U.S. patent application number 15/153185 was filed with the patent office on 2016-09-08 for materials for electronic devices.
The applicant listed for this patent is Merck Patent GmbH. Invention is credited to Arne Buesing, Dominik Joosten, Philipp Stoessel.
Application Number | 20160260911 15/153185 |
Document ID | / |
Family ID | 44504448 |
Filed Date | 2016-09-08 |
United States Patent
Application |
20160260911 |
Kind Code |
A1 |
Stoessel; Philipp ; et
al. |
September 8, 2016 |
MATERIALS FOR ELECTRONIC DEVICES
Abstract
The present invention relates to an electronic device comprising
anode, cathode and at least one organic layer which comprises a
compound of the formula (I) to (IV). The invention furthermore
encompasses the use of compounds of the formula (I) to (IV) in an
electronic device and to a compound of the formula (Ic) to
(IVc).
Inventors: |
Stoessel; Philipp;
(Frankfurt Am Main, DE) ; Buesing; Arne;
(Frankfurt Am Main, DE) ; Joosten; Dominik;
(Frankfurt Am Main, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Merck Patent GmbH |
Darmstadt |
|
DE |
|
|
Family ID: |
44504448 |
Appl. No.: |
15/153185 |
Filed: |
May 12, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13805927 |
Dec 20, 2012 |
9379330 |
|
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PCT/EP2011/002668 |
May 30, 2011 |
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15153185 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K 2211/1088 20130101;
H01L 51/5096 20130101; B32B 9/00 20130101; H01L 51/0085 20130101;
Y02E 10/549 20130101; B32B 2457/202 20130101; H01L 51/0061
20130101; C09K 2211/1011 20130101; H01L 51/0036 20130101; C09K
2211/1044 20130101; C09K 2211/1059 20130101; H01L 51/0067 20130101;
H01L 51/0037 20130101; H01L 51/0072 20130101; H01L 51/0081
20130101; H01L 51/5024 20130101; H01L 51/5072 20130101; H01L
51/0056 20130101; C09K 11/06 20130101; H01L 51/5056 20130101; H01L
51/5016 20130101; H01L 51/5088 20130101; H01L 51/0058 20130101;
H05B 33/14 20130101; C07D 235/00 20130101; H01L 51/5012 20130101;
C07D 487/04 20130101; H01L 51/006 20130101; C09K 2211/1014
20130101; H01L 51/0071 20130101; H01L 51/0094 20130101; C09K
2211/1029 20130101; C09K 2211/1007 20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00; C07D 487/04 20060101 C07D487/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 22, 2010 |
DE |
102010024542.9 |
Claims
1-15. (canceled)
16. An electronic device comprising anode, cathode and at least one
organic layer, wherein the organic layer comprises at least one
compound of the following formulae (I) to (IV) ##STR00394## where
the following applies to the symbols occurring: X is a single bond;
L is a divalent, or in the case of k=3, 4, 5 or 6 a tri-, tetra-,
penta- or hexavalent group respectively, selected from C.dbd.O,
C.dbd.NR.sup.1, Si(R.sup.1).sub.2, P(.dbd.O)(R.sup.1), SO,
SO.sub.2, alkylene groups having 1 to 20 C atoms, alkenylene or
alkynylene groups having 2 to 20 C atoms, where, in the case of the
groups mentioned, one or more CH.sub.2 groups is optionally
replaced by Si(R.sup.1).sub.2, O, S, C.dbd.O, C.dbd.NR.sup.1,
C.dbd.O--O, C.dbd.O--NR.sup.1, NR.sup.1, P(.dbd.O)(R.sup.1), SO or
SO.sub.2 and where one or more H atoms in the above-mentioned
groups is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2,
aromatic or heteroaromatic ring systems having 5 to 60 aromatic
ring atoms, each of which is optionally substituted by one or more
radicals R.sup.1, and any desired combinations of 1, 2, 3, 4 or 5
identical or different groups selected from the above-mentioned
groups; or L is a single bond, where k in this case must be equal
to 2; R.sup.0 is on each occurrence, identically or differently, H,
D, F, Cl, Br, I, C(.dbd.O)R.sup.1, OSO.sub.2R.sup.1, COOR.sup.1,
CON(R.sup.1).sub.2, a straight-chain alkyl group having 1 to 40 C
atoms or a branched or cyclic alkyl group having 3 to 40 C atoms or
an alkenyl or alkynyl group having 2 to 40 C atoms, where the
above-mentioned groups may each be substituted by one or more
radicals R.sup.1 and where one or more CH.sub.2 groups in the
above-mentioned groups is optionally replaced by Si(R.sup.1).sub.2,
Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.1, P(.dbd.O)(R.sup.1), SO, SO.sub.2, NR.sup.1, --O--,
--S--, --COO-- or --CONR.sup.1-- and where one or more H atoms in
the above-mentioned groups is optionally replaced by D, F, Cl, Br,
I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system
having 5 to 60 aromatic ring atoms, which may in each case be
substituted by one or more radicals R.sup.1, or an aralkyl or
heteroaralkyl group having 5 to 60 aromatic ring atoms, which is
optionally substituted by one or more radicals R.sup.1, or a
combination of these systems, furthermore, two or more adjacent
radicals R.sup.0 is optionally linked to one another here and form
an aliphatic or aromatic ring, or a radical R.sup.0 is optionally
linked to an adjacent radical R via a single bond or a divalent
group Y and form an aliphatic or aromatic ring; R is equal to
C(.dbd.O)R.sup.1, OSO.sub.2R.sup.1, COOR.sup.1, CON(R.sup.1).sub.2,
a straight-chain alkyl group having 1 to 40 C atoms or a branched
or cyclic alkyl group having 3 to 40 C atoms or an alkenyl or
alkynyl group having 2 to 40 C atoms, where the above-mentioned
groups may each be substituted by one or more radicals R.sup.1 and
where one or more CH.sub.2 groups in the above-mentioned groups is
optionally replaced by Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2,
Sn(R.sup.1).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se, C.dbd.NR.sup.1,
P(.dbd.O)(R.sup.1), SO, SO.sub.2, NR.sup.1, --O--, --S--, --COO--
or --CONR.sup.1-- and where one or more H atoms in the
above-mentioned groups is optionally replaced by D, F, Cl, Br, I,
CN or NO.sub.2, or an aromatic or heteroaromatic ring system having
5 to 60 aromatic ring atoms, which may in each case be substituted
by one or more radicals R.sup.1, or an aralkyl or heteroaralkyl
group having 5 to 60 aromatic ring atoms, which is optionally
substituted by one or more radicals R.sup.1, or a combination of
these systems, where furthermore the radical R is optionally linked
to one or more adjacent radicals R.sup.0 via a single bond or a
divalent group Y; Y is on each occurrence, identically or
differently, a divalent group selected from C.dbd.O, C.dbd.S,
C.dbd.NR.sup.1, C(R.sup.1).sub.2, Si(R.sup.1).sub.2, NR.sup.1,
PR.sup.1, P(.dbd.O)R.sup.1, O, S, SO and SO.sub.2; R.sup.1 is on
each occurrence, identically or differently, H, D, F, Cl, Br, I,
CHO, N(R.sup.2).sub.2, C(.dbd.O)R.sup.2, P(.dbd.O)(R.sup.2).sub.2,
S(.dbd.O)R.sup.2, S(.dbd.O).sub.2R.sup.2, CN, NO.sub.2,
Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, OSO.sub.2R.sup.2, OH,
COOR.sup.2, CON(R.sup.2).sub.2, a straight-chain alkyl, alkoxy or
thioalkyl group having 1 to 40 C atoms or a branched or cyclic
alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an
alkenyl or alkynyl group having 2 to 40 C atoms, where the
above-mentioned groups may each be substituted by one or more
radicals R.sup.2 and where one or more CH.sub.2 groups in the
above-mentioned groups is optionally replaced by Si(R.sup.2).sub.2,
Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.2, P(.dbd.O)(R.sup.2), SO, SO.sub.2, NR.sup.2, --O--,
--S--, --COO-- or --CONR.sup.2-- and where one or more H atoms in
the above-mentioned groups is optionally replaced by D, F, Cl, Br,
I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system
having 5 to 60 aromatic ring atoms, which may in each case be
substituted by one or more radicals R.sup.2, or an aryloxy or
heteroaryloxy group having 5 to 60 aromatic ring atoms, which is
optionally substituted by one or more radicals R.sup.2, or a
combination of these systems, where two or more radicals R.sup.1 is
optionally linked to one another and may form an aliphatic or
aromatic ring; R.sup.2 is, identically or differently on each
occurrence, H, D, F or an aliphatic, aromatic and/or heteroaromatic
organic radical having 1 to 20 C atoms, in which, in addition, one
or more H atoms is optionally replaced by D or F; two or more
substituents R.sup.2 here may also be linked to one another and
form an aliphatic or aromatic ring; and k is equal to 2, 3, 4, 5 or
6.
17. The electronic device according to claim 16, wherein the
compound of one of the formulae (I) to (IV) represents a compound
of one of the formulae (Ia), (Ib), (IIa), (IIb), (Ma), (IIIb),
(IVa) and (IVb) ##STR00395## where the symbols occurring are as
defined in claim 16 and furthermore: Ar.sup.1 and Ar.sup.2 are,
identically or differently, an aryl group containing 6 to 60
aromatic ring atoms or a heteroaryl group containing 5 to 60
aromatic ring atoms, each of which is optionally substituted by one
or more radicals R.sup.1; and is optionally linked, analogously to
the definition indicated in claim 16, to one or more radicals
R.sup.0 and/or an adjacent group Ar.sup.1 or Ar.sup.2 via a single
bond or via a divalent group Y.
18. The electronic device according to claim 16, wherein that the
compound of one of the formulae (I) to (IV) represents a compound
of one of the formulae (Ic), (IIc), (IIIc) and (IVc) ##STR00396##
where the symbols occurring are as defined in claim 16 and
furthermore: Ar.sup.1 and Ar.sup.2 are, identically or differently,
an aryl group containing 6 to 60 aromatic ring atoms or a
heteroaryl group containing 5 to 60 aromatic ring atoms, each of
which is optionally substituted by one or more radicals R.sup.1;
and R is optionally linked, analogously to the definition indicated
in claim 16, to one or more adjacent groups Ar.sup.1 and Ar.sup.2
via a single bond or via a divalent group Y.
19. The electronic device according to claim 16, wherein the
radical R represents an aryl or heteroaryl group having 5 to 20
aromatic ring atoms, which may in each case be substituted by one
or more radicals R.sup.1, or represents an aralkyl or heteroaralkyl
group having 5 to 20 aromatic ring atoms, which is optionally
substituted by one or more radicals R.sup.1, where the radical R
may furthermore be linked to one of the groups Ar.sup.1 and
Ar.sup.2 via a single bond or via a divalent group Y.
20. The electronic device according to claim 16, wherein k is equal
to 2 or 3.
21. The electronic device according to claim 16, wherein the
compound of one of the formulae (I) to (IV) represents a compound
of one of the formulae (IX-1) to (IX-3) and (X-1) ##STR00397##
where the symbols occurring are as defined in claim 16 and
furthermore Z is on each occurrence, identically or differently,
CR.sup.1 or N, where not more than two adjacent groups Z may
simultaneously be equal to N.
22. The electronic device according to claim 16, wherein the device
is an organic integrated circuit (O-IC), organic field-effect
transistor (O-FET), organic thin-film transistor (O-TFT), organic
light-emitting transistor (O-LET), organic solar cell (O-SC),
organic optical detector, organic photoreceptor, organic
field-quench device (O-FQD), light-emitting electrochemical cell
(LEC), organic laser diode (O-laser) and organic electroluminescent
device (OLED).
23. The electronic device according to claim 22, wherein the device
is an OLED.
24. The electronic device according to claim 16, wherein the
compound of one of the formulae (I) to (IV) is employed as
hole-transport material in a hole-transport layer or hole-injection
layer and/or is employed as matrix material in an emitting
layer.
25. A compound of one of the formulae (Ic) to (IVc) ##STR00398##
wherein Ar.sup.1 and Ar.sup.2 are, identically or differently, an
aryl group containing 6 to 60 aromatic ring atoms or a heteroaryl
group containing 5 to 60 aromatic ring atoms, each of which is
optionally substituted by one or more radicals R.sup.1; and R is an
aromatic or heteroaromatic ring system having 5 to 20 aromatic ring
atoms, which may in each case be substituted by one or more
radicals R.sup.1, or an aralkyl or heteroaralkyl group having 5 to
20 aromatic ring atoms, may be substituted by one or more radicals
R.sup.1, where the radical R may furthermore be linked to an
adjacent group Ar.sup.1 or Ar.sup.2 via a single bond or via a
divalent group Y; X is a single bond; L is a divalent, or in the
case of k=3, 4, 5 or 6 a tri-, tetra-, penta- or hexavalent group
respectively, selected from C.dbd.O, C.dbd.NR.sup.1,
Si(R.sup.1).sub.2, P(.dbd.O)(R.sup.1), SO, SO.sub.2, alkylene
groups having 1 to 20 C atoms, alkenylene or alkynylene groups
having 2 to 20 C atoms, where, in the case of the groups mentioned,
one or more CH.sub.2 groups is optionally replaced by
Si(R.sup.1).sub.2, O, S, C.dbd.O, C.dbd.NR.sup.1, C.dbd.O--O,
C.dbd.O--NR.sup.1, NR.sup.1, P(.dbd.O)(R.sup.1), SO or SO.sub.2 and
where one or more H atoms in the above-mentioned groups is
optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, aromatic or
heteroaromatic ring systems having 5 to 60 aromatic ring atoms,
each of which is optionally substituted by one or more radicals
R.sup.1, and any desired combinations of 1, 2, 3, 4 or 5 identical
or different groups selected from the above-mentioned groups; or L
is a single bond, where k in this case must be equal to 2; Y is on
each occurrence, identically or differently, a divalent group
selected from C.dbd.O, C.dbd.S, C.dbd.NR.sup.1, C(R.sup.1).sub.2,
Si(R.sup.1).sub.2, NR.sup.1, PR.sup.1, P(.dbd.O)R.sup.1, O, S, SO
and SO.sub.2; R.sup.1 is on each occurrence, identically or
differently, H, D, F, Cl, Br, I, CHO, N(R.sup.2).sub.2,
C(.dbd.O)R.sup.2, P(.dbd.O)(R.sup.2).sub.2, S(.dbd.O)R.sup.2,
S(.dbd.O).sub.2R.sup.2, CN, NO.sub.2, Si(R.sup.2).sub.3,
B(OR.sup.2).sub.2, OSO.sub.2R.sup.2, OH, COOR.sup.2,
CON(R.sup.2).sub.2, a straight-chain alkyl, alkoxy or thioalkyl
group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy
or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl
group having 2 to 40 C atoms, where the above-mentioned groups may
each be substituted by one or more radicals R.sup.2 and where one
or more CH.sub.2 groups in the above-mentioned groups is optionally
replaced by Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2,
Sn(R.sup.2).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se, C.dbd.NR.sup.2,
P(.dbd.O)(R.sup.2), SO, SO.sub.2, NR.sup.2, --O--, --S--, --COO--
or --CONR.sup.2-- and where one or more H atoms in the
above-mentioned groups is optionally replaced by D, F, Cl, Br, I,
CN or NO.sub.2, or an aromatic or heteroaromatic ring system having
5 to 60 aromatic ring atoms, which may in each case be substituted
by one or more radicals R.sup.2, or an aryloxy or heteroaryloxy
group having 5 to 60 aromatic ring atoms, which is optionally
substituted by one or more radicals R.sup.2, or a combination of
these systems, where two or more radicals R.sup.1 is optionally
linked to one another and may form an aliphatic or aromatic ring;
R.sup.2 is, identically or differently on each occurrence, H, D, F
or an aliphatic, aromatic and/or heteroaromatic organic radical
having 1 to 20 C atoms, in which, in addition, one or more H atoms
is optionally replaced by D or F; two or more substituents R.sup.2
here may also be linked to one another and form an aliphatic or
aromatic ring; and k is equal to 2, 3, 4, 5 or 6.
26. An oligomer, polymer or dendrimer comprising one or more
compounds according to claim 25, where the bond(s) to the polymer,
oligomer or dendrimer may be localised at any position substituted
by R or R.sup.1 in formula (Ic) to (IVc).
27. A formulation comprising at least one compound according to
claim 25 and at least one solvent.
28. A formulation comprising at least one polymer, oligomer or
dendrimer according to claim 26 and at least one solvent.
29. A process for the preparation of the compound of the formula
(Ic) to (IVc) according to the invention according to claim 25,
which comprises at least one of the two steps a) and b) indicated
below is carried out: a) deprotonation at the 5- or 6-N atom of the
benzimidazoquinazoline skeleton and subsequent reaction with an
electrophilic compound, so that a bond is formed between the 5- or
6-N atom and the electrophilic compound; b) organometallic coupling
under Hartwig-Buchwald or Ullmann conditions between the 5- or 6-N
atom of the benzimidazoquinazoline skeleton and an aryl group Ar,
which is employed as starting material Ar-Hal, where Hal is any
suitable leaving group.
30. An electronic device which comprises the compound according to
claim 25.
31. An organic electroluminescent device which comprises the
compound according to claim 25.
32. An electronic device which comprises the at least one polymer,
oligomer or dendrimer according to claim 26.
33. An organic electroluminescent device which comprises the
compound according to claim at least one polymer, oligomer or
dendrimer according to claim 26.
34. An organic electroluminescent device which comprises the
compound according to claim 25 as hole-transport material, as
matrix material, as emitter material, as electron-blocking
material, as hole-injection material, as hole-blocking material
and/or as electron-transport material.
35. An organic electroluminescent device which comprises said at
least one polymer, oligomer or dendrimer as claimed in claim 26 as
a hole-transport material, as matrix material, as emitter material,
as electron-blocking material, as hole-injection material, as
hole-blocking material and/or as electron-transport material.
Description
[0001] The present invention relates to an electronic device
comprising at least one compound of the formula (I) to (IV), to the
use of compounds of the formula (I) to (IV) in an electronic device
and to a compound of the formula (Ic) to (IVc).
[0002] Electronic devices in the sense of the present invention are
preferably organic electroluminescent devices, but may also
represent other electronic devices, as described in greater detail
later.
[0003] The general structure of an organic electroluminescent
device (OLED) is revealed, inter alia, by U.S. Pat. No. 4,539,507,
U.S. Pat. No. 5,151,629, EP 0676461 and WO 1998/27136.
[0004] With respect to the performance data and lifetime of organic
electroluminescent devices, considerable advances have been
achieved in recent years. However, there is a further need for
improvement, in particular in the following points: [0005] 1. An
increase in the power efficiency of the devices is desirable.
[0006] 2. There is still a need for improvement in the operating
lifetime of the devices, in particular in the case of blue
emission. [0007] 3. A reduction in the operating voltage of the
devices is desirable. This is of major importance, in particular,
for mobile applications.
[0008] Thus, there continues to be a demand for novel functional
materials for organic electroluminescent devices which have a
positive influence on the performance data of the devices, in
particular in the points mentioned above.
[0009] Furthermore, generally in the area of materials for organic
electroluminescent devices, there is interest in the provision of
novel, alternative compounds which are suitable for use in the said
devices and with which comparably good performance data as with
compounds which are already known can be achieved.
[0010] Inter alia, arylamine compounds are known in the prior art
as hole-transport and -injection materials for organic
electroluminescent devices. Materials of this type based on an
indenofluorene skeleton are disclosed, for example, in WO
2006/100896 and WO 2006/122630.
[0011] However, the hole-transporting materials known in the prior
art frequently have low electron stability, which reduces the
lifetime of electronic devices comprising these compounds.
[0012] There is therefore, in particular, a demand for novel
compounds for use as hole-transport and/or hole-injection materials
in the above-mentioned devices.
[0013] Inter alia, carbazole derivatives, for example
bis(carbazolyl)biphenyl, are known in the prior art as matrix
materials for phosphorescent dopants. Also known is the use of
ketones (WO 2004/093207), phosphine oxides and sulfones (WO
2005/003253) as matrix materials for phosphorescent dopants. Metal
complexes, for example BAlq or zinc(II)
bis[2-(2-benzothiazole)phenolate], are also used as matrix
materials for phosphorescent dopants.
[0014] However, there continues to be a demand for alternative
matrix materials for phosphorescent dopants, in particular those
which effect an improvement in the performance data of the
electronic devices.
[0015] Also of particular interest is the provision of alternative
materials as matrix components of mixed-matrix systems. A
mixed-matrix system in the sense of this application is taken to
mean a system in which two or more different compounds are used in
an emitting layer mixed together with an (alternatively also
several) dopant compounds. These systems are, in particular, of
interest in the case of phosphorescent organic electroluminescent
devices. For more detailed information, reference is made to the
application WO 2010/108579.
[0016] Compounds known in the prior art which may be mentioned for
use as matrix components in mixed-matrix systems are, inter alia,
CBP (biscarbazolylbiphenyl) and TCTA (triscarbazolyltriphenylamine)
(first component). Suitable as second component are compounds such
as, for example, benzophenone derivatives, diazaphospholes (WO
2010/054730) and triazines. However, there continues to be a demand
for alternative compounds for use as matrix components in
mixed-matrix systems. In particular, there is a demand for
compounds which effect an improvement in the operating voltage and
lifetime of the electronic devices.
[0017] Overall, further improvements are desirable with respect to
the efficiency and lifetime of fluorescent and/or phosphorescent
organic electroluminescent devices. Potential for improvement
furthermore exists in the case of the operating voltage of the
electronic devices.
[0018] The present invention provides novel organic
electroluminescent devices in order to achieve the technical object
described above.
[0019] The invention thus relates to an electronic device
comprising anode, cathode and at least one organic layer,
characterised in that the organic layer comprises at least one
compound of the following formulae (I) to (IV)
##STR00001##
where the following applies to the symbols occurring: [0020] X is
on each occurrence, identically or differently, a single bond,
C.dbd.O, C.dbd.S, C.dbd.NR.sup.1, C(R.sup.1).sub.2,
C(R.sup.1).sub.2--C(R.sup.1).sub.2, CR.sup.1.dbd.CR.sup.1,
Si(R.sup.1).sub.2, NR.sup.1, PR.sup.1, P(.dbd.O)R.sup.1, O, S, SO
or SO.sub.2; [0021] L is a divalent, or in the case of k=3, 4, 5 or
6 a tri-, tetra-, penta- or hexavalent group respectively, selected
from C.dbd.O, C.dbd.NR.sup.1, Si(R.sup.1).sub.2,
P(.dbd.O)(R.sup.1), SO, SO.sub.2, alkylene groups having 1 to 20 C
atoms, alkenylene or alkynylene groups having 2 to 20 C atoms,
where, in the case of the groups mentioned, one or more CH.sub.2
groups may be replaced by Si(R.sup.1).sub.2, O, S, C.dbd.O,
C.dbd.NR.sup.1, C.dbd.O--O, C.dbd.O--NR.sup.1, NR.sup.1,
P(.dbd.O)(R.sup.1), SO or SO.sub.2 and where one or more H atoms in
the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN
or NO.sub.2, aromatic or heteroaromatic ring systems having 5 to 60
aromatic ring atoms, each of which may be sub-stituted by one or
more radicals R.sup.1, and any desired combinations of 1, 2, 3, 4
or 5 identical or different groups selected from the
above-mentioned groups; or L is a single bond, where k in this case
must be equal to 2; [0022] R.sup.0 is on each occurrence,
identically or differently, H, D, F, Cl, Br, I, C(.dbd.O)R.sup.1,
OSO.sub.2R.sup.1, COOR.sup.1, CON(R.sup.1).sub.2, a straight-chain
alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl
group having 3 to 40 C atoms or an alkenyl or alkynyl group having
2 to 40 C atoms, where the above-mentioned groups may each be
substituted by one or more radicals R.sup.1 and where one or more
CH.sub.2 groups in the above-mentioned groups may be replaced by
Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C.dbd.O,
C.dbd.S, C.dbd.Se, C.dbd.NR.sup.1, P(.dbd.O)(R.sup.1), SO,
SO.sub.2, NR.sup.1, --O--, --S--, --COO-- or --CONR.sup.1-- and
where one or more H atoms in the above-mentioned groups may be
replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or
heteroaromatic ring system having 5 to 60 aromatic ring atoms,
which may in each case be substituted by one or more radicals
R.sup.1, or an aralkyl or heteroaralkyl group having 5 to 60
aromatic ring atoms, which may be substituted by one or more
radicals R.sup.1, or a combination of these systems, furthermore
two or more adjacent radicals R.sup.0 may be linked to one another
here and form an aliphatic or aromatic ring, or a radical R.sup.0
may be linked to an adjacent radical R via a single bond or a
divalent group Y and form an aliphatic or aromatic ring;
[0023] R is equal to C(.dbd.O)R.sup.1, OSO.sub.2R.sup.1,
COOR.sup.1, CON(R.sup.1).sub.2, a straight-chain alkyl group having
1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40
C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms,
where the above-mentioned groups may each be substituted by one or
more radicals R.sup.1 and where one or more CH.sub.2 groups in the
above-mentioned groups may be replaced by Si(R.sup.1).sub.2,
Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.1, P(.dbd.O)(R.sup.1), SO, SO.sub.2, NR.sup.1, --O--,
--S--, --COO-- or --CONR.sup.1-- and where one or more H atoms in
the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN
or NO.sub.2, or an aromatic or heteroaromatic ring system having 5
to 60 aromatic ring atoms, which may in each case be substituted by
one or more radicals R.sup.1, or an aralkyl or heteroaralkyl group
having 5 to 60 aromatic ring atoms, which may be substituted by one
or more radicals R.sup.1, or a combination of these systems, where
furthermore the radical R may be linked to one or more adjacent
radicals R.sup.0 via a single bond or a divalent group Y; [0024] Y
is on each occurrence, identically or differently, a divalent group
selected from C.dbd.O, C.dbd.S, C.dbd.NR.sup.1, C(R.sup.1).sub.2,
Si(R.sup.1).sub.2, NR.sup.1, PR.sup.1, P(.dbd.O)R.sup.1, O, S, SO
and SO.sub.2; [0025] R.sup.1 is on each occurrence, identically or
differently, H, D, F, Cl, Br, I, CHO, N(R.sup.2).sub.2,
C(.dbd.O)R.sup.2, P(.dbd.O)(R.sup.2).sub.2, S(.dbd.O)R.sup.2,
S(.dbd.O).sub.2R.sup.2, CN, NO.sub.2, Si(R.sup.2).sub.3,
B(OR.sup.2).sub.2, OSO.sub.2R.sup.2, OH, COOR.sup.2,
CON(R.sup.2).sub.2, a straight-chain alkyl, alkoxy or thioalkyl
group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy
or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl
group having 2 to 40 C atoms, where the above-mentioned groups may
each be substituted by one or more radicals R.sup.2 and where one
or more CH.sub.2 groups in the above-mentioned groups may be
replaced by Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2,
Sn(R.sup.2).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se, C.dbd.NR.sup.2,
P(.dbd.O)(R.sup.2), SO, SO.sub.2, NR.sup.2, --O--, --S--, --COO--
or --CONR.sup.2-- and where one or more H atoms in the
above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or
NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to
60 aromatic ring atoms, which may in each case be substituted by
one or more radicals R.sup.2, or an aryloxy or heteroaryloxy group
having 5 to 60 aromatic ring atoms, which may be substituted by one
or more radicals R.sup.2, or a combination of these systems, where
two or more radicals R.sup.1 may be linked to one another and may
form an aliphatic or aromatic ring; [0026] R.sup.2 is, identically
or differently on each occurrence, H, D, F or an aliphatic,
aromatic and/or heteroaromatic organic radical having 1 to 20 C
atoms, in which, in addition, one or more H atoms may be replaced
by D or F; two or more substituents R.sup.2 here may also be linked
to one another and form an aliphatic or aromatic ring; and [0027] k
is equal to 2, 3, 4, 5 or 6.
[0028] Preferred embodiments of compounds of the formula (I), (II),
(III) and (IV) are the following compounds of the formula (Ia),
(Ib), (IIa), (IIb), (IIIa), (IIIb), (IVa) and (IVb)
##STR00002##
where the symbols occurring are as defined above and furthermore:
[0029] Ar.sup.1, Ar.sup.2 are, identically or differently, an aryl
group containing 6 to 60 aromatic ring atoms or a heteroaryl group
containing 5 to 60 aromatic ring atoms, each of which may be
substituted by one or more radicals R.sup.1; and [0030] R may be
linked, analogously to the above-mentioned definition, to one or
more radicals R.sup.0 and/or an adjacent group Ar.sup.1 or Ar.sup.2
via a single bond or via a divalent group Y.
[0031] Particularly preferred embodiments of compounds of the
formulae (I), (II), (III) and (IV) are the compounds of the
formulae (Ic), (IIc), (IIIc) and (IVc) shown below
##STR00003##
where the symbols occurring are as defined above and furthermore:
[0032] Ar.sup.1, Ar.sup.2 are, identically or differently, an aryl
group containing 6 to 60 aromatic ring atoms or a heteroaryl group
containing 5 to 60 aromatic ring atoms, each of which may be
substituted by one or more radicals R.sup.1; and [0033] R may be
linked, analogously to the above-mentioned definition, to one or
more adjacent groups Ar.sup.1 and Ar.sup.2 via a single bond or via
a divalent group Y.
[0034] The groups
##STR00004##
drawn adjacent to the heterocycles in the above-mentioned formulae
denote that a group Ar.sup.1 or Ar.sup.2, as defined above, is
condensed onto the heterocycle in question, so that it forms a
common condensed heteroaryl group with the heterocycle. The
preferred embodiments of the compounds of the formula (I) to (IV)
mentioned in later sections illustrate this principle.
[0035] It is preferred in accordance with the invention for the
groups Ar.sup.1 and Ar.sup.2 to be selected, identically or
differently, from aryl groups having 6 to 20 aromatic ring atoms,
which may be substituted by one or more radicals R.sup.1, and
heteroaryl groups having 5 to 20 aromatic ring atoms, which may be
substituted by one or more radicals R.sup.1. The groups Ar.sup.1
and Ar.sup.2 are particularly preferably selected on each
occurrence, identically or differently, from aryl groups having 6
to 14 aromatic ring atoms, which may be substituted by one or more
radicals and heteroaryl groups having 5 to 14 aromatic ring atoms,
which may be substituted by one or more radicals R.
[0036] In the sense of this invention, condensed aromatic or
heteroaromatic rings are generally taken to mean rings which have
at least two adjacent aromatic ring atoms in common with one
another. A corresponding definition also applies analogously to
aliphatic rings.
[0037] Furthermore, the formulation that a ring is condensed onto
another ring is in the sense of this invention taken to mean that
the condensed-on ring has at least two adjacent ring atoms in
common with the first ring.
[0038] An aryl group in the sense of this invention contains 6 to
60 C atoms; a heteroaryl group in the sense of this invention
contains 1 to 60 C atoms and at least one heteroatom, with the
proviso that the sum of C atoms and heteroatoms is at least 5. The
heteroatoms are preferably selected from N, P, O and/or S. An aryl
group or heteroaryl group here is taken to mean either a simple
aromatic ring, i.e. benzene, or a simple heteroaromatic ring, for
example pyridine, pyrimidine, thiophene, etc., or a condensed
(fused) aryl or heteroaryl group, for example naphthalene,
anthracene, phenanthrene, quinoline, isoquinoline, carbazole,
etc.
[0039] An aryl or heteroaryl group, which may in each case be
substituted by the above-mentioned radicals R.sup.1 or R.sup.2 and
which may be linked to the aromatic or heteroaromatic ring system
via any desired positions, is taken to mean, in particular, groups
derived from benzene, naphthalene, anthracane, phenanthrene,
pyrene, dihydropyrene, chrysene, perylene, fluoranthene,
benzanthracene, benzophenanthrene, tetracene, pentacene,
benzopyrene, 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,
benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline,
pyrazine, phenazine, 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.
[0040] An aralkyl group in the sense of this invention is an alkyl
group which is substituted by an aryl group, where the term aryl
group is to be understood as defined above and alkyl group is
defined as a non-aromatic organic radical having 1-40 atoms, in
which, in addition, individual H atoms or CH.sub.2 groups may be
substituted by the groups mentioned above in the definition of R
and R.sup.1.
[0041] A heteroaralkyl group in the sense of this invention is an
alkyl group which is substituted by a heteroaryl group, where the
term heteroaryl group is to be understood as defined above and
alkyl group is defined as a non-aromatic organic radical having
1-40 atoms, in which, in addition, individual H atoms or CH.sub.2
groups may be substituted by the groups mentioned above in the
definition of R and R.sup.1.
[0042] An aromatic ring system in the sense of this invention
contains 6 to 60 C atoms in the ring system. A heteroaromatic ring
system in the sense of this invention contains 5 to 60 aromatic
ring atoms, at least one of which is a heteroatom. The heteroatoms
are preferably selected from N, O and/or S. An aromatic or
heteroaromatic ring system in the sense of this invention is
intended to be taken to mean a system which does not necessarily
contain only aryl or heteroaryl groups, but instead in which, in
addition, a plurality of aryl or heteroaryl groups may be connected
by a non-aromatic unit (preferably less than 10% of the atoms other
than H), such as, for example, a C, Si, N or O atom or a carbonyl
group. Thus, for example, systems such as 9,9'-spirobifluorene,
9,9'-diarylfluorene, triarylamine, diaryl ether, stilbene, etc.,
are also intended to be taken to be aromatic ring systems in the
sense of this invention, as are systems in which two or more aryl
groups are connected, for example, by a linear or cyclic alkyl,
alkenyl or alkynyl group or by a silyl group. Furthermore, systems
in which two or more aryl or heteroaryl groups are linked to one
another via single bonds, such as, for example, biphenyl, terphenyl
or bipyridine, are also intended to be taken to be aromatic or
heteroaromatic ring systems in the sense of this invention.
[0043] An aromatic or heteroaromatic ring system having 5-60
aromatic ring atoms, which may also in each case be substituted by
radicals as defined above and which may be linked via any desired
positions on the aromatic or heteroaromatic group, is taken to
mean, in particular, groups derived from benzene, naphthalene,
anthracene, benzanthracene, phenanthrene, benzophenanthrene,
pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene,
benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene,
fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene,
tetrahydropyrene, cis- or trans-indenofluorene, 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, fluorubin, 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 combinations of these
groups.
[0044] For the purposes of the present invention, a straight-chain
alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl
group having 3 to 40 C atoms or an alkenyl or alkynyl group having
2 to 40 C atoms, where, in addition, individual H atoms or CH.sub.2
groups in the above-mentioned groups may be substituted by the
groups mentioned above in the case of the definition of the
radicals R and R.sup.1, is preferably taken to mean the radicals
methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl,
t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl,
n-hexyl, cyclohexyl, neohexyl, 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 or octynyl. An alkoxy or thioalkyl group having 1 to 40 C
atoms is preferably taken 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,
2,2,2-trifluoroethoxy, 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.
[0045] Preferred embodiments of the compounds of the formula (Ic)
to (IVc) are illustrated by the following formulae (V) to (X)
##STR00005##
where furthermore: [0046] X.sup.1 is selected from C.dbd.O,
C.dbd.S, C.dbd.NR.sup.1, C(R.sup.1).sub.2,
C(R.sup.1).sub.2--C(R.sup.1).sub.2, NR.sup.1, PR.sup.1,
P(.dbd.O)R.sup.1, O, S, SO and SO.sub.2; [0047] Z is on each
occurrence, identically or differently, CR.sup.1 or N, where not
more than two adjacent groups Z may simultaneously be equal to N;
and the other symbols occurring are as defined above.
[0048] In a preferred embodiment of the invention, not more than
three groups Z in a formula are equal to N, and the remaining
groups Z are equal to CR.sup.1. In a particularly preferred
embodiment, all groups Z in a formula are equal to CR.sup.1.
[0049] In a further preferred embodiment of the invention, the
group X is selected from a single bond, C.dbd.O, C.dbd.NR.sup.1,
C(R.sup.1).sub.2, CR.sup.1.dbd.CR.sup.1, NR.sup.1, O and S. X is
particularly preferably selected from a single bond, C.dbd.O and
C(R.sup.1).sub.2.
[0050] If the group X represents a group of the formula
C(R.sup.1).sub.2, it is a preferred embodiment that the two
radicals R.sup.1 which are bonded to the same C atom are linked to
one another and form an aliphatic or aromatic ring.
[0051] In a further preferred embodiment of the invention, the
group X.sup.1 is selected from C.dbd.O, C.dbd.NR.sup.1,
C(R.sup.1).sub.2, CR.sup.1.dbd.CR.sup.1, NR.sup.1, O and S. X.sup.1
is particularly preferably selected from C.dbd.O and
C(R.sup.1).sub.2.
[0052] If the group X' represents a group of the formula
C(R.sup.1).sub.2, it is a preferred embodiment that the two
radicals R.sup.1 which are bonded to the same C atom are linked to
one another and form an aliphatic or aromatic ring.
[0053] In a further preferred embodiment of the invention, R.sup.0
is on each occurrence, identically or differently, H, D, F, CI, Br,
I, N(R.sup.1).sub.2, C(.dbd.O)R.sup.1, CN, Si(R.sup.1).sub.3,
COOR.sup.1, CON(R.sup.1).sub.2, a straight-chain alkyl, alkoxy or
thioalkyl group having 1 to 10 C atoms or a branched or cyclic
alkyl, alkoxy or thioalkyl group having 3 to 10 C atoms or an
alkenyl or alkynyl group having 2 to 10 C atoms, where the
above-mentioned groups may each be substituted by one or more
radicals R.sup.1 and where one or more non-adjacent CH.sub.2 groups
in the above-mentioned groups may be replaced by Si(R.sup.1).sub.2,
C.dbd.O, C.dbd.NR.sup.1, SO, SO.sub.2, NR.sup.1, --O--, --S--,
--COO-- or --CONR.sup.1-- and where one or more H atoms in the
above-mentioned groups may be replaced by D, F, Cl, Br, I or CN, or
an aromatic or heteroaromatic ring system having 5 to 20 aromatic
ring atoms, which may in each case be substituted by one or more
radicals R.sup.1, or an aryloxy or heteroaryloxy group having 5 to
20 aromatic ring atoms, which may be substituted by one or more
radicals R.sup.1, or a combination of these systems, furthermore,
two or more adjacent radicals R.sup.0 may be linked to one another
and form an aliphatic or aromatic ring or a radical R.sup.0 may be
linked to an adjacent radical R via a single bond or a divalent
group Y and form an aliphatic or aromatic ring.
[0054] In a further preferred embodiment of the invention, the
radical R is a straight-chain alkyl group having 1 to 10 C atoms or
a branched or cyclic alkyl group having 3 to 10 C atoms or an
alkenyl or alkynyl group having 2 to 10 C atoms, where the
above-mentioned groups may each be substituted by one or more
radicals R.sup.1 and where one or more non-adjacent CH.sub.2 groups
in the above-mentioned groups may be replaced by C.dbd.O,
C.dbd.NR.sup.1, P(.dbd.O)(R.sup.1), SO, SO.sub.2, NR.sup.1, --O--,
--S--, --COO-- or --CONR.sup.1-- and where one or more H atoms in
the above-mentioned groups may be replaced by D, F, CI, Br, I or
CN, or an aromatic or heteroaromatic ring system having 5 to 20
aromatic ring atoms, which may in each case be substituted by one
or more radicals R.sup.1, or an aralkyl or heteroaralkyl group
having 5 to 20 aromatic ring atoms, which may be substituted by one
or more radicals R.sup.1, or a combination of these systems, and
where the radical R may furthermore be linked to one of the groups
Ar.sup.1 and Ar.sup.2 via a single bond or via a divalent group
Y.
[0055] The radical R is particularly preferably an aryl or
heteroaryl group having 5 to 20 aromatic ring atoms, which may in
each case be substituted by one or more radicals R.sup.1, or an
aralkyl or heteroaralkyl group having 5 to 20 aromatic ring atoms,
which may be substituted by one or more radicals R.sup.1, where the
radical R may furthermore be linked to one of the groups Ar.sup.1
and Ar.sup.2 via a single bond or via a divalent group Y.
[0056] The radical R is again more preferably selected from
benzene, pyridine, pyrimidine, pyridazine, pyrazine and triazine,
where the said groups may be substituted by one or more radicals
R.sup.1 and where the radical R may be linked to one of the groups
Ar.sup.1 and Ar.sup.2 via a single bond or via a divalent group
Y.
[0057] In a preferred embodiment, the divalent group Y is selected,
identically or differently, from C.dbd.O, C.dbd.NR.sup.1,
C(R.sup.1).sub.2, NR.sup.1, O, S and SO.sub.2.
[0058] In a further preferred embodiment, R.sup.1 is on each
occurrence, identically or differently, H, D, F, CI, Br, I,
N(R.sup.2).sub.2, C(.dbd.O)R.sup.2, CN, Si(R.sup.2).sub.3,
COOR.sup.2, CON(R.sup.2).sub.2, a straight-chain alkyl, alkoxy or
thioalkyl group having 1 to 10 C atoms or a branched or cyclic
alkyl, alkoxy or thioalkyl group having 3 to 10 C atoms or an
alkenyl or alkynyl group having 2 to 10 C atoms, where the
above-mentioned groups may each be substituted by one or more
radicals R.sup.2 and where one or more non-adjacent CH.sub.2 groups
in the above-mentioned groups may be replaced by Si(R.sup.2).sub.2,
C.dbd.O, C.dbd.NR.sup.2, SO, SO.sub.2, NR.sup.2, --O--, --S--,
--COO-- or --CONR.sup.2-- and where one or more H atoms in the
above-mentioned groups may be replaced by D, F, Cl, Br, I or CN, or
an aromatic or heteroaromatic ring system having 5 to 20 aromatic
ring atoms, which may in each case be substituted by one or more
radicals R.sup.2, or an aryloxy or heteroaryloxy group having 5 to
20 aromatic ring atoms, which may be substituted by one or more
radicals R.sup.2, or a combination of these systems, where two or
more radicals R.sup.1 may be linked to one another and may form an
aliphatic or aromatic ring.
[0059] L is preferably a divalent, or for k=3, 4, 5 or 6 a tri-,
tetra-, penta- or hexavalent group respectively, selected from
C.dbd.O, NR.sup.1, P(.dbd.O)(R.sup.1), 0, S, alkylene groups having
1 to 10 C atoms, alkenylene groups having 2 to 10 C atoms, where,
in the groups mentioned, one or more CH.sub.2 groups may be
replaced by C.dbd.O, NR.sup.1, P(.dbd.O)(R.sup.1), 0 or S, aryl or
heteroaryl groups having 5 to 20 aromatic ring atoms and aromatic
or heteroaromatic ring systems of the formulae (L-1) or (L-2),
##STR00006##
where: [0060] Ar.sup.3, Ar.sup.4 and Ar.sup.5 is, identically or
differently, an aryl or heteroaryl group having 5 to 20 aromatic
ring atoms, which may in each case be substituted by one or more
radicals R.sup.1; [0061] E is C.dbd.O, P(.dbd.O)(R.sup.1), SO or
SO.sub.2; [0062] i is on each occurrence, identically or
differently, 0 or 1; [0063] m, n are, identically or differently,
1, 2 or 3, preferably 1 or 2; [0064] o, p are, identically or
differently, 0, 1, 2 or 3, preferably 0, 1 or 2, where both indices
o and p cannot simultaneously be zero; and the symbols * mark the
bonds from the group L to the remainder of the compound.
[0065] In a preferred embodiment of the invention, k is equal to 2,
3 or 4. k is very particularly preferably equal to 2 or 3.
[0066] Particularly preferred embodiments of compounds of the
formula (V) to (X) are represented by the formulae (V-1) to (V-6),
(VI-1) to (VI-2), (VII-1) to (VII-6), (VIII-1) to (VIII-2), (IX-1)
to (IX-3) and (X-1):
##STR00007## ##STR00008## ##STR00009## ##STR00010##
where the symbols occurring are as defined above and furthermore
[0067] Z is on each occurrence, identically or differently,
CR.sup.1 or N, where not more than two adjacent groups Z may
simultaneously be equal to N.
[0068] The above-mentioned preferred embodiments of the groups Z,
Y, L, R.sup.1, R.sup.2 and of the index k also apply to the
compounds of the formulae (V-1) to (V-6), (VI-1) to (VI-2), (VII-1)
to (VII-6), (VIII-1) to (VIII-2), (IX-1) to (IX-3) and (X-1).
[0069] Two or more radicals R.sup.1 as constituents of groups
Z.dbd.CR.sup.1 in aromatic or heteroaromatic rings in the
above-mentioned formulae may be connected to one another and form a
ring which is condensed onto the aromatic or heteroaromatic
ring.
[0070] It is furthermore preferred for the compounds for use in the
electroluminescent devices according to the invention to carry as
substituent R, R.sup.1 or R.sup.2 at least one group which is
selected from electron-deficient heteroaryl groups, aromatic or
heteroaromatic ring systems and from arylamine groups, where the
above-mentioned electron-deficient heteroaryl groups are preferably
selected from pyridine, pyrimidine, pyridazine, pyrazine, triazine
and benzimidazole, each of which may be substituted by one or more
of the radicals defined above, and where the above-mentioned
aromatic or heteroaromatic ring systems are preferably selected
from naphthyl, anthracenyl, phenanthrenyl, benzanthracenyl,
pyrenyl, biphenyl, terphenyl and quaterphenyl, each of which may be
substituted by one or more of the radicals defined above, and where
the above-mentioned arylamine compounds preferably represent
compounds of the following formula (A)
##STR00011##
where the symbol * marks the bond to the remainder of the compound
and furthermore Ar.sup.3, Ar.sup.4, Ar.sup.5 are as defined above,
Ar.sup.4 and Ar.sup.5 may be linked to one another by a single bond
or by a divalent group Y, and q can be equal to 0, 1, 2, 3, 4 or
5.
[0071] Examples of compounds for use in the electronic devices
according to the invention are shown in the following table:
TABLE-US-00001 ##STR00012## 1 ##STR00013## 2 ##STR00014## 3
##STR00015## 4 ##STR00016## 5 ##STR00017## 6 ##STR00018## 7
##STR00019## 8 ##STR00020## 9 ##STR00021## 10 ##STR00022## 11
##STR00023## 12 ##STR00024## 13 ##STR00025## 14 ##STR00026## 15
##STR00027## 16 ##STR00028## 17 ##STR00029## 18 ##STR00030## 19
##STR00031## 20 ##STR00032## 21 ##STR00033## 22 ##STR00034## 23
##STR00035## 24 ##STR00036## 25 ##STR00037## 26 ##STR00038## 27
##STR00039## 28 ##STR00040## 29 ##STR00041## 30 ##STR00042## 31
##STR00043## 32 ##STR00044## 33 ##STR00045## 34 ##STR00046## 35
##STR00047## 36 ##STR00048## 37 ##STR00049## 38 ##STR00050## 39
##STR00051## 40 ##STR00052## 41 ##STR00053## 42 ##STR00054## 43
##STR00055## 44 ##STR00056## 45 ##STR00057## 46 ##STR00058## 47
##STR00059## 48 ##STR00060## 49 ##STR00061## 50 ##STR00062## 51
##STR00063## 52 ##STR00064## 53 ##STR00065## 54 ##STR00066## 55
##STR00067## 56 ##STR00068## 57 ##STR00069## 58 ##STR00070## 59
##STR00071## 60 ##STR00072## 61 ##STR00073## 62 ##STR00074## 63
##STR00075## 64 ##STR00076## 65 ##STR00077## 66 ##STR00078## 67
##STR00079## 68 ##STR00080## 69 ##STR00081## 70 ##STR00082## 71
##STR00083## 72 ##STR00084## 73 ##STR00085## 74 ##STR00086## 75
##STR00087## 76 ##STR00088## 77 ##STR00089## 78 ##STR00090## 79
##STR00091## 80 ##STR00092## 81 ##STR00093## 82 ##STR00094## 83
##STR00095## 84 ##STR00096## 85 ##STR00097## 86 ##STR00098## 87
##STR00099## 88 ##STR00100## 89 ##STR00101## 90 ##STR00102## 91
##STR00103## 92 ##STR00104## 93 ##STR00105## 94 ##STR00106## 95
##STR00107## 96 ##STR00108## 97 ##STR00109## 98 ##STR00110## 99
##STR00111## 100 ##STR00112## 101 ##STR00113## 102 ##STR00114## 103
##STR00115## 104 ##STR00116## 105 ##STR00117## 106 ##STR00118## 107
##STR00119## 108 ##STR00120## 109 ##STR00121## 110 ##STR00122## 111
##STR00123## 112 ##STR00124## 113 ##STR00125## 114
[0072] The present invention furthermore relates to compounds of
the formula (Ic), (IIc), (IIIc) or (IVc), in which R is defined as
follows:
[0073] R is an aromatic or heteroaromatic ring system having 5 to
20 aromatic ring atoms, which may in each case be substituted by
one or more radicals R.sup.1, or an aralkyl or heteroaralkyl group
having 5 to 20 aromatic ring atoms, which may be substituted by one
or more radicals R.sup.1, where the radical R may furthermore be
linked to an adjacent group Ar.sup.1 or Ar.sup.2 via a single bond
or via a divalent group Y.
[0074] The above-mentioned preferred embodiments of the compounds
of the formula (Ic) to (IVc) are likewise preferred in this
connection.
[0075] Particular preference is given to the embodiments of the
formulae (V) to (X) and (V-1) to (V-6), (VI-1) to (VI-2), (VII-1)
to (VII-6), (VIII-1) to (VIII-2), (IX-1) to (IX-3) and (X-1).
[0076] In an even more preferred embodiment of the compounds
according to the invention, R is an aryl or heteroaryl group having
5 to 20 aromatic ring atoms, which may in each case be substituted
by one or more radicals R.sup.1.
[0077] The compounds according to the invention can be prepared by
synthetic steps known to the person skilled in the art, such as,
for example, bromination, Suzuki coupling, Hartwig-Buchwald
coupling, etc.
[0078] Examples of synthetic routes which lead to the compounds
according to the invention will be shown below.
[0079] 5- or 6-substituted benzimidazo[2,1-b]quinazolin-12(6H)-ones
can be obtained from the parent structure
benzimidazo[2,1-b]quinazolin-12(6H)-one (CAS [4149-00-2], cf.
patent application SU 1182043) by deprotonation using bases in
aprotic or protic media with generation of the corresponding anion
and reaction thereof with electrophiles ("E.sup.+") (Scheme 1).
##STR00126##
[0080] In aprotic solvents, such as, for example, DMF, NMP, DMSO
and ether, the 6-isomers are typically obtained regioselectively,
whereas the 5-isomers are obtained in protic solvents.
Electrophiles which can be used are a wide range of classes of
compound, such as, for example, alkyl and aralkyl halides,
sulfonates and sulfates, carboxylates, carboxylic anhydrides and
carbonyl halides, silicon-halogen compounds, phosphorus-halogen
compounds and halogenated electron-deficient heterocycles, such as
diazines or triazines (Scheme 2).
##STR00127##
[0081] Under the conditions of a palladium- or copper-catalysed
C--N coupling, benzimidazo[2,1-b]quinazolin-12(6H)-ones furthermore
react to give the 5-aryl-substituted derivatives (Scheme 3). This
represents a further possible synthetic route for the preparation
of this type of compounds according to the invention.
##STR00128##
[0082] Halogenated benzimidazo[2,1-b]quinazolin-12(6H)-ones (cf. R.
D. Carpenter, et al., J. Org. Chem. 2007, 72, 1, 284) can firstly
be N-functionalised by the processes shown above and subsequently
functionalised further by means of conventional methods of C--C
coupling or C--N coupling (Scheme 4). This process is not
restricted to the position of the C--C coupling or C--N coupling
shown in Scheme 4. The use of isomeric mono-, di- or oligobromides
of benzimidazo[2,1-b]quinazolin-12(6H)-ones enables the preparation
of a multiplicity of derivatives of the compounds shown in Scheme 4
which have a different substitution pattern.
##STR00129##
[0083] The reduction of the carbonyl function to the parent
structure of the 6,12-dihydrobenzimidazo[2,1-b]quinazolines can be
carried out, for example, using lithium aluminium hydride under
conditions which are familiar to the person skilled in the art (W.
H. W. Lunn, J. Org. Chem. 1972, 37, 4, 607, Scheme 5, first line).
A reaction with suitable Grignard reagents and subsequent
acid-catalysed dehydrating cyclisation results in compounds
according to the invention which have a Spiro C atom (Scheme 5,
second line).
##STR00130##
[0084] The examples shown above are based on the skeleton of
benzimidazo[2,1-b]quinazolin-12(6H)-one (cf. Scheme 1). However,
the synthetic methods shown are not restricted to this skeleton.
The imidazo[1,2-a]pyrimidin-5(1H)-ones and the
pyrimido[1,2-a]benzimidazol-4(10H)-ones and derivatives thereof can
also be reacted analogously, enabling the preparation of compounds
according to the invention based on these skeletons.
[0085] The invention thus furthermore relates to a process for the
preparation of the compounds of the formula (Ic) to (IVc) according
to the invention, characterised in that at least one of the two
steps a) and b) indicated below is carried out:
[0086] a) deprotonation at the 5- or 6-N atom of the
benzimidazoquinazoline skeleton and subsequent reaction with an
electrophilic compound, so that a bond is formed between the 5- or
6-N atom and the electrophilic compound; [0087] b) organometallic
coupling under Hartwig-Buchwald or Ullmann conditions between the
5- or 6-N atom of the benzimidazoquinazoline skeleton and an aryl
group Ar, which is employed as starting material Ar-Hal, where Hal
is any desired suitable leaving group, such as, for example,
halide.
[0088] The compounds of the formula (Ic) to (IVc) described above,
in particular compounds which are substituted by reactive leaving
groups, such as bromine, iodine, chlorine, boronic acid or boronic
acid ester, can be used as monomers for the preparation of
corresponding oligomers, dendrimers or polymers. The
oligomerisation or polymerisation here is preferably carried out
via the halogen functionality or the boronic acid
functionality.
[0089] The invention therefore furthermore relates to oligomers,
polymers or dendrimers comprising one or more compounds of the
formula (Ic) to (IVc), where the bond(s) to the polymer, oligomer
or dendrimer may be localised at any desired positions substituted
by R or R.sup.1 in formula (Ic) to (IVc). Depending on the linking
of the compound of the formula (Ic) to (IVc), the compound is part
of a side chain of the oligomer or polymer or part of the main
chain. An oligomer in the sense of this invention is taken to mean
a compound which is built up from at least three monomer units. A
polymer in the sense of the invention is taken to mean a compound
which is built up from at least ten monomer units. The polymers,
oligomers or dendrimers according to the invention may be
conjugated, partially conjugated or non-conjugated. The oligomers
or polymers according to the invention may be linear, branched or
dendritic. In the structures linked in a linear manner, the units
of the formula (Ic) to (IVc) may be linked directly to one another
or they may be linked to one another via a divalent group, for
example via a substituted or unsubstituted alkylene group, via a
heteroatom or via a divalent aromatic or heteroaromatic group. In
branched and dendritic structures, three or more units of the
formula (Ic) to (IVc) may, for example, be linked via a trivalent
or polyvalent group, for example via a trivalent or polyvalent
aromatic or heteroaromatic group, to give a branched or dendritic
oligomer or polymer.
[0090] The same preferences as described above for compounds of the
formula (Ic) to (IVc) apply to the recurring units of the formula
(Ic) to (IVc) in oligomers, dendrimers and polymers.
[0091] For the preparation of the oligomers or polymers, the
monomers according to the invention are homopolymerised or
copolymerised with further monomers. Suitable and preferred
comonomers are selected from fluorenes (for example in accordance
with EP 842208 or WO 2000/22026), spirobifluorenes (for example in
accordance with EP 707020, EP 894107 or WO 2006/061181),
para-phenylenes (for example in accordance with WO 1992/18552),
carbazoles (for example in accordance with WO 2004/070772 or WO
2004/113468), thiophenes (for example in accordance with EP
1028136), dihydrophenanthrenes (for example in accordance with WO
2005/014689 or WO 2007/006383), cis- and trans-indenofluorenes (for
example in accordance with WO 2004/041901 or WO 2004/113412),
ketones (for example in accordance with WO 2005/040302),
phenanthrenes (for example in accordance with WO 2005/104264 or WO
2007/017066) or also a plurality of these units. The polymers,
oligomers and dendrimers usually also contain further units, for
example emitting (fluorescent or phosphorescent) units, such as,
for example, vinyltriarylamines (for example in accordance with WO
2007/068325) or phosphorescent metal complexes (for example in
accordance with WO 2006/003000), and/or charge-transport units, in
particular those based on triarylamines.
[0092] The polymers, oligomers and dendrimers according to the
invention have advantageous properties, in particular long
lifetimes, high efficiencies and good colour coordinates.
[0093] The polymers and oligomers according to the invention are
generally prepared by polymerisation of one or more types of
monomer, at least one monomer of which results in recurring units
of the formula (Ic) to (IVc) in the polymer. Suitable
polymerisation reactions are known to the person skilled in the art
and are described in the literature. Particularly suitable and
preferred polymerisation reactions which result in C--C or C--N
links are the following:
(A) SUZUKI polymerisation; (B) YAMAMOTO polymerisation; (C) STILLE
polymerisation; and (D) HARTWIG-BUCHWALD polymerisation.
[0094] The way in which the polymerisation can be carried out by
these methods and the way in which the polymers can then be
separated off from the reaction medium and purified is known to the
person skilled in the art and is described in detail in the
literature, for example in WO 2003/048225, WO 2004/037887 and WO
2004/037887.
[0095] The present invention thus also relates to a process for the
preparation of the polymers, oligomers and dendrimers according to
the invention, which is characterised in that they are prepared by
SUZUKI polymerisation, YAMAMOTO polymerisation, STILLE
polymerisation or HARTWIG-BUCHWALD polymerisation. The dendrimers
according to the invention can be prepared by processes known to
the person skilled in the art or analogously thereto. Suitable
processes are described in the literature, such as, for example, in
Frechet, Jean M. J.; Hawker, Craig J., "Hyperbranched polyphenylene
and hyperbranched polyesters: new soluble, three-dimensional,
reactive polymers", Reactive & Functional Polymers (1995),
26(1-3), 127-36; Janssen, H. M.; Meijer, E. W., "The synthesis and
characterization of dendritic molecules", Materials Science and
Technology (1999), 20 (Synthesis of Polymers), 403-458; Tomalia,
Donald A., "Dendrimer molecules", Scientific American (1995),
272(5), 62-6; WO 2002/067343 A1 and WO 2005/026144 A1.
[0096] The invention also relates to formulations comprising at
least one compound of the formula (Ic) to (IVc) or at least one
polymer, oligomer or dendrimer containing at least one unit of the
formula (Ic) to (IVc) and at least one solvent, preferably an
organic solvent.
[0097] The formulations according to the invention are used, for
example, in the production of organic electroluminescent devices,
which is described in greater detail in a following section.
[0098] The compounds of the formula (I) to (IV) are suitable for
use in electronic devices, in particular in organic
electroluminescent devices (OLEDs). Depending on the substitution,
the compounds are employed in various functions and in various
layers of the organic electroluminescent device. Furthermore, the
choice of the group X or X.sup.1 plays a role in the case of the
compounds.
[0099] For example, compounds according to the invention which are
substituted at least by an arylamino group are particularly
suitable for use as hole-transport or hole-injection materials.
Furthermore, in the case of compounds for the preferred use as
hole-transport or hole-injection materials, it is preferred for X
or X.sup.1 to represent a group of the formula C(R.sup.1).sub.2 or
NR.sup.1.
[0100] Furthermore, compounds according to the invention which are
substituted by at least one electron-deficient heteroaryl group are
particularly suitable for use as matrix materials for
phosphorescent dopants and/or for use as electron-transport
materials. In the case of compounds for the preferred use as matrix
materials for phosphorescent dopants and/or as electron-transport
materials, it is furthermore preferred for X to represent a single
bond or a group of the formula C.dbd.O, C.dbd.S, C.dbd.NR.sup.1, O,
S, SO or SO.sub.2 or for X.sup.1 to represent a group of the
formula C.dbd.O, C.dbd.S, C.dbd.NR.sup.1, O, S, SO or SO.sub.2.
[0101] Furthermore, compounds according to the invention which are
substituted by one or more aromatic or heteroaromatic ring systems
are particularly suitable for use as fluorescent dopants.
[0102] The invention therefore furthermore relates to the use of
the compounds of the formula (I) to (IV) in electronic devices. The
electronic devices here are preferably selected from the group
consisting of 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 optical detectors, organic
photoreceptors, organic field-quench devices (O-FQDs),
light-emitting electrochemical cells (LECs), organic laser diodes
(O-lasers) and particularly preferably organic electroluminescent
devices (OLEDs).
[0103] The invention furthermore relates, as already mentioned
above, to an organic electroluminescent device comprising anode,
cathode and at least one organic layer, characterised in that the
organic layer comprises a compound of the formula (I) to (IV).
[0104] The organic electroluminescent device comprises at least one
electroluminescent layer. The electroluminescent layer may comprise
a compound of the formula (I) to (IV), but the compound of the
formula (I) to (IV) may also be present additionally or exclusively
in another layer of the device, for example a hole- or
electron-transport layer.
[0105] These other layers which may optionally be present in the
organic electroluminescent device according to the invention are
selected, for example, from in each case one or more hole-injection
layers, hole-transport layers, hole-blocking layers,
electron-transport layers, electron-injection layers,
electron-blocking layers, exciton-blocking layers, interlayers,
charge-generation layers (IDMC 2003, Taiwan; Session 21 OLED (5),
T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi,
J. Kido, Multiphoton Organic EL Device Having Charge Generation
Layer) and/or organic or inorganic p/n junctions. However, it
should be pointed out that each of these layers does not
necessarily have to be present and the choice of layers is always
dependent on the compounds used and in particular also on whether
the electroluminescent device is fluorescent or phosphorescent.
[0106] The organic electroluminescent device may also comprise a
plurality of emitting layers. These emission layers in this case
particularly preferably have in total a plurality of emission
maxima between 380 nm and 750 nm, resulting overall in white
emission, i.e. various emitting compounds which are able to
fluoresce or phosphoresce and which emit blue and yellow, orange or
red light are used in the emitting layers. Particular preference is
given to systems having three emitting layers, where at least one
of these layers comprises at least one compound of the formula (I)
to (IV) and where the three layers exhibit blue, green and orange
or red emission (for the basic structure see, for example, WO
2005/011013). Alternatively and/or additionally, the compounds of
the formula (I) to (IV) may also be present in the hole-transport
layer or another layer. Emitters which have broad-band emission
bands and thus exhibit white emission are likewise suitable for
white emission.
[0107] It is preferred in accordance with the invention for the
compound of the formula (I) to (IV) to be employed in an electronic
device comprising one or more phosphorescent dopants. The compound
here can be used in various layers, preferably in a hole-transport
layer, a hole-injection layer or in the emitting layer.
[0108] However, the compound of the formula (I) to (IV) can also be
employed in accordance with the invention in an electronic device
comprising one or more fluorescent dopants.
[0109] Suitable phosphorescent dopants (=triplet emitters) are, in
particular, compounds which emit light, preferably in the visible
region, on suitable excitation and in addition contain at least one
atom having an atomic number greater than 20, preferably greater
than 38 and less than 84, particularly preferably greater than 56
and less than 80. The phosphorescent emitters used are preferably
compounds which contain copper, molybdenum, tungsten, rhenium,
ruthenium, osmium, rhodium, iridium, palladium, platinum, silver,
gold or europium, in particular compounds which contain iridium,
platinum or copper.
[0110] For the purposes of the present invention, all luminescent
iridium, platinum or copper complexes are regarded as
phosphorescent compounds.
[0111] Examples of the emitters described above are revealed by the
applications WO 2000/70655, WO 2001/41512, WO 2002/02714, WO
2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 2005/033244, WO
2005/019373 and US 2005/0258742. In general, all phosphorescent
complexes as used in accordance with the prior art for
phosphorescent OLEDs and as are known to the person skilled in the
art in the area of organic electroluminescent devices are suitable.
The person skilled in the art will also be able to employ further
phosphorescent complexes without inventive step in combination with
the compounds of the formula (I) to (IV) according to the invention
in organic electroluminescent devices.
[0112] Examples of suitable phosphorescent emitter compounds are
furthermore revealed by the following table:
TABLE-US-00002 ##STR00131## ##STR00132## ##STR00133## ##STR00134##
##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139##
##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144##
##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149##
##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154##
##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159##
##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164##
##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169##
##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174##
##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179##
##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184##
##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189##
##STR00190## ##STR00191## ##STR00192## ##STR00193## ##STR00194##
##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199##
##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204##
##STR00205## ##STR00206## ##STR00207## ##STR00208## ##STR00209##
##STR00210## ##STR00211## ##STR00212## ##STR00213## ##STR00214##
##STR00215## ##STR00216## ##STR00217## ##STR00218## ##STR00219##
##STR00220## ##STR00221## ##STR00222## ##STR00223## ##STR00224##
##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229##
##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234##
##STR00235## ##STR00236## ##STR00237## ##STR00238## ##STR00239##
##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244##
##STR00245## ##STR00246## ##STR00247## ##STR00248## ##STR00249##
##STR00250## ##STR00251## ##STR00252## ##STR00253## ##STR00254##
##STR00255##
##STR00256## ##STR00257## ##STR00258## ##STR00259## ##STR00260##
##STR00261## ##STR00262## ##STR00263## ##STR00264## ##STR00265##
##STR00266## ##STR00267## ##STR00268## ##STR00269## ##STR00270##
##STR00271##
[0113] In a preferred embodiment of the present invention, the
compounds of the formula (I) to (IV) are employed as matrix
material in combination with one or more dopants, preferably
phosphorescent dopants.
[0114] A dopant is taken to mean the component whose proportion in
the mixture is the smaller in a system comprising a matrix material
and a dopant. Correspondingly, a matrix material is taken to mean
the component whose proportion in the mixture is the greater in a
system comprising a matrix material and a dopant.
[0115] The proportion of the matrix material in the emitting layer
is in this case between 50.0 and 99.9% by vol., preferably between
80.0 and 99.5% by vol. and particularly preferably between 92.0 and
99.5% by vol. for fluorescent emitting layers and between 85.0 and
97.0% by vol. for phosphorescent emitting layers.
[0116] Correspondingly, the proportion of the dopant is between 0.1
and 50.0% by vol., preferably between 0.5 and 20.0% by vol. and
particularly preferably between 0.5 and 8.0% by vol. for
fluorescent emitting layers and between 3.0 and 15.0% by vol. for
phosphorescent emitting layers.
[0117] An emitting layer of an organic electroluminescent device
may also comprise systems comprising a plurality of matrix
materials (mixed-matrix systems) and/or a plurality of dopants. In
this case too, the dopants are generally the materials whose
proportion in the system is the smaller and the matrix materials
are the materials whose proportion in the system is the greater. In
individual cases, however, the proportion of an individual matrix
material in the system may be smaller than the proportion of an
individual dopant.
[0118] In a preferred embodiment of the invention, the compounds of
the formula (I) to (IV) are used as a component of mixed-matrix
systems. The mixed-matrix systems preferably comprise two or three
different matrix materials, particularly preferably two different
matrix materials. Preferably, one of the two materials here
represents a material having hole-transporting properties and the
other material represents a material having electron-transporting
properties. The two different matrix materials here may be present
in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly
preferably 1:10 to 1:1 and very particularly preferably 1:4 to
1:1.
[0119] The mixed-matrix systems may comprise one or more dopants.
The dopant compound or the dopant compounds together have, in
accordance with the invention, a proportion of 0.1 to 50.0% by vol.
in the mixture as a whole and preferably a proportion of 0.5 to
20.0% by vol. in the mixture as a whole. Correspondingly, the
matrix components together have a proportion of 50.0 to 99.9% by
vol. in the mixture as a whole and preferably a proportion of 80.0
to 99.5% by vol. in the mixture as a whole.
[0120] Mixed-matrix systems are preferably employed in
phosphorescent organic electroluminescent devices.
[0121] Particularly suitable matrix materials, which can be
employed in combination with the compounds according to the
invention as matrix components of a mixed-matrix system, are
aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides
or sulfones, for example in accordance with WO 2004/013080, WO
2004/093207, WO 2006/005627 or WO 2010/006680, triarylamines,
carbazole derivatives, for example CBP (N,N-biscarbazolylbiphenyl)
or the carbazole derivatives disclosed in WO 2005/039246, US
2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851,
indolocarbazole derivatives, for example in accordance with WO
2007/063754 or WO 2008/056746, azacarbazole derivatives, for
example in accordance with EP 1617710, EP 1617711, EP 1731584, JP
2005/347160, bipolar matrix materials, for example in accordance
with WO 2007/137725, silanes, for example in accordance with WO
2005/111172, azaboroles or boronic esters, for example in
accordance with WO 2006/117052, triazine derivatives, for example
in accordance with WO 2010/015306, WO 2007/063754 or WO
2008/056746, zinc complexes, for example in accordance with EP
652273 or WO 2009/062578, diazasilole or tetraazasilole
derivatives, for example in accordance with WO 2010/054729,
diazaphosphole derivatives, for example in accordance with WO
2010/054730, or indenocarbazole derivatives, for example in
accordance with WO 2010/136109.
[0122] Preferred phosphorescent dopants for use in mixed-matrix
systems comprising the compounds according to the invention are the
phosphorescent dopants mentioned in the above table.
[0123] In a further preferred embodiment of the invention, the
compounds of the formula (I) to (IV) are employed as hole-transport
material. The compounds are then preferably employed in a
hole-transport layer and/or in a hole-injection layer. A
hole-injection layer in the sense of this invention is a layer
which is directly adjacent to the anode. A hole-transport layer in
the sense of this invention is a layer which is located between the
hole-injection layer and the emission layer. The hole-transport
layer may be directly adjacent to the emission layer.
[0124] If the compounds of the formula (I) to (IV) are used as
hole-transport material or as hole-injection material, it may be
preferred for them to be doped with electron-acceptor compounds,
for example with F.sub.4-TCNQ or with compounds as described in EP
1476881 or EP 1596445. In a further preferred embodiment of the
invention, a compound of the formula (I) to (IV) is used as
hole-transport material in combination with a hexaazatriphenylene
derivative as described in US 2007/0092755. The hexaazatriphenylene
derivative is particularly preferably employed in its own layer
here.
[0125] If the compound of the formula (I) to (IV) is employed as
hole-transport material in a hole-transport layer, the compound can
be employed as pure material, i.e. in a proportion of 100%, in the
hole-transport layer or it can be employed in combination with one
or more further compounds in the hole-transport layer.
[0126] In a further embodiment of the invention, the compounds of
the formula (I) to (IV) are employed as fluorescent dopants in an
electroluminescent layer. In this case, the compounds are
preferably used as green or blue emitters.
[0127] Preferred matrix materials for use in combination with the
compounds of the formula (I) to (IV) as fluorescent dopants are
mentioned in one of the following sections.
[0128] The materials preferably employed for the respective
functions in the electronic devices according to the invention are
mentioned below.
[0129] Preferred fluorescent emitter materials are selected from
the class of the monostyrylamines, the distyrylamines, the
tristyrylamines, the tetrastyrylamines, the styrylphosphines, the
styryl ethers and the arylamines. A monostyrylamine is taken to
mean a compound which contains one substituted or unsubstituted
styryl group and at least one, preferably aromatic, amine. A
distyrylamine is taken to mean a compound which contains two
substituted or unsubstituted styryl groups and at least one,
preferably aromatic, amine. A tristyrylamine is taken to mean a
compound which contains three substituted or unsubstituted styryl
groups and at least one, preferably aromatic, amine. A
tetrastyrylamine is taken to mean a compound which contains four
substituted or unsubstituted styryl groups and at least one,
preferably aromatic, amine. The styryl groups are particularly
preferably stilbenes, which may also be further substituted.
Corresponding styrylphosphines and styryl ethers are defined
analogously to the amines. An arylamine or aromatic amine in the
sense of this invention is taken to mean a compound which contains
three substituted or unsubstituted aromatic or heteroaromatic ring
systems bonded directly to the nitrogen. At least one of these
aromatic or heteroaromatic ring systems is preferably a condensed
ring system, particularly preferably having at least 14 aromatic
ring atoms. Preferred examples thereof are aromatic
anthracenamines, aromatic anthracenediamines, aromatic pyrenamines,
aromatic pyrenediamines, aromatic chrysenamines or aromatic
chrysenediamines. An aromatic anthracenamine is taken to mean a
compound in which one diarylamino group is bonded directly to an
anthracene group, preferably in the 9-position. An aromatic
anthracenediamine is taken to mean a compound in which two
diarylamino groups are bonded directly to an anthracene group,
preferably in the 9,10-position. Aromatic pyrenamines,
pyrenediamines, chrysenamines and chrysenediamines are defined
analogously thereto, where the diarylamino groups are preferably
bonded to the pyrene in the 1-position or in the 1,6-position.
Further preferred emitter materials are selected from
indenofluorenamines or indenofluorenediamines, for example in
accordance with WO 2006/122630, benzoindenofluorenamines or
benzoindenofluorenediamines, for example in accordance with WO
2008/006449, and dibenzoindenofluorenamines or
dibenzoindenofluorenediamines, for example in accordance with WO
2007/140847. Examples of emitter materials from the class of the
styrylamines are substituted or unsubstituted tristilbenamines or
the emitter materials described in WO 2006/000388, WO 2006/058737,
WO 2006/000389, WO 2007/065549 and WO 2007/115610. Preference is
furthermore given to the condensed hydrocarbons disclosed in WO
2010/012328.
[0130] Furthermore, the compounds of the formula (I) to (IV) are
preferably used as fluorescent emitter materials.
[0131] Suitable emitter materials are furthermore the structures
depicted in the following table, and the derivatives of these
structures disclosed in JP 2006/001973, WO 2004/047499, WO
2006/098080, WO 2007/065678, US 2005/0260442 and WO
2004/092111.
TABLE-US-00003 ##STR00272## ##STR00273## ##STR00274## ##STR00275##
##STR00276## ##STR00277## ##STR00278## ##STR00279## ##STR00280##
##STR00281## ##STR00282## ##STR00283## ##STR00284## ##STR00285##
##STR00286## ##STR00287## ##STR00288## ##STR00289## ##STR00290##
##STR00291## ##STR00292## ##STR00293## ##STR00294## ##STR00295##
##STR00296## ##STR00297## ##STR00298## ##STR00299## ##STR00300##
##STR00301## ##STR00302## ##STR00303## ##STR00304## ##STR00305##
##STR00306## ##STR00307## ##STR00308## ##STR00309## ##STR00310##
##STR00311## ##STR00312## ##STR00313## ##STR00314## ##STR00315##
##STR00316## ##STR00317## ##STR00318## ##STR00319##
[0132] Suitable matrix materials, preferably for fluorescent
dopants, are materials from various classes of substance. Preferred
matrix materials are selected from the classes of the oligoarylenes
(for example 2,2',7,7'-tetraphenylspirobifluorene in accordance
with EP 676461 or dinaphthylanthracene), in particular the
oligoarylenes containing condensed aromatic groups, the
oligoarylenevinylenes (for example DPVBi or spiro-DPVBi in
accordance with EP 676461), the polypodal metal complexes (for
example in accordance with WO 2004/081017), the hole-conducting
compounds (for example in accordance with WO 2004/058911), the
electron-conducting compounds, in particular ketones, phosphine
oxides, sulfoxides, etc. (for example in accordance with WO
2005/084081 and WO 2005/084082), the atropisomers (for example in
accordance with WO 2006/048268), the boronic acid derivatives (for
example in accordance with WO 2006/117052) or the benzanthracenes
(for example in accordance with WO 2008/145239). Suitable matrix
materials are furthermore preferably the compounds according to the
invention. Apart from the compounds according to the invention,
particularly preferred matrix materials are selected from the
classes of the oligoarylenes, comprising naphthalene, anthracene,
benzanthracene and/or pyrene or atropisomers of these compounds,
the oligoarylenevinylenes, the ketones, the phosphine oxides and
the sulfoxides. Very particularly preferred matrix materials, apart
from the compounds according to the invention, are selected from
the classes of the oligoarylenes, comprising anthracene,
benzanthracene, benzophenanthrene and/or pyrene or atropisomers of
these compounds. An oligoarylene in the sense of this invention is
intended to be taken to mean a compound in which at least three
aryl or arylene groups are bonded to one another.
[0133] Suitable matrix materials, preferably for fluorescent
dopants, are, for example, the materials depicted in the following
table, and derivatives of these materials, as disclosed in WO
2004/018587, WO 2008/006449, U.S. Pat. No. 5,935,721, US
2005/0181232, JP 2000/273056, EP 681019, US 2004/0247937 and US
2005/0211958.
TABLE-US-00004 ##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## ##STR00358##
##STR00359##
[0134] Besides the compounds of the formula (I) to (IV), suitable
charge-transport materials, as can be used in the hole-injection or
hole-transport layer or in the electron-transport layer of the
organic electroluminescent device according to the invention, are,
for example, the compounds disclosed in Y. Shirota et al., Chem.
Rev. 2007, 107(4), 953-1010, or other materials as are employed in
these layers in accordance with the prior art.
[0135] The cathode of the organic electroluminescent device
preferably comprises metals having a low work function, metal
alloys or multilayered structures comprising various metals, such
as, for example, alkaline-earth metals, alkali metals, main-group
metals or lanthanoids (for example Ca, Ba, Mg, Al, In, Mg, Yb, Sm,
etc.). Also suitable are alloys comprising an alkali metal or
alkaline-earth metal and silver, for example an alloy comprising
magnesium and silver. In the case of multilayered structures,
further metals which have a relatively high work function, such as,
for example, Ag or Al, can also be used in addition to the said
metals, in which case combinations of the metals, such as, for
example, Ca/Ag, Ba/Ag or Mg/Ag, are generally used. It may also be
preferred to introduce a thin interlayer of a material having a
high dielectric constant between a metallic cathode and the organic
semiconductor. Suitable for this purpose are, for example, alkali
metal fluorides or alkaline-earth metal fluorides, but also the
corresponding oxides or carbonates (for example LiF, Li.sub.2O,
BaF.sub.2, MgO, NaF, CsF, Cs.sub.2CO.sub.3, etc.). Furthermore,
lithium quinolinate (LiQ) can be used for this purpose. The layer
thickness of this layer is preferably between 0.5 and 5 nm.
[0136] The anode preferably comprises materials having a high work
function. The anode preferably has a work function of greater than
4.5 eV vs. vacuum. Suitable for this purpose are on the one hand
metals having a high redox potential, such as, for example, Ag, Pt
or Au. On the other hand, metal/metal oxide electrodes (for example
Al/Ni/NiO.sub.x, Al/PtO.sub.x) may also be preferred. For some
applications, at least one of the electrodes must be transparent or
partially transparent in order to facilitate either irradiation of
the organic material (organic solar cells) or the coupling-out of
light (OLEDs, O-lasers). Preferred anode materials here are
conductive mixed metal oxides. Particular preference is given to
indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is
furthermore given to conductive, doped organic materials, in
particular conductive doped polymers.
[0137] The device is appropriately (depending on the application)
structured, provided with contacts and finally sealed, since the
lifetime of the devices according to the invention is shortened in
the presence of water and/or air.
[0138] In a preferred embodiment, the organic electroluminescent
device according to the invention is characterised in that one or
more layers are applied by means of a sublimation process, in which
the materials are applied by vapour deposition in vacuum
sublimation units at an initial pressure of less than 10.sup.-5
mbar, preferably less than 10.sup.-6 mbar. However, it is also
possible here for the initial pressure to be even lower, for
example less than 10.sup.-7 mbar.
[0139] Preference is likewise given to an organic
electroluminescent device, characterised in that one or more layers
are applied by means of the OVPD (organic vapour phase deposition)
process or with the aid of carrier-gas sublimation, in which the
materials are applied at a pressure of between 10.sup.-5 mbar and 1
bar. A special case of this process is the OVJP (organic vapour jet
printing) process, in which the materials are applied directly
through a nozzle and are thus structured (for example M. S. Arnold
et al., Appl. Phys. Lett. 2008, 92, 053301).
[0140] Preference is furthermore given to an organic
electroluminescent device, characterised in that one or more layers
are produced from solution, such as, for example, by spin coating,
or by means of any desired printing process, such as, for example,
screen printing, flexographic printing, nozzle printing or offset
printing, but particularly preferably LITI (light induced thermal
imaging, thermal transfer printing) or ink-jet printing. Soluble
compounds of the formula (I) to (IV) are necessary for this
purpose. High solubility can be achieved through suitable
substitution of the compounds.
[0141] For the production of an organic electroluminescent device
according to the invention, it is furthermore preferred to apply
one or more layers from solution and one or more layers by a
sublimation process.
[0142] The organic electroluminescent devices comprising one or
more compounds of the formula (I) to (IV) can be employed in
accordance with the invention in displays, as light sources in
lighting applications and as light sources in medical and/or
cosmetic applications (for example light therapy).
[0143] On use of the compounds of the formula (I) to (IV) in
organic electroluminescent devices, one or more of the advantages
indicated below can be achieved: [0144] on use of the compounds of
the formula (I) to (IV) as matrix materials for phosphorescent
emitters, high power efficiency and a low operating voltage of the
devices can be achieved [0145] on use of the compounds of the
formula (I) to (IV) as hole-transport materials, preferably in a
hole-transport layer, high power efficiency and a low operating
voltage of the devices can be achieved [0146] using the compounds
of the formula (I) to (IV), devices can be produced which have a
long lifetime.
[0147] The use of the compounds of the formula (I) to (IV) is not
restricted to the functions hole-transport material and matrix
material for phosphorescent emitters. For example, the use as
electron-transport material and/or as matrix material in
mixed-matrix systems is furthermore possible.
[0148] The invention is explained in greater detail by the
following working examples without thereby intending to imply a
restriction to the examples explicitly disclosed.
USE EXAMPLES
A) Synthesis Examples
[0149] The following syntheses are carried out, unless indicated
otherwise, under a protective-gas atmosphere in dried solvents. The
solvents and reagents can be purchased from ALDRICH or ABCR.
Benzimidazo[2,1-b]quinazolin-12(6H)-one [4149-00-2] was prepared in
accordance with SU 1182043,
6,12-dihydrobenzimidazo[2,1-b]quinazoline [32675-34-6] was prepared
in accordance with W. H. W. Lumm et al., J. Org. Chem. 1972, 37, 4,
607 and 5H-benzimidazo[1,2-a]benzimidazole [28890-99-5] was
prepared in accordance with A. Reddouane et al., Bull, Soc. Chim.
Belges 96, 10, 787, 1987.
Example 1
Matrix M1
##STR00360##
[0151] A mixture of 23.5 g (100 mmol) of
benzimidazo[2,1-b]quinazolin-12(6H)-one, 34.0 g (110 mmol) of
1-bromo-3,5-diphenylbenzene [103068-20-8], 20.7 g (150 mmol) of
potassium carbonate, 3.8 g (20 mmol) of copper iodide, 200 g of
glass beads (diameter 3 mm) and 300 ml of NMP is heated at
200.degree. C. for 20 h with vigorous stirring. After cooling, a
mixture of 200 ml of water and 200 ml of ethanol is added, the
mixture is stirred for a further 30 min., the suspension is
filtered through a slotted frit in order to separate off the glass
beads, the solid is then filtered off with suction, washed three
times with 100 ml of ethanol each time and dried in vacuo. The
solid is subjected to continuous hot extraction with o-xylene
through an aluminium oxide bed (aluminium oxide, basic, activity
grade 1), subsequently recrystallised five times from NMP and three
times from o-dichlorobenzene and then subjected to fractional
sublimation in vacuo (pressure about 10.sup.-5 mbar, temperature
about 320.degree. C.). Yield: 21.3 g (46 mmol), 46%; purity: 99.9%
according to HPLC.
[0152] The following compounds are prepared analogously:
TABLE-US-00005 Ex. Bromide Product Yield 2 ##STR00361##
##STR00362## 46% 3 ##STR00363## ##STR00364## 45% 4 ##STR00365##
##STR00366## 38% 5 ##STR00367## ##STR00368## 52% 6 ##STR00369##
##STR00370## 36% 7 ##STR00371## ##STR00372## 44% 8 ##STR00373##
##STR00374## 28%
Example 9
Matrix M9
##STR00375##
[0154] A suspension of 23.5 g (100 mmol) of
benzimidazo[2,1-b]quinazolin-12(6H)-one, 2.6 g (110 mmol) of sodium
hydride and 29.4 g (110 mmol) of 1-chloro-3,5-diphenyltriazine
[3842-55-5] in 300 ml of DMF is stirred at 120.degree. C. for 16 h.
After cooling, 100 ml of ethanol are added dropwise, and 100 ml of
water are then added, the solid is filtered off with suction,
washed three times with 100 ml of a mixture of ethanol/water (1:1,
vv) each time, three times with 100 ml of ethanol each time and
then dried in vacuo. After recrystallisation of the solid three
times from NMP, the product is recrystallised a further seven times
from o-dichlorobenzene and then subjected to fractional sublimation
in vacuo (pressure about 10.sup.-5 mbar, temperature about
340.degree. C.). Yield: 30.2 g (67 mmol), 67%; purity: 99.9%
according to HPLC.
[0155] The following compounds are prepared analogously:
TABLE-US-00006 Ex. Diazine/triazine Product Yield 10 ##STR00376##
##STR00377## 59% 11 ##STR00378## ##STR00379## 63%
Example 12
Hole Conductor HTM 12
##STR00380##
[0157] 7.6 g (200 mmol) of lithium aluminium hydride are added in
portions to a vigorously stirred suspension, cooled to 0.degree.
C., of 46.4 g (100 mmol) of
6-[1,1;3',1'']-terphenyl-5'-yl-6,12-dihydrobenzimidazo[2,1-b]quinazoline
(Ex. 1) in 1000 ml of diethylene glycol dimethyl ether. The
reaction mixture is allowed to warm slowly to room temperature over
the course of 4 h and is then stirred for a further 12 h. A mixture
of 7.6 ml of water and 50 ml of diethylene glycol dimethyl ether,
7.6 ml of NaOH solution (10% by weight) and then 23.0 ml of water
is added dropwise to the reaction mixture with vigorous stirring.
The salts are filtered off with suction, rinsed with 100 ml of
diethylene glycol dimethyl ether and removed in vacuo. After
recrystallisation of the solid five times from NMP, the product is
subjected to fractional sublimation in vacuo (pressure about
10.sup.-5 mbar, temperature about 320.degree. C.). Yield: 17.5 g
(39 mmol), 39%; purity: 99.9% according to HPLC.
[0158] The following compounds are prepared analogously:
TABLE-US-00007 Benzimidazo[2,1-b]- Ex. quinazolin-12(6H)-one
Product Yield 13 ##STR00381## ##STR00382## 46% 14 ##STR00383##
##STR00384## 45%
Example 15
Hole Conductor HTM 15
##STR00385##
[0160] A mixture of 207 g (100 mmol) of
5H-benzimidazo[1,2-a]benzimidazole, 34.0 g (110 mmol) of
1-bromo-3,5-diphenylbenzene [103068-20-8], 20.7 g (150 mmol) of
potassium carbonate, 3.8 g (20 mmol) of copper iodide, 200 g of
glass beads (diameter 3 mm) and 300 ml of NMP is heated at
200.degree. C. for 20 h with vigorous stirring. After cooling, a
mixture of 200 ml of water and 200 ml of ethanol is added, the
mixture is stirred for a further 30 min., the suspension is
filtered through a slotted frit in order to separate off the glass
beads, the solid is then filtered off with suction, washed three
times with 100 ml of ethanol each time and dried in vacuo. The
solid is subjected to continuous hot extraction with o-xylene
through an aluminium oxide bed (aluminium oxide, basic, activity
grade 1), subsequently recrystallised twice from NMP and five times
from o-dichlorobenzene and then subjected to fractional sublimation
in vacuo (pressure about 10.sup.-5 mbar, temperature about
310.degree. C.). Yield: 9.6 g (22 mmol), 22%; purity: 99.9%
according to HPLC.
B) Device Examples
Example 16
Production of OLEDs
[0161] OLEDs according to the invention and OLEDs in accordance
with the prior art are produced by a general process in accordance
with WO 04/058911, which is adapted to the circumstances described
here (layer-thickness variation, materials used).
[0162] The results for various OLEDs are presented in Examples 17
to 35 below (see Tables 1, 2 and 3). Glass plates which have been
coated with structured ITO (indium tin oxide) in a thickness of 150
nm are coated with 20 nm of PEDOT
(poly(3,4-ethylenedioxy-2,5-thiophene), applied by spin coating
from water, purchased from H. C. Starck, Goslar, Germany) for
improved processing. These coated glass plates form the substrates
to which the OLEDs are applied. The OLEDs have in principle the
following layer structure: substrate/hole-injection layer (HIL1,
comprising HIL1, 20 nm)/hole-transport layer (HTL, comprising HTM1
(reference) or the HTMs according to the invention, 20
nm)/electron-blocking layer (EBL, 20 nm)/emission layer (EML
comprising matrix materials M1 to M11 M according to the invention,
40 nm)/electron-transport layer (ETL, comprising ETL1, 20
nm)/electron-injection layer (EIL, comprising LiF, 1 nm) and
finally a cathode. The cathode is formed by an aluminium layer with
a thickness of 100 nm. The precise structure of the OLEDs, in
particular the structure of the hole-conductor or emitter layer,
and the results obtained with these OLEDs on use of the compounds
according to the invention as matrix materials for phosphorescent
emitters is shown in Table 1 for green-emitting OLEDs and in Table
2 for blue-emitting OLEDs. Table 3 shows the results for the use of
compounds according to the invention both as matrix materials for
phosphorescent emitters and also as hole-transport materials.
[0163] The materials used for the production of the OLEDs are shown
in Table 4.
[0164] All materials are applied by thermal vapour deposition in a
vacuum chamber. The emission layer here always consists of at least
one matrix material (host material) and an emitting dopant (dopant,
emitter), with which the matrix material or matrix materials is
admixed in a certain proportion by volume by co-evaporation.
[0165] The as yet unoptimised OLEDs are characterised by standard
methods. For this purpose, the electroluminescence spectra, the
current efficiency (measured in cd/A) and the voltage are
determined. The efficiencies and voltages indicated in the tables
relate to the corresponding values at an operating luminance of
1000 cd/m.sup.2.
TABLE-US-00008 TABLE 1 Green-emitting OLEDs Ex. EML Efficiency
[cd/A] Voltage [V] CIE, x/y 17 M1:TEG1 (15%) 41.2 4.8 0.33/0.62 18
M2:TEG1 (15%) 37.9 4.7 0.33/0.62 19 M3:TEG1 (15%) 44.0 4.8
0.33/0.62 20 M4:TEG2 (15%) 52.0 4.5 0.32/0.61 21 M5:TEG2 (15%) 55.3
4.4 0.32/0.61 22 M6:TEG2 (15%) 48.0 4.4 0.32/0.61 23 M7:TEG2 (15%)
45.5 4.3 0.32/0.61 24 M8:TEG2 (15%) 34.6 4.5 0.32/0.61 25 M9:TEG2
(15%) 50.0 4.3 0.36/0.58 26 M10:TEG2 (15%) 45.0 4.1 0.36/0.58 27
M11:TEG2 (15%) 52.7 4.2 0.36/0.58
TABLE-US-00009 TABLE 2 Blue-emitting OLEDs Ex. EML Efficiency
[cd/A] Voltage [V] CIE, x/y 28 M1:TEB1 (15%) 22.4 6.8 0.16/0.26 29
M5:TEB1 (15%) 24.0 6.6 0.16/0.27 30 M1:TEB2 (15%) 32.3 4.9
0.17/0.38 31 M5:TEB2 (15%) 28.1 4.8 0.17/0.38
TABLE-US-00010 TABLE 3 Green-emitting OLEDs Ex. HTM/EML Efficiency
[cd/A] Voltage [V] CIE, x/y 32 HTM12/ 48.3 4.4 0.32/0.61 M6:TEG2
(15%) 33 HTM13/ 52.1 4.3 0.32/0.61 M6:TEG2 (15%) 34 HTM14/ 53.0 4.3
0.32/0.61 M6:TEG2 (15%) 35 HTM15/ 46.7 4.1 0.32/0.61 M6:TEG2
(15%)
TABLE-US-00011 TABLE 4 Structural formulae of the materials used
##STR00386## HIL1 ##STR00387## HTM1 (NPB) ##STR00388## EBL
##STR00389## ETM1 (Alq) ##STR00390## TEG1 ##STR00391## TEG2
##STR00392## TEB1 ##STR00393## TEB2
[0166] As is clearly evident from the examples shown above, the
materials according to the invention are particularly suitable for
use as matrix materials for phosphorescent emitters and as hole
conductors, where they result in high efficiencies and low
operating voltages.
* * * * *