.0% 0.33/0.63 I10 3.5 59 53 15.9%
0.34/0.62 I11 3.4 58 54 15.5% 0.34/0.63
TABLE-US-00015 TABLE 3 Structural formulae of the materials for the
OLEDs ##STR00192## HATCN ##STR00193## SpA1 ##STR00194## SpMA1
##STR00195## LiQ ##STR00196## IC2 ##STR00197## ST2 ##STR00198## IC1
##STR00199## IC3 ##STR00200## TEG1 ##STR00201## TER1 ##STR00202##
SdT1 ##STR00203## SdT2 ##STR00204## 5d ##STR00205## 5a ##STR00206##
5b ##STR00207## 5c ##STR00208## 5e ##STR00209## 5f ##STR00210## 5g
##STR00211## 5h ##STR00212## 5i ##STR00213## 7c ##STR00214## 7d
* * * * *