Materials for electronic devices

Abstract

The present invention relates to materials for electronic devices. In particular, the present invention relates to compounds according to formula (1), which are suitable for use in electronic devices, especially in organic electroluminescent devices.

Description

[0001] This invention patent application is a divisional application of the invention patent application with international application number PCT / EP2014 / 002586, international application date September 24, 2014, application number 201480057646.1 entering the Chinese national phase, and invention name “Materials for electronic devices”. Technical Field

[0002] The present invention relates to materials for electronic devices. In particular, the present invention relates to materials for electronic devices, especially for organic electroluminescent devices. Background Art

[0003] The development of functional compounds for use in electronic devices is currently the subject of intensive research. A particular aim here is to develop compounds with which improvements in the properties of electronic devices can be achieved in one or more relevant aspects, such as power efficiency, lifetime or color coordinates of the emitted light.

[0004] According to the present invention, the term "electronic device" is understood to refer to devices including: organic integrated circuits (OICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic light emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field quenching devices (OFQDs), organic light emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs).

[0005] Of particular interest is the provision of compounds for use in the following electronic devices known as OLEDs.The general structure of OLEDs and their mode of operation are known to those skilled in the art and are described in particular in US 4539507, US 5151629, EP 0676461 and WO 1998 / 27136.

[0006] With regard to the performance data of OLEDs, further improvements are still needed, especially with regard to widespread commercial use, for example in display devices or as light sources. Of particular importance in this regard are the lifetime, efficiency and operating voltage of OLEDs, as well as the color values ​​achieved. Especially in the case of blue-emitting OLEDs, there is potential for improvement in the lifetime of the device. In addition, compounds that are desired to be used as functional materials in electronic devices have high thermal stability and a high glass transition temperature and can be sublimated without decomposition.

[0007] Document CN 102030701A describes compounds having an indeno[1,2,3-jk]fluorene skeleton. Document US 2006 / 0094859 A1 describes polymers having a plurality of bridged biphenyl units. Summary of the invention

[0008] It is an object of the present invention to provide compounds which are suitable for use, for example, as matrix materials and / or as hole-transport / electron-blocking materials or exciton-blocking materials and / or as electron-transport or hole-blocking materials in fluorescent or phosphorescent OLEDs, in particular phosphorescent OLEDs.

[0009] For clarity, the numbering of indeno[1,2,3-jk]fluorene is shown below:

[0010]

[0011] Therefore, the present invention provides compounds of formula (1)

[0012]

[0013] The symbols that appear are as follows:

[0014] Z is the same or different in each case and is CR 1 or N;

[0015] Ar 1 are identical or different in each case and are aromatic rings having 5 to 60 atoms and may be replaced by one or more R 3 Aromatic or heteroaromatic ring system substituted with a radical; at the same time, two Ar 1 The group may also be connected by a single bond or selected from N(R 4 )、C(R 4 )2. The bridging groups of O and S are bridged to each other;

[0016] R 1 are identical or different in each case and are H, D, F, Cl, Br, I, CN, NO2, N(Ar 1 )2,N(R 3 )2,C(=O)Ar 1 , C(=O)R 3 , P(=O)(Ar 1 )2,P(=O)(R 3 )2,B(OR 3 )2,CHO,Si(R 3 )2, OSO2R 3 , S(=O)R 3 , S(=O)2R 3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, wherein the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 3 groups, and one or more adjacent or non-adjacent CH2 groups may be replaced by -R 3 C=CR 3 -, -C≡C-, C=O, C=S, C=Se, C=NR 3 、-C(=O)-NR 3 -、P(=O)(R 3 )、-C(=O)-O-、Si(R 3 )2. NR 3 , -O-, -S-, SO or SO2, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or have 6 to 60 aromatic ring atoms and in each case may be replaced by one or more R 3 an aromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and which may in each case be substituted with one or more R 3 A heteroaromatic ring system substituted with a radical, wherein two or more R 1 The groups may be linked to each other and may form rings;

[0017] R 2 are identical or different in each case and are H, D, F, Cl, Br, I, CN, NO2, N(Ar 1 )2,N(R 3 )2,C(=O)Ar 1 , C(=O)R 3 , P(=O)(Ar 1 )2,P(=O)(R 3 )2,B(OR 3 )2,CHO,Si(R 3 )2, OSO2R 3 , S(=O)R 3 , S(=O)2R 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, wherein the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 3 groups, and one or more adjacent or non-adjacent CH2 groups may be replaced by -R 3 C=CR3 -, -C≡C-, C=O, C=S, C=Se, C=NR 3 、-C(=O)-NR 3 -、P(=O)(R 3 )、-C(=O)-O-、Si(R 3 )2. NR 3 , -O-, -S-, SO or SO2, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or have 6 to 60 aromatic ring atoms and in each case may be replaced by one or more R 3 an aromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and which may in each case be substituted with one or more R 3 Group-substituted heteroaromatic ring systems;

[0018] R 3 are identical or different in each case and are H, D, F, Cl, Br, I, CN, NO2, N(R 4 )2,C(=O)Ar 1 , C(=O)R 4 , P(=O)(Ar 1 )2,B(OR 4 )2,CHO,Si(R 4 )2, OSO2R 4 , S(=O)R 4 , S(=O)2R 4 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, wherein the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 4 groups, and one or more adjacent or non-adjacent CH2 groups may be replaced by -R 4 C=CR 4 -, -C≡C-, C=O, C=S, C=Se, C=NR 4 、-C(=O)-NR 4 -、P(=O)(R 4 )、-C(=O)-O-、Si(R 4 )2. NR 4 , -O-, -S-, SO or SO2, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or have 6 to 60 aromatic ring atoms and in each case may be replaced by one or more R 4an aromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and which may in each case be substituted with one or more R 4 A heteroaromatic ring system substituted with a radical, wherein two or more R 4 The groups may be linked to each other and may form rings;

[0019] R 4 are identical or different in each case and are H, D, F, CN, or an aliphatic radical having 1 to 20 carbon atoms or an aromatic ring system having 6 to 60 aromatic ring atoms or a heteroaromatic ring system having 5 to 60 aromatic ring atoms, wherein one or more hydrogen atoms in the aliphatic radical, the aromatic ring system or the heteroaromatic ring system may be replaced by D, F, Cl, Br, I, CN or an alkyl radical having 1 to 5 carbon atoms, wherein two or more R 4 The groups may be linked to each other and may form rings;

[0020] Where R in formula (1) 2 and / or at least one R 1 Contains at least one aromatic or heteroaromatic ring system; and

[0021] When at least one R 1 When containing at least one aromatic or heteroaromatic ring system, in all R 1 and R 2 The total number of aromatic ring atoms in is at least 12; and

[0022] When R 1 When it does not contain an aromatic or heteroaromatic ring system, R 2 Contains at least 24 aromatic ring atoms and does not contain an additional indeno[1,2,3-jk]fluorene skeleton bonded via the 12 position. DETAILED DESCRIPTION

[0023] Aryl groups in the context of the present invention contain 6 to 60 aromatic ring atoms; heteroaryl groups in the context of the present invention contain in principle 5 to 60 aromatic ring atoms, at least one of which is a heteroatom; the heteroatom is preferably selected from N, O and / or S. This is the basic definition. If other preferences are stated in the description of the present invention, for example with regard to the number of aromatic ring atoms or heteroatoms present, these preferences apply.

[0024] Aryl or heteroaryl groups are understood here to mean simple aromatic rings, i.e. benzene, or simple heteroaromatic rings, such as pyridine, pyrimidine, thiophene, etc., or fused (condensed) aromatic or heteroaromatic polycyclic rings, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline or carbazole. The fused (condensed) aromatic or heteroaromatic polycyclic rings in the context of the present application are composed of two or more simple aromatic or heteroaromatic rings fused to each other. In contrast, aromatic systems such as biphenyl or bipyridine, which are interconnected by single bonds, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

[0025] Aryl or heteroaryl groups which may each be substituted by the abovementioned radicals and which may be attached to the aromatic or heteroaromatic system via any desired position are understood in particular to mean radicals derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, Perylene, fluoranthene, benzanthracene, triphenylene, 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, phenanthroline azine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthimidazole, pyridimidazole, pyrazimidazole, quinoxalineimidazole, Azoles, benzo Azoles, naphtho Azoles, anthracenes Azoles, phenanthracenes Azoles, Isopropylamine oxazole, 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.

[0026] An aromatic ring system in the context of the present invention contains 6 to 60 aromatic ring atoms in the ring system. A heteroaromatic ring system in the context of the present invention contains 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system in the context of the present invention is understood to mean a system which does not necessarily comprise only aryl or heteroaryl groups, but in which two or more aryl or heteroaryl groups can also be bonded via non-aromatic units (preferably less than 10% of non-H atoms), such as, for example, sp 3 -hybridized carbon, silicon, nitrogen or oxygen atoms, sp 2 -hybridized carbon or nitrogen atoms or sp-hybridized carbon atoms. For example, systems such as 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are also considered as aromatic ring systems in the context of the present invention, and similarly, systems in which two or more aryl groups are connected by, for example, linear or cyclic alkyl, alkenyl or alkynyl groups or by silyl groups are also considered as aromatic ring systems in the context of the present invention. In addition, systems in which two or more aryl or heteroaryl groups are connected to each other by single bonds, for example, systems such as biphenyl, terphenyl or diphenyltriazine, are also considered as aromatic or heteroaromatic ring systems in the context of the present invention.

[0027] An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms which may in each case also be substituted by radicals as defined above and which may be linked to the aromatic or heteroaromatic system via any desired position is understood to mean in particular radicals derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, triphenylene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, isophenyl, terphenyl, triphenyl, tetraphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, trimer indene, isotrimer indene, spirotrimer indene, spiroisotrimer indene, 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, phenanthroline azine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthimidazole, pyridimidazole, pyrazimidazole, quinoxalineimidazole, Azoles, benzo Azoles, naphtho Azoles, anthracenes Azoles, phenanthracenes Azoles, Isopropylamine azole, 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, phen Oxazine, phenothiazine, fluorescent red ring, 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 a combination of these groups.

[0028] In the context of the present invention, straight-chain alkyl radicals having 1 to 40 carbon atoms and branched or cyclic alkyl radicals having 3 to 40 carbon atoms and alkenyl or alkynyl radicals having 2 to 40 carbon atoms, in which individual hydrogen atoms or CH2 radicals may also be substituted by the radicals mentioned above in the definition of the radicals, are preferably understood to mean the following radicals: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methyl- cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl radical. Alkoxy or thioalkyl radicals having 1 to 40 carbon atoms are preferably understood as meaning methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

[0029] In the context of the present specification, the expression that two or more groups together can form a ring should in particular be understood to mean that the two groups are linked to one another via a chemical bond. This is exemplified by the following scheme:

[0030]

[0031] Additionally, however, the above wording should also be understood to mean that if one of the two groups is hydrogen, the second group is bonded to the position to which the hydrogen atom is bonded to form a ring. This should be exemplified by the following scheme:

[0032]

[0033] In a preferred embodiment of the invention, not more than one Z group per ring is N and the other Z groups are in each case identical or different and are CR 1In one particularly preferred embodiment of the invention, all Z groups are in each case identical or different and are CR 1 .

[0034] When at least one R 1 When containing at least one aromatic or heteroaromatic ring system, in all R 1 and R 2 The total number of aromatic ring atoms in is at least 12; preferably at least 18, more preferably at least 24.

[0035] When R 1 When it does not contain an aromatic or heteroaromatic ring system, R 2 Contains at least 24 aromatic ring atoms and does not contain additional indeno[1,2,3-jk]fluorene skeletons.

[0036] This implements R 2 The indeno[1,2,3-jk]fluorene skeleton has a certain flexibility and a minimum size, which has a positive effect on the stability of the compound, especially in the case of use in sublimation. In particular, position 12 in the indeno[1,2,3-jk]fluorene skeleton is the most acidic position in the skeleton. Therefore, these bonds are particularly unstable. If other indeno[1,2,3-jk]fluorene skeletons are also present in the compound, it becomes not only very large, but also potentially less stable.

[0037] Preferably, R 1 and / or R 2 It does not contain any fused aromatic or heteroaromatic ring systems having more than 14 aromatic ring atoms.

[0038] Also preferably, all R 1 and R 2 The total number of aromatic ring atoms contained together does not exceed 84, preferably does not exceed 60.

[0039] Therefore, a preferred embodiment of the compound of formula (1) is a compound of the following formula (2):

[0040]

[0041] The symbols used therein are as defined above.

[0042] In a preferred embodiment of the present invention, R in the above formula 1 are in each case identical or different and are H, D, F, Cl, Br, CN, NO2, N(Ar 1 )2,N(R 3 )2,C(=O)Ar 1 , C(=O)R 3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 3 groups, and one or more non-adjacent CH2 groups may be replaced by Si(R 3 )2, -S- and -O-, and one or more hydrogen atoms may be replaced by D or F, or have 6 to 30 aromatic ring atoms and in each case may be replaced by one or more R 3 an aromatic ring system substituted with a radical, or having 5 to 30 aromatic ring atoms and which may in each case be substituted with one or more R 3 A heteroaromatic ring system substituted with a radical, wherein two or more R 1 The groups may be linked to each other and may form a ring.

[0043] In another preferred embodiment of the present invention, R 1 are in each case identical or different and are H, D, F, CN, NO2, N(Ar 1 )2,N(R 3 )2,C(=O)Ar 1 , C(=O)R 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 3 groups, and one or more non-adjacent CH2 groups may be replaced by Si(R 3 )2, -S- and -O-, and one or more hydrogen atoms may be replaced by D or F, or have 6 to 30 aromatic ring atoms and in each case may be replaced by one or more R 3 an aromatic ring system substituted with a radical, or having 5 to 30 aromatic ring atoms and which may in each case be substituted with one or more R 3 A heteroaromatic ring system substituted with a radical, wherein two or more R 1 The groups may be linked to each other and may form a ring.

[0044] In another preferred embodiment of the present invention, R 1 are in each case identical or different and are H, D, F, CN, NO2, N(Ar 1 )2,N(R 3)2, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms or an alkenyl or alkynyl group having 2 to 10 carbon atoms, wherein the alkyl, alkoxy, alkenyl or alkynyl group may in each case be replaced by one or more R 3 groups, and one or more non-adjacent CH2 groups may be replaced by Si(R 3 )2, -S- and -O-, and one or more hydrogen atoms may be replaced by D or F, or have 6 to 30 aromatic ring atoms and in each case may be replaced by one or more R 3 an aromatic ring system substituted with a radical, or having 5 to 30 aromatic ring atoms and which may in each case be substituted with one or more R 3 A heteroaromatic ring system substituted with a radical, wherein two or more R 1 The groups may be linked to each other and may form a ring.

[0045] In a preferred embodiment of the present invention, R in the above formula 2 are in each case identical or different and are H, D, F, Cl, Br, CN, NO2, N(Ar 1 )2,N(R 3 )2,C(=O)Ar 1 , C(=O)R 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 3 groups, and one or more non-adjacent CH2 groups may be replaced by Si(R 3 )2, -S- and -O-, and one or more hydrogen atoms may be replaced by D or F, or have 6 to 30 aromatic ring atoms and in each case may be replaced by one or more R 3 an aromatic ring system substituted with a radical, or having 5 to 30 aromatic ring atoms and which may in each case be substituted with one or more R 3 Group-substituted heteroaromatic ring systems.

[0046] In another preferred embodiment of the present invention, R 2 are in each case identical or different and are H, D, F, CN, NO2, N(Ar 1 )2,N(R 3 )2,C(=O)Ar 1 , C(=O)R 3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 3 groups, and one or more non-adjacent CH2 groups may be replaced by Si(R 3 )2, -S- and -O-, and one or more hydrogen atoms may be replaced by D or F, or have 6 to 30 aromatic ring atoms and in each case may be replaced by one or more R 3 an aromatic ring system substituted with a radical, or having 5 to 30 aromatic ring atoms and which may in each case be substituted with one or more R 3 Group-substituted heteroaromatic ring systems.

[0047] In another preferred embodiment of the present invention, R 2 are identical or different in each case and are H, D, F, CN, N(Ar 1 )2,N(R 3 )2, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms or an alkenyl or alkynyl group having 2 to 10 carbon atoms, wherein the alkyl, alkoxy, alkenyl or alkynyl group may in each case be replaced by one or more R 3 groups, and one or more non-adjacent CH2 groups may be replaced by Si(R 3 )2, -S- and -O-, and one or more hydrogen atoms may be replaced by D or F, or have 6 to 30 aromatic ring atoms and in each case may be replaced by one or more R 3 an aromatic ring system substituted with a radical, or having 5 to 30 aromatic ring atoms and which may in each case be substituted with one or more R 3 Group-substituted heteroaromatic ring systems.

[0048] In another preferred embodiment of the present invention, R 2 has 6 to 30 aromatic ring atoms and may be replaced by one or more R 3 Aromatic ring systems substituted with radicals.

[0049] In another embodiment of the present invention, R in the above formula 3 are identical or different in each case and are H, D, F, CN, N(R 4 )2,C(=O)R 4 、Si(R 4)2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 4 groups, and one or more adjacent or non-adjacent CH2 groups may be replaced by Si(R 4 )2. NR 4 , -O- or -S-, and one or more hydrogen atoms may be replaced by D, F or CN, or have 6 to 18 aromatic ring atoms and in each case may be replaced by one or more R 4 an aromatic ring system substituted with a radical, or having 5 to 18 aromatic ring atoms and which may in each case be replaced by one or more R 4 A heteroaromatic ring system substituted with a radical, wherein two or more R 4 The groups may be linked to each other and may form a ring.

[0050] In another embodiment of the present invention, R at at least one of the 5-position and the 10-position in the indeno[1,2,3-jk]fluorene skeleton is 1 are in each case identical or different and are H, D, F, CN, NO2, N(Ar 1 )2,N(R 3 )2,C(=O)Ar 1 , P(=O)(Ar 1 )2,P(=O)(R 3 )2,Si(R 3 )2, OSO2R 3 , S(=O)R 3 , S(=O)2R 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, wherein the alkyl, alkoxy, thioalkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 3 groups, and one or more adjacent or non-adjacent CH2 groups may be replaced by -R 3 C=CR 3 -, -C≡C-, C=O, C=S, C=Se, C=NR 3 、-C(=O)-NR 3 -、P(=O)(R 3 )、-C(=O)-O-、Si(R 3 )2. NR 3, -O-, -S-, SO or SO2, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or have 6 to 60 aromatic ring atoms and in each case may be replaced by one or more R 3 an aromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and which may in each case be substituted with one or more R 3 A heteroaromatic ring system substituted with a radical, wherein two or more R 1 The groups may be linked to each other and may form a ring. More preferably, if present in each case, R at positions 5 and 10 of the indeno[1,2,3-jk]fluorene skeleton is 1 Does not contain Cl, Br, I, B (OR 3 )2 and any group in CHO.

[0051] For compounds processed by vacuum evaporation, the alkyl groups here preferably have not more than 4 carbon atoms. For compounds processed from solution, suitable compounds are also those substituted with alkyl groups having up to 10 carbon atoms or with oligoarylene groups, such as o-, m-, p- or branched terphenyl or quaterphenyl groups.

[0052] In another preferred embodiment of the present invention, at least one R 1 is not H; preferably, at least one R 1 Contains aromatic or heteroaromatic ring systems.

[0053] For R 1 and R 2 Particularly preferred aromatic ring systems are selected from the group consisting of phenyl, o-, m- or p-biphenyl, o-, m- or p-terphenyl, o-, m-, p- or branched quaterphenyl, fluorene, spirobifluorene, each of which may be replaced by one or more R 3 Group substitution.

[0054] For R 1 and R 2 Particularly preferred aromatic ring systems are selected in particular from structures of the following formulae:

[0055]

[0056]

[0057]

[0058] wherein the structure may be represented by one or more R 3 group substituted, and R 3 is as defined above. Preferably, R 3These are aliphatic groups having 1 to 20 carbon atoms or aromatic ring systems having 6 to 24 aromatic ring atoms or heteroaromatic ring systems having 5 to 24 aromatic ring atoms, preferably aliphatic groups having 1 to 10 carbon atoms or aromatic ring systems having 6 to 18 aromatic ring atoms.

[0059] Particularly preferred heteroaromatic ring systems R 1 and R 2 Contains triazine, pyrimidine, pyrazine, pyridazine, pyridine, benzothiophene, benzofuran, indole, carbazole, azacarbazole, diazacarbazole, dibenzothiophene and / or dibenzofuran as heteroaryl groups. Here, the heteroaromatic ring system is especially selected from the following structures of formula (H-1) to (H-14):

[0060]

[0061] The heteroaromatic groups can be replaced by R 3 The heteroaromatic group may be attached to the indeno[1,2,3-jk]fluorene skeleton at any position, wherein the bond may also replace NR 3 exists and where R 3 is as defined for formula (1), and the bond to the indeno[1,2,3-jk]fluorene skeleton may also be connected via a divalent aromatic or heteroaromatic ring system, preferably a divalent ring system of one of formulas (Ar3-1) to (Ar3-12), more preferably one of formulas (Ar3-1) to (Ar3-4). Preferably, R 3 It is an aliphatic group having 1 to 20 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms, or a heteroaromatic ring system having 5 to 24 aromatic ring atoms, preferably an aliphatic group having 1 to 10 carbon atoms, or an aromatic ring system having 6 to 18 aromatic ring atoms.

[0062] When R 1 or R 2 N(Ar 1 )2 group, the group is preferably selected from the following structures of formula (3) and (4):

[0063]

[0064] And, when R 1 or R 2 When it is an aromatic or heteroaromatic ring system as a triarylamine group or a triheteroarylamine group, the group is preferably selected from the structure of the following formula (5):

[0065]

[0066] The symbols used are as defined above, the dotted bonds represent the bonds to the indeno[1,2,3-jk]fluorene basic skeleton, and in addition:

[0067] Ar 2 are identical or different in each case and are aromatic rings having 5 to 24 atoms and may be replaced by one or more R 3 Aromatic or heteroaromatic ring system substituted with groups; all Ar 2 and Ar 3 The sum of the aromatic ring atoms of the radical does not exceed 60;

[0068] Ar 3 in each case a ring having 5 to 24 aromatic ring atoms which can be replaced by said plurality of R 3 a substituted aromatic or heteroaromatic ring system in the group;

[0069] E is selected from a single bond, C(R 3 )2. NR 3 , O and S.

[0070] For the formula Ar in formula (3) 1 and Ar in formula (5) 2 , the preferred ring systems are structures of formula (H-1) to (H-15), wherein these can be replaced by R at all unoccupied positions 3 The heteroaromatic group may be substituted with a nitrogen atom of the formula at any unoccupied position, and the structures of formulae (A-1) to (A-25), wherein the structures may be substituted with one or more R 3 The dotted bond is the bond to the nitrogen atom of the formula, and R 3 As defined above.

[0071] Most preferably, at least one Ar in formula (5) 2 are selected from structures (A-2) to (A-25) and (H-7) to (H-9); preferably, the two Ar in formula (5) 2 All are selected from structures (A-2) to (A-25) and (H-7) to (H-9).

[0072] Most preferably, at least one Ar in formula (3) 1 are selected from structures (A-2) to (A-17) and (H-7) to (H-9); preferably, the two Ar in formula (5) 2 All are selected from structures (A-2) to (A-17) and (H-7) to (H-9).

[0073] Preferably, Ar 3 A divalent group selected from the following formulas (Ar3-1) to (Ar3-12):

[0074]

[0075]

[0076] wherein E is the same or different at each occurrence and is selected from -C(R 3 )2-, -C(=O)-, -O-, -S-, -(S=O)-, -S(=O)2-, -NR 3 - a divalent group, wherein R 3 is as defined for formula (1). More preferably, Ar 3 It is one of the structures (Ar3-1) to (Ar3-4).

[0077] In a preferred embodiment, the compound comprises exactly 1, 2, 3, 4 or 5, preferably 1, 2 or 3, more preferably 1 or 2 R selected from formula (3), (4) and (5), preferably selected from formula (3) and (5) 1 and / or R 2 Group.

[0078] In another embodiment, the compound comprises exactly one R selected from formula (3), (4) and (5) 1 or R 2 Group.

[0079] Preferred embodiments of the compound of formula (1) are compounds of formula (1-3a) to (1-3g) and formula (1-5a) to (1-5g):

[0080]

[0081]

[0082]

[0083] Where R 1 , R 2 ,Ar 1 ,Ar 2 and Ar 3 As defined above.

[0084] In a preferred embodiment of the present invention, if there is R 2 , then in R 2 In the 6-membered aryl ring system directly adjacent to the indeno[1,2,3-jk]fluorene skeleton, there is no nitrogen atom, preferably a heteroatom, in the para position relative to the indeno[1,2,3-jk]fluorene skeleton. The same applies to the fused aromatic ring system comprising a carbazole structure bonded to the 3-position of the indeno[1,2,3-jk]fluorene skeleton. Surprisingly, it has been found that such compounds are not as stable as compounds with a nitrogen atom in the ortho or meta position.

[0085] Therefore, when R2 In the case of a heteroaromatic ring system, a compound having a heteroatom, preferably a nitrogen atom, at the ortho- or meta-position of the indeno[1,2,3-jk]fluorene skeleton is preferred.

[0086] In a preferred embodiment, when R as the heteroaromatic ring system 2 When a triarylamine group or triheteroarylamine group or a carbazole structure directly bonded to the indeno[1,2,3-jk]fluorene skeleton is included, the nitrogen atom is arranged at the meta position or the ortho position relative to the indeno[1,2,3-jk]fluorene skeleton.

[0087] In a preferred embodiment of the present invention, Ar in formula (1-5a) 3 is selected from structures (Ar3-2) to (Ar3-11); preferably, the bond to the indeno[1,2,3-jk]fluorene skeleton is at position 1, 2 or 4 in formula (Ar3-5), and is not at the para position to the bond to nitrogen in formulas (Ar3-7) and (Ar3-9). More preferably, Ar 3 Selected from structures (Ar3-2) and (Ar3-3).

[0088] Therefore, a preferred embodiment of the compound of formula (1-5a) is a compound of the following formula

[0089]

[0090] Where R 1 and Ar 2 is as defined above and the compound may be replaced at unoccupied positions by one or more R 3 The group may be substituted, but is preferably unsubstituted.

[0091] In a preferred embodiment of the present invention, when R is present in formula (1-3a) to (1-3g), (1-5a) to (1-5g) or formula (1-5a-1) and (1-5a-2), 1 and R 2 When R 1 and R 2 None or R 1 and R 2 Exactly one of the radicals is another radical selected from the group consisting of formulae (3), (4) and (5).

[0092] In a preferred embodiment of the present invention, when R is present in formulas (1-3a) to (1-3g) and (1-5a) to (1-5g) or formulas (1-5a-1) and (1-5a-2), 1 and R 2 When R 1 and R 2 None or R 1 and R 2Exactly one of them is another group selected from the group consisting of formulae (3), (4) and (5), and at least one other R 1 and / or R 2 , if present, is an aromatic or heteroaromatic ring system, more preferably an aromatic or heteroaromatic ring system of formula (A-1) to (A-25) or (H-1) to (H-14), most preferably an aromatic ring system of formula (A-1) to (A-25).

[0093] In a preferred embodiment of the present invention, the more than one R 1 They do not together form an aromatic or heteroaromatic ring system fused to the indeno[1,2,3-jk]fluorene skeleton.

[0094] According to the use of the compound of the present invention, different substituents R 1 and R 2 .

[0095] When the compound of the formula (1) or (2) is used as a matrix material for a phosphorescent emitter, preferably at least one R 1 and / or R 2 N(Ar 1 )2、C(=O)Ar 1 , P(=O)(Ar 1 )2 or having 5 to 60 aromatic ring atoms and may be replaced by one or more R 3 More preferably, in this case, at least one R 1 and / or R 2 Selected from formula (3), (4) and (5) and the preceding embodiments thereof.

[0096] When the compound of formula (1) or (2) is used as a host material for a fluorescent emitter, it is preferred that at least one R 1 and / or R 2 is an aromatic or heteroaromatic ring system comprising at least one aryl group having at least three fused six-membered rings, preferably anthracene.

[0097] When the compound of formula (1) or (2) is used as a fluorescent emitter, it is preferred that at least one R 1 and / or R 2 An aromatic or heteroaromatic ring system containing at least one aryl group or an aromatic ring system having at least two fused six-membered rings bonded to the indeno[1,2,3-jk]fluorene skeleton, preferably directly or via a phenyl group. The fused aryl group is preferably selected from anthracene, pyrene, phenanthrene, Monobenzoindenofluorene and dibenzoindenofluorene.

[0098] When the compound of formula (1) or (2) is used as an electron transport material, it is preferred that at least one R 1and / or R 2 The radical is an electron-deficient heteroaromatic ring system having 5 to 40 aromatic ring atoms, preferably 5 to 25 aromatic ring atoms, which may be replaced by one or more R 3 An electron-deficient heteroaromatic ring system in the context of the present invention is a heteroaromatic ring system which comprises at least one electron-deficient heteroaryl group which is a 6-membered heteroaryl group having at least one nitrogen atom or a 5-membered heteroaryl group having at least two heteroatoms.

[0099] Particularly preferred electron-deficient heteroaromatic ring systems R 1 and / or R 2 Contains at least one group selected from the following as a heteroaryl group: triazine, pyrimidine, pyrazine, pyridazine, pyridine, imidazole, pyrazole, Azoles, oxadiazole, triazole, thiazole, thiadiazole, benzimidazole, quinoline, isoquinoline and quinoxaline. These heteroaromatic ring systems are especially selected from the structures of formula (H-1), (H-2), (H-3), (H-14), wherein R 3 is as defined above and the structure is bonded to the indeno[1,2,3-jk]fluorene backbone via a single bond or via a phenyl group at an unoccupied position.

[0100] When the compound of formula (1) or (2) is used as a hole transport material or as a light-emitting compound, it is preferred that at least one R 1 and / or R 2 The group is N(Ar 1 )2, a triarylamino group or an electron-rich heteroaromatic ring system having 5 to 40 aromatic ring atoms, especially 5 to 25 aromatic ring atoms, which heteroaromatic ring system may be substituted by one or more R 3 The electron-rich heteroaromatic ring system in the context of the present invention is a heteroaromatic ring system which comprises at least one electron-rich heteroaryl group, which is a 5-membered heteroaryl group having exactly one heteroatom, which may also be fused to one or more aryl groups.

[0101] Particularly preferred electron-rich heteroaromatic ring systems R 1 and / or R 2 The following are included as heteroaryl groups: pyrrole, furan, thiophene, benzothiophene, benzofuran, indole, carbazole, dibenzothiophene, dibenzofuran and / or azacarbazole. These electron-rich heteroaromatic ring systems are especially selected from the structures of the above formulae (H-4) to (H-13).

[0102] In one embodiment of the present invention, the above preferred embodiments can be combined with each other as required.

[0103] Examples of preferred compounds according to the above-mentioned embodiment or compounds preferably used for electronic devices are compounds of the following structures (1) to (55):

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] The synthesis of the compounds of the invention can be carried out by methods and reaction types known in the art, such as Friedel-Crafts reaction, palladium-catalyzed intramolecular CH arylation, Buchwald coupling and Suzuki coupling and Grignard reaction.

[0111] A preferred first method for preparing compounds of the invention starts with the basic structures depicted as reactants in Scheme 1. In some cases, these are commercially available; in other cases, they can be prepared from simple commercially available compounds in a few synthetic steps:

[0112] Solution 1

[0113]

[0114] R: organic group (if any)

[0115] X: halogen or other reactive leaving group

[0116] Y: OH, halogen or other reactive leaving group

[0117] Such compounds can be obtained, for example, by reacting fluorenone with an appropriately substituted aryl halide in a Grignard reaction:

[0118] Option 1a:

[0119]

[0120] R: organic group (if any)

[0121] X: halogen or other reactive leaving group

[0122] In the next step, the desired R 2 Introduce into the obtained compound to replace the Y group. 2When aromatic ring systems are involved, this is preferably accomplished via a Friedel-Crafts reaction.

[0123] Solution 2

[0124]

[0125] R: organic group (if any)

[0126] X: halogen or other reactive leaving group

[0127] A: Activated organic group (if present)

[0128] Due to the Friedel-Crafts reaction, it is not possible to introduce electron-deficient aromatic systems. In this respect, this reaction pathway is particularly suitable for unsubstituted or alkylated aromatic compounds or arylamines (A is N(Ar)2). At the same time, the Friedel-Crafts reaction also determines the position of any activating groups present in the para position.

[0129] In the next step, the indeno[1,2,3-jk]fluorene skeleton is constructed in an intramolecular ring-closure reaction:

[0130] Solution 3

[0131]

[0132] R: organic group (if any)

[0133] X: halogen or other reactive leaving group

[0134] A: Activated organic group (if present)

[0135] A preferred second method for preparing compounds of the invention starts with benzophenone derivatives depicted as reactants in Scheme 4. In some cases, these are commercially available; in other cases, they can be prepared from simple commercially available compounds in a few synthetic steps:

[0136] Solution 4

[0137]

[0138] R: organic group (if any)

[0139] W: organic group (if present), especially N(Ar)2

[0140] X: halogen or other reactive leaving group

[0141] In a preferred embodiment of the second method, the starting compound is constructed by a Grignard reaction on the CN group:

[0142] Option 4a

[0143]

[0144] R: organic group (if any)

[0145] W: organic group (if any)

[0146] X: halogen or other reactive leaving group

[0147] Here, the benzonitrile compound is followed by R 2 Several W groups can also form a ring, and also a fused (condensed) ring, or together form an aromatic or heteroaromatic ring system, such as carbazole. W is preferably an R2N group, wherein R is preferably identical or different and is an aryl or heteroaryl group.

[0148] In a particularly preferred embodiment of the method, the W group is an alkylamine or an arylamine. The latter can be introduced by Buchwald coupling:

[0149] Option 4b

[0150]

[0151] R: H or an organic group, preferably an aryl or heteroaryl group

[0152] X: halogen or other reactive leaving group

[0153] In a particularly preferred embodiment, the alkylamine or arylamine group is in the ortho or meta position to the nitrile group:

[0154] Option 4c:

[0155]

[0156] Compounds from Scheme 4 are reacted with substituted biphenyl compounds in a Grignard reaction:

[0157] Solution 5

[0158]

[0159] R: organic group (if any)

[0160] W: organic group (if any)

[0161] X: halogen or other reactive leaving group

[0162] In the next step, an intramolecular electrophilic reaction is used to construct the first part of the indeno[1,2,3-jk]fluorene backbone:

[0163] Solution 6

[0164]

[0165] In the next step, the indeno[1,2,3-jk]fluorene skeleton is constructed in an intramolecular ring-closure reaction under transition metal catalysis:

[0166] Solution 7:

[0167]

[0168] R: organic group (if any)

[0169] W: organic group (if present), especially N(Ar)2

[0170] X: halogen or other reactive leaving group

[0171] Since in this process of the present invention, the R of the indeno[1,2,3-jk]fluorene skeleton is not introduced by Friedel-Crafts reaction, 2 , so we can get 2 Particular preference is given to groups in the meta and ortho positions relative to the indeno[1,2,3-jk]fluorene skeleton, and particular preference is given to nitrogen substituents at these positions such as arylamines.

[0172] Solution 8:

[0173]

[0174] The synthetic methods shown above are exemplary and may be modified in an appropriate manner by one skilled in the art of organic synthesis if this is advantageous for the synthesis of a particular embodiment of the compounds of the invention.

[0175] The present invention therefore also provides a process for preparing compounds of the formula (1) or (2), characterized in that, starting from a fluorenone derivative, an addition reaction on the keto group and a preferably transition metal-catalyzed coupling reaction for ring closure to give the indeno[1,2,3-jk]fluorene skeleton are carried out.

[0176] Therefore, the present invention also provides another method for preparing a compound having an indeno[1,2,3-jk]fluorene skeleton, preferably a compound of formula (1) or (2), characterized in that a biaryl derivative is used to add the ketone group in an aromatic ketone having a leaving group at the ortho position of the ketone group, and then the indeno[1,2,3-jk]fluorene skeleton is constructed by an intramolecular electrophilic reaction, preferably a transition metal-catalyzed intramolecular coupling reaction.

[0177] The above compounds of the invention, in particular those substituted with reactive leaving groups such as bromine, iodine, chlorine, boric acid or boric esters, can be used as monomers for the preparation of the corresponding oligomers, dendrimers or polymers. Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boric acid, boric esters, amines, alkenyl or alkynyl groups with terminal C-C double bonds or C-C triple bonds, oxiranes, oxetanes, groups participating in cycloaddition reactions, for example 1,3-dipolar cycloaddition reactions, such as dienes or azides, carboxylic acid derivatives, alcohols and silanes.

[0178] The present invention therefore also provides oligomers, polymers or dendrimers comprising one or more compounds of formula (1) or (2), wherein one or more bonds to the polymer, oligomer or dendrimer may be located in the region of formula (1) where R 1 and / or R 2 The substitution can be at any desired position. According to the connection of the compounds of the invention, said compounds are part of a side chain or part of the main chain of an oligomer or polymer.

[0179] An oligomer in the context of the present invention is understood to mean a compound formed from at least three monomer units. A polymer in the context of the present invention is understood to mean a compound formed from at least ten monomer units.

[0180] The polymers, oligomers or dendrimers of the invention may be conjugated, partially conjugated or non-conjugated. The oligomers or polymers of the invention may be linear, branched or dendritic.

[0181] In structures with linear links, the units of formula (1) or (2) may be directly linked to one another, or they may be linked to one another via divalent groups, for example via substituted or unsubstituted alkylene groups, via heteroatoms or via divalent aromatic or heteroaromatic groups.

[0182] In a branched or dendritic structure, for example 3, 5 or more units of formula (1) or (2) may be linked via trivalent or higher valent groups, for example via trivalent or higher valent aromatic or heteroaromatic groups, to give a branched or dendritic oligomer or polymer.

[0183] For the recurring units of the formula (1) or (2) in oligomers, dendrimers and polymers, the same preferences apply as described above for the compounds according to the invention.

[0184] In one embodiment of the invention, the bonds to the oligomer, polymer or dendrimer are not located at both the 5- and 10-positions.

[0185] To prepare the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with further monomers. Suitable and preferred comonomers are selected from fluorene (for example according to EP 842208 or WO 2000 / 22026), spirobifluorene (for example according to EP 707020, EP 894107 or WO 2006 / 061181), p-phenylene (for example according to WO 1992 / 18552), carbazole (for example according to WO 2004 / 070772 or WO 2004 / 113468), thiophene (for example according to EP 1028136), dihydrophenanthrene (for example according to WO 2005 / 014689 or WO 2007 / 006383), cis- and trans-indenofluorene (for example according to WO 2004 / 041901 or WO 2004 / 113412), ketone (for example according to WO 2005 / 040302), phenanthrene (for example according to WO The polymers, oligomers and dendrimers generally also comprise further units, for example luminescent (fluorescent or phosphorescent) units, for example vinyltriarylamines (for example according to WO 2007 / 068325) or phosphorescent metal complexes (for example according to WO 2006 / 003000), and / or charge transport units, in particular those based on triarylamines.

[0186] The polymers, oligomers and dendrimers of the invention have advantageous properties, especially high lifetime, high efficiency and good color coordinates.

[0187] The polymers and oligomers of the invention are generally prepared by polymerization of one or more monomer types, in which at least one monomer leads to a repeating unit of formula (1) or (2) in the polymer. Suitable polymerization reactions are known to those skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions leading to CC and CN bonds are as follows:

[0188] (A) SUZUKI polymerization;

[0189] (B) YAMAMOTO polymerization;

[0190] (C) STILLE polymerization; and

[0191] (D) HARTWIG-BUCHWALD polymerization.

[0192] The manner in which the polymerization is carried out by these processes and the manner in which the polymer is subsequently isolated 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.

[0193] The invention therefore also provides a process for preparing the polymers, oligomers and dendrimers according to the invention, characterised in that they are prepared by polymerisation according to SUZUKI, polymerisation according to YAMAMOTO, polymerisation according to STILLE or polymerisation according to HARTWIG-BUCHWALD. The dendrimers according to the invention can be prepared by methods known to those skilled in the art or in a similar field. Suitable methods are described in the literature, for example in Frechet, Jean MJ; Hawker, Craig J., "Hyperbranched polyphenylene and hyperbranched polyesters: new soluble, three-dimensional, reactive polymers", Reactive & Functional Polymers (1995), 26 (1-3), 127-36; Janssen, HM; Meijer, EW, "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 / 067343A1 and WO2005 / 026144A1.

[0194] In order to process the compounds of the invention from the liquid phase, for example by spin coating or by printing methods, preparations of the compounds of the invention are required. These preparations may be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents may preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dimethoxybenzene, alkane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene Naphthalene, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or a mixture of these solvents.

[0195] The invention therefore also provides a preparation, in particular a solution, dispersion or emulsion, comprising at least one compound of the formula (1) or (2) or at least one polymer, oligomer or dendrimer comprising at least one unit of the formula (1) or (2) and at least one solvent, preferably an organic solvent. The manner in which such solutions can be prepared is known to the person skilled in the art and is described, for example, in WO 2002 / 072714, WO 2003 / 019694 and the literature cited therein.

[0196] The compounds of formula (1) or (2) are suitable for use in electronic devices, in particular in organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds are used in different functions and in different layers of organic electroluminescent devices. Preferably, the compounds are used as hole transport materials in hole transport or hole injection layers, as matrix materials in light-emitting layers, as electron blocking materials, as exciton blocking materials and / or as materials for intermediate layers.

[0197] The present invention therefore also provides the use of compounds of formula (1) or (2) in electronic devices, and provides electronic devices themselves comprising one or more compounds of formula (1) or (2). These electronic devices 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 quenching devices (O-FQDs), light emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and more preferably selected from organic electroluminescent devices (OLEDs). Particularly preferred are organic electroluminescent devices comprising an anode, a cathode and at least one light emitting layer, characterized in that at least one organic layer comprises at least one compound of formula (1) or (2), which organic layer may be a light emitting layer, a hole transport layer or another layer.

[0198] In addition to cathode, anode and light-emitting layer, the organic electroluminescent device may further include additional layers. These layers are selected from 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, China; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, multiphoton organic EL devices with charge generation layers (Multiphoton Organic EL Device Having Charge Generation Layer)) and / or organic or inorganic p / n junctions. However, it should be noted that these layers do not necessarily need to exist, and the selection of layers generally depends on the compound used and in particular also on whether the device is a fluorescent electroluminescent device or a phosphorescent electroluminescent device.

[0199] The organic electroluminescent device may further comprise several emitting layers. More preferably, in this case these emitting layers have a total of several emitting peaks between 380 nm and 750 nm, so that the overall result is white luminescence; in other words, a plurality of emitting compounds are used in the emitting layer, the compounds being fluorescent or phosphorescent and the compounds emitting blue, yellow, green, orange or red light. Particularly preferred are three-layer systems, i.e. systems having three emitting layers, wherein at least one of these layers comprises at least one compound of formula (1) or (2), and wherein the three layers exhibit blue, green and orange or red luminescence (for the basic construction, see, for example, WO 2005 / 011013). Alternatively and / or additionally, the compounds of the invention may also be present in a hole transport layer and / or in an intermediate layer. It should be noted that, in order to produce white light, instead of a plurality of emitting compounds emitting light in a specific color, a emitting compound emitting light in a wide wavelength range used alone may also be suitable.

[0200] According to the present invention, preferably the compound of formula (1) or (2) is used in an electronic device comprising one or more phosphorescent dopants. In this case, the compound can be used in different layers, preferably in a hole transport layer, a hole injection layer or a light-emitting layer. According to the present invention, the compound of formula (1) or (2) can also be used in an electronic device comprising one or more fluorescent dopants.

[0201] The term "phosphorescent dopant" generally encompasses compounds in which light emission is achieved via a spin-forbidden transition, for example a transition from an excited triplet state or a state with a higher spin quantum number, such as a quintet state.

[0202] Suitable phosphorescent dopants (=triplet emitters) are, in particular, compounds which emit light, preferably in the visible region, when suitably excited, and which furthermore comprise at least one atom having an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. Preferred phosphorescent emitters used are compounds comprising copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds comprising iridium, platinum or copper.

[0203] In the context of the present invention, all luminescent iridium, platinum or copper complexes are regarded as phosphorescent compounds.

[0204] Examples of the above-mentioned luminophores can be found in the following applications: WO 00 / 70655, WO 01 / 41512, WO 02 / 02714, WO 02 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373 and US 2005 / 0258742. In general, all phosphorescent complexes known to those skilled in the art for phosphorescent OLEDs according to the prior art and in the field of organic electroluminescent devices are suitable. Those skilled in the art can also use other phosphorescent complexes and compounds of formula (1) or (2) in organic electroluminescent devices without using creative skills.

[0205] Specific examples of suitable phosphorescent emitter compounds can also be found in the table of phosphorescent dopants shown below.

[0206] In a preferred embodiment of the invention, the compounds of the formula (1) or (2) are used as hole-transport materials. In this case, the compounds are preferably used in a hole-transport layer and / or in a hole-injection layer.

[0207] The hole injection layer in the context of the present invention is a layer directly adjacent to the anode. The hole transport layer in the context of the present invention is a layer between the hole injection layer and the light-emitting layer. The hole transport layer may be directly adjacent to the light-emitting layer. When the compounds of formula (1) or (2) are used as hole transport materials or as hole injection materials, they are preferably doped with electron acceptor compounds, for example with F4-TCNQ or with compounds described in EP 1476881 or EP 1596445. In another preferred embodiment of the present invention, the compounds of formula (1) or (2) are used as hole transport materials in combination with hexaazatriphenylene derivatives as described in US 2007 / 0092755. It is particularly preferred to use hexaazatriphenylene derivatives in a separate layer.

[0208] If the compound of the formula (1) or (2) is used as hole transport material in a hole transport layer, the compound can be used as pure material, ie in a proportion of 100%, or it can be used in the hole transport layer in combination with one or more further compounds.

[0209] In a further embodiment of the invention, the compounds of the formula (1) or (2) are used as matrix materials in combination with one or more dopants, preferably phosphorescent dopants.

[0210] A dopant in a system comprising a matrix material and a dopant is understood to mean a component having a smaller proportion in the mixture. Correspondingly, a matrix material in a system comprising a matrix material and a dopant is understood to mean a component having a larger proportion in the mixture.

[0211] In this case, the proportion of the matrix material in the light-emitting layer is between 50.0% and 99.9% by volume, preferably between 80.0% and 99.5% by volume, more preferably between 92.0% and 99.5% by volume for the fluorescent light-emitting layer, and between 85.0% and 97.0% by volume for the phosphorescent light-emitting layer.

[0212] Accordingly, the proportion of the dopant is between 0.1% and 50.0% by volume, preferably between 0.5% and 20.0% by volume, more preferably between 0.5% and 8.0% by volume for the fluorescent emitting layer, and between 3.0% and 15.0% by volume for the phosphorescent emitting layer.

[0213] The light-emitting layer of the organic electroluminescent device may also include a system containing multiple host materials (mixed host system) and / or multiple dopants. In this case as well, the dopants are usually those materials with a smaller proportion in the system, and the host materials are those materials with a larger proportion in the system. However, in individual cases, the proportion of a single host material in the system may be less than the proportion of a single dopant.

[0214] In a preferred embodiment of the invention, the compound of formula (1) or (2) is used as a component of a mixed matrix system. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. The two different matrix materials may be present in a ratio of 1:10 to 1:1, preferably in a ratio of 1:4 to 1:1.

[0215] The mixed matrix system may contain one or more dopants. According to the invention, the one or more dopant compounds together have a proportion of 0.1% to 50.0% by volume of the total mixture, preferably a proportion of 0.5% to 20.0% by volume of the total mixture. Correspondingly, the matrix component together has a proportion of 50.0% to 99.9% by volume of the total mixture, preferably a proportion of 80.0% to 99.5% by volume of the total mixture.

[0216] Preference is given to using mixed-matrix systems in phosphorescent organic electroluminescent devices.

[0217] Particularly suitable matrix materials which can be used in combination with the compounds according to the invention as matrix components of mixed-matrix systems are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 04 / 013080, WO 04 / 093207, WO 06 / 005627 or WO 10 / 006680, triarylamines, carbazole derivatives, for example CBP (N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 05 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 08 / 086851, indolocarbazole derivatives, for example according to WO 07 / 063754 or WO 08 / 056746, azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1617723 or EP 1617734. 1731584, JP 2005 / 347160, bipolar matrix materials, for example according to WO 07 / 137725, silanes, for example according to WO 05 / 111172, azaboroles or boric esters, for example according to WO 06 / 117052, triazine derivatives, for example according to applications WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes, for example according to EP 652273 or WO 09 / 062578, diazasilole and tetraazasilole derivatives, for example according to WO 10 / 054729, diazaphosphole derivatives, for example according to WO 10 / 054730, or indenocarbazole derivatives, for example according to WO 10 / 136109.

[0218] Preferred phosphorescent dopants for use in mixed-matrix systems comprising the compounds according to the invention are the phosphorescent dopants listed in the following table.

[0219] In another preferred embodiment of the present invention, the compound of formula (1) or (2) is used in the intermediate layer. The intermediate layer is preferably used in an organic electroluminescent device comprising a plurality of light-emitting layers, for example, in a white light-emitting OLED having a red light-emitting layer, a green light-emitting layer and a blue light-emitting layer. More preferably, the intermediate layer is arranged between the two light-emitting layers. In a preferred embodiment of the present invention, the intermediate layer comprising the compound of the present invention is arranged between the blue light-emitting layer and the green light-emitting layer of a white light-emitting OLED, the white light-emitting OLED comprising a red light-emitting layer, a green light-emitting layer and a blue light-emitting layer. More preferably, the blue light-emitting layer is a fluorescent layer, and the green light-emitting layer is a phosphorescent layer.

[0220] The compounds listed in the following table are particularly suitable phosphorescent emitters.

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232] Preferred fluorescent dopants are selected from the class of arylamines. Arylamines or aromatic amines in the context of the present invention are understood to mean compounds containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, more preferably a fused ring system with at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic Amine or aromatic Aromatic anthraceneamines are understood to mean compounds in which one diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are bonded directly to anthracene groups, preferably in the 9- and 10-positions. Amine or aromatic Diamines, wherein the diarylamino groups in the pyrene are preferably bonded in the 1-position or the 1,6-position. Other preferred fluorescent dopants are selected from: indenofluorenamines and indenofluorenediamines, for example according to WO 2006 / 122630, benzoindenofluorenamines and benzoindenofluorenediamines, for example according to WO 2008 / 006449, and dibenzoindenofluorenamines and dibenzoindenofluorenediamines, for example according to WO 2007 / 140847. Also preferred are the fused hydrocarbons disclosed in WO 2010 / 012328.

[0233] In addition, suitable fluorescent dopants are derivatives of these structures disclosed in JP 2006100 1973, WO 2004 / 047499, WO 2006 / 098080, WO 2007 / 065678, US 2005 / 0260442 and WO 2004 / 092111.

[0234] Preferred matrix materials for fluorescent dopants include materials from various classes of matter. Preferred matrix materials are selected from the class of oligoarylenes (e.g. 2,2′,7,7′-tetraphenylspirobifluorene according to EP 676461, or dinaphthylanthracene), in particular oligoarylenes comprising fused aromatic groups, oligoarylenevinylenes (e.g. DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (e.g. according to WO 2004 / 081017), hole-conducting compounds (e.g. according to WO 2004 / 058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides and the like (e.g. according to WO 2005 / 084081 and WO 2005 / 084082), atropisomers (e.g. according to WO 2006 / 048268), boronic acid derivatives (e.g. according to WO 2006 / 117052), or benzanthracene (e.g. according to WO 2008 / 145239). Particularly preferred matrix materials are selected from the class of oligoarylenes comprising naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, oligoarylene vinylenes, ketones, phosphine oxides and sulfoxides. Very particularly preferred matrix materials are selected from the class of oligoarylenes comprising anthracene, benzanthracene, triphenylene and / or pyrene or atropisomers of these compounds. Oligoarylenes in the context of the present invention are understood to mean compounds in which at least three aryl or arylene groups are bonded to one another.

[0235] In addition to the compounds according to the invention, preferred matrix materials for phosphorescent dopants are carbazole derivatives (for example CBP (N,N-biscarbazolylbiphenyl) or compounds according to WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851), triarylamines, azacarbazoles (for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160), indolocarbazole derivatives, for example according to WO 2007 / 063754 or WO 2008 / 056746, ketones (for example according to WO 2004 / 093207 or WO 2010 / 006680), phosphine oxides, sulfoxides and sulfones (for example according to WO 2005 / 003253), oligophenylenes, aromatic amines (for example according to US 2005 / 0069729), bipolar matrix materials (for example according to WO 07 / 137725), silanes (for example according to WO 2005 / 111172), azaboroles or boric esters, for example according to WO 2006 / 117052, triazine derivatives, for example according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes (for example according to WO 20091062578), aluminum complexes (for example BAlq), diazasilole and tetraazasilole derivatives, for example according to WO 2010 / 054730, indenocarbazole derivatives, for example according to WO 2010 / 136109 and WO 2011 / 000455, or diazaphospholes, for example according to WO 2010 / 054730.

[0236] Suitable charge transport materials which 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, in addition to the compounds 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 which are used in these layers according to the prior art.

[0237] The preferred cathode is a metal, metal alloy or multilayer structure with a low work function, which is composed of a variety of metals such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable is an alloy consisting of an alkali metal or alkaline earth metal and silver, such as an alloy consisting of magnesium and silver. In the case of a multilayer structure, in addition to the metals mentioned, other metals with a relatively high work function, such as Ag or Al, can also be used, in which case a combination of metals, such as Ca / Ag, Ba / Ag or Mg / Ag, is usually used. It is also preferred to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials that can be used for this purpose are alkali metal or alkaline earth metal fluorides, as well as corresponding oxides or carbonates (e.g. LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Hydroxyquinoline lithium (LiQ) can also be used for this purpose. The layer thickness of this layer is preferably between 0.5nm and 5nm.

[0238] Preferred anodes are materials with high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, metals with high redox potential are suitable for this purpose, such as Ag, Pt or Au. Secondly, metal / metal oxide electrodes (such as Al / Ni / NiO x 、Al / PtO x ) may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to enable the organic material to radiate (organic solar cells) or emit light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Also preferred are conductive doped organic materials, especially conductive doped polymers.

[0239] The electronic device is appropriately structured (depending on the application), contact-connected and finally sealed, since the lifetime of the device according to the invention is shortened in the presence of water and / or air.

[0240] In a preferred embodiment, the organic electroluminescent device according to the invention is characterized in that one or more layers are applied by a sublimation process. In this case, the organic electroluminescent device is applied in a vacuum sublimation system at a temperature of less than 10 -5 mbar, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of 10 mbar. However, in this case, the initial pressure may be even lower, for example less than 10 -7 millibar.

[0241] Preference is likewise given to an organic electroluminescent device, characterized in that one or more layers are applied by the OVPD (organic vapor phase deposition) method or by means of carrier gas sublimation. -5 The material is applied at a pressure between 1 mbar and 1 mbar. A special example of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and is thus structured (eg MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0242] In addition, preferred organic electroluminescent devices are characterized in that one or more layers are produced from a solution, for example by spin coating, or by any printing method such as screen printing, flexographic printing, nozzle printing or lithographic printing, but more preferably LITI (photothermography, thermal transfer printing) or inkjet printing. For this purpose, soluble compounds of formula (1) or (2) are required. High solubility can be achieved by suitable substitution of the compounds.

[0243] Preference is also given to producing the organic electroluminescent device of the invention by applying one or more layers from solution and by applying one or more layers by sublimation methods.

[0244] Organic electroluminescent devices comprising one or more compounds according to the invention can be used in displays, as light sources in lighting applications and as light sources in medical and / or cosmetic applications, for example light therapy.

[0245] A particular feature of the compounds of the invention is that, when they are used in organic electroluminescent devices, they result in good power efficiency, low operating voltage and long lifetime of the devices.

[0246] Furthermore, the compounds are oxidatively and thermally stable and have a high glass transition temperature, which is advantageous for processability, for example from solution or from the gas phase, and also for use in electronic devices.

[0247] Furthermore, the compounds have a high hole mobility, which is highly desirable in particular when used as hole transport materials or hole injection materials.

[0248] The present invention is described in detail by the following application examples, but the present invention is not limited to the scope of the examples.

[0249] Example

[0250] Unless otherwise stated, the following syntheses were performed under a protective gas atmosphere. The reactants were available from ALDRICH or ABCR (palladium(II) acetate, tri-o-tolylphosphine, inorganic materials, solvents).

[0251] Example 1: 9-(2-bromophenyl)-9H-fluoren-9-ol

[0252]

[0253] By using 70 ℃ oil bath with heating, using iodine activated magnesium turnings 2.68g (110 mmoles), and 25.9g (110 mmoles) of 1,2-dibromobenzene, 0.8mL of 1,2-dichloroethane, 50mL of 1,2-dimethoxyethane, 500mL of THF mixture, to prepare the corresponding Grignard reagent. Once the magnesium is fully reacted, the mixture is cooled to room temperature and then a solution of 18.0g (100 mmoles) of fluorenone [486-25-9] in 300mL of THF is added dropwise, and the reaction mixture is heated to 50 ℃ for 4 hours and then stirred at room temperature for another 12 hours. Add 100mL of water, stir the mixture briefly, remove the organic phase and remove the solvent under reduced pressure. Subsequently, the residue is stirred for 2 hours at 80 ℃ with 500mL of heptane. After cooling, the precipitated solid was filtered off with suction and washed once with 100 mL of heptane and twice with 100 mL of ethanol each time and finally from the two Recrystallized from oxane / EtOH. Yield: 24.6 g (73 mmol), 73%; 1 H NMR purity was about 98%.

[0254] In a similar manner, the following compounds were obtained:

[0255]

[0256]

[0257]

[0258] Example 2: Bis(biphenyl-4-yl){4-[9-(2-bromophenyl)-9H-fluoren-9-yl]phenyl}amine

[0259] 16.85 g (50 mmol) of 9-(2-bromophenyl)-9H-fluoren-9-ol and 19.88 g (50 mmol) of bis(biphenyl-4-yl)aniline [122215-84-3], 15 g (100 mmol, 8.8 mL) of trifluoromethanesulfonic acid [1493-13-6] and 300 mL of distilled water were added. The mixture of 2-(4-oxane)-1-nitropropane was heated under reflux for 24 hours. After cooling, 200 mL of water were added, the mixture was stirred for a further 30 minutes, the organic phase was removed and the latter was filtered through a short bed of Celite, and then the solvent was removed under reduced pressure. The residue was recrystallized twice from toluene / heptane. Yield: 26.1 g (36.5 mmol), 73%; according to 1 H NMR purity was about 98%.

[0260] In a similar manner, the following compounds were obtained:

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269] Example 3: 4-Biphenyl-2-(9,9′-dimethylfluorenyl)amino-3-benzonitrile

[0270] A mixture of 9.1 g (50 mmol) of 1-bromo-3-benzonitrile, 21.7 g (60 mmol) of 4-biphenyl-2-(9,9′-dimethylfluorenyl)amine [897671-69-1], 7.7 g (80 mmol) of sodium tert-butoxide, 1.4 g (5 mmol) of tricyclohexylamine, 561 mg (2.5 mmol) of palladium(II) acetate and 300 mL of mesitylene is heated under reflux for 24 hours. After cooling, 200 mL of water are added, the mixture is stirred for a further 30 minutes, the organic phase is removed and the latter is filtered through a short bed of diatomaceous earth and the solvent is then removed under reduced pressure. The residue is recrystallized five times from heptane. Yield: 16.8 g (36.5 mmol), 73%; according to 1 H NMR purity was about 98%.

[0271] In a similar manner, the following compounds were obtained:

[0272]

[0273]

[0274]

[0275] Example 4: {3-[biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amino]phenyl}-(2-bromophenyl)methanone

[0276]

[0277] The corresponding Grignard reagent was prepared by heating with iodine activated magnesium turnings 2.68 g (110 mmoles) and a mixture of 25.9 g (110 mmoles) of 1,2-dibromobenzene, 0.8 mL of 1,2-dichloroethane, 50 mL of 1,2-dimethoxyethane, and 500 mL of THF using a 70 ° C oil bath. Once the magnesium was fully reacted, the mixture was cooled to room temperature and then a solution of 46.2 g (100 mmoles) of 4-biphenyl-2-(9,9'-dimethylfluorenyl)amino-3-benzonitrile in 300 mL of THF was added dropwise, and the reaction mixture was heated to 50 ° C for 4 hours and then stirred at room temperature for another 12 hours. 100 mL of water was added, the mixture was stirred briefly, the organic phase was removed and the solvent was removed under reduced pressure. Subsequently, the residue was stirred at 80 ° C for 6 hours with 500 mL of MNP and 5 mL of acetic acid. After cooling, the precipitated solid was filtered off with suction and washed once with 100 mL of heptane and twice with 100 mL of ethanol each time and finally from the two Recrystallized from oxane / EtOH. Yield: 26.6 g (43 mmol), 39%; 1 H NMR purity was about 98%.

[0278] In a similar manner, the following compounds were obtained:

[0279]

[0280]

[0281]

[0282] Example 5: Biphenyl-4-yl-{3-[9-(2-bromophenyl)-9H-fluoren-9-yl]phenyl}-(9,9-dimethyl-9H-fluoren-2-yl)amine

[0283]

[0284] The corresponding Grignard reagent is prepared by heating with iodine activated magnesium turnings 1.4 g (55 mmoles) and a mixture of 12.9 g (55 mmoles) of 2-bromobiphenyl, 0.8 mL of 1,2-dichloroethane, 50 mL of 1,2-dimethoxyethane, 300 mL of THF and 200 mL of toluene using a 70°C oil bath. Once the magnesium is completely reacted, the mixture is cooled to room temperature and then a solution of 31.1 g (50 mmoles) of {3-[biphenyl-4-yl-(9,9-dimethyl-9H-fluorene-2-yl)amino]phenyl}-(2-bromophenyl)methanone in 400 mL of THF is added dropwise, and the reaction mixture is heated to 50°C for 4 hours and then stirred at room temperature for another 12 hours. 100 mL of water is added, the mixture is briefly stirred, the organic phase is removed and the solvent is removed under reduced pressure. The residue was suspended in 500 mL of glacial acetic acid heated to 40° C., 0.5 mL of concentrated sulfuric acid was added to the suspension, and the mixture was stirred at 100° C. for 4 hours. After cooling, the precipitated solid was filtered off with suction and washed once with 100 mL of glacial acetic acid and three times with 100 mL of ethanol each time, and finally washed with 100 mL of ethanol from the distilled water. Recrystallized from oxane. Yield: 26.9 g (28 mmol), 68%; 1 H NMR purity was about 98%.

[0285] In a similar manner, the following compounds were obtained:

[0286]

[0287]

[0288]

[0289]

[0290] Synthesis of the compounds of the present invention:

[0291] Example 6: Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(4-indeno[1,2,3-jk]fluoren-7b-ylphenyl)amine

[0292]

[0293] A mixture of 38 g (53 mmoles) of bis(biphenyl-4-yl){4-[9-(2-bromophenyl)-9H-fluorene-9-yl]phenyl}amine, 2.4 g (20 mmoles) of palladium acetate (II), 5.6 g (21.3 mmoles) of triphenylphosphine, 28.14 g (267 mmoles) of sodium carbonate, 7.26 g (32 mmoles) of benzyltriethylammonium chloride and 500 mL of N,N-dimethylacetamide was heated under reflux for 24 hours. After cooling, 200 mL of water was added, the mixture was stirred for another 30 minutes, the organic phase was removed and the latter was filtered through a short diatomaceous earth bed, and then the solvent was removed under reduced pressure. The residue was recrystallized five times from DMF / heptane and finally sublimed twice (p about 10 -6 mbar, T=320-330° C.). Yield: 14.5 g (22.8 mmol), 43%; purity: 99.9% according to HPLC.

[0294] In a similar manner, the following compounds were obtained:

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304] Part B: OLED Manufacturing

[0305] The OLEDs according to the invention and OLEDs according to the prior art are produced by the general method according to WO 04 / 058911, which is adapted to the cases described here (layer thicknesses, variation of materials).

[0306] In the following inventive examples I1 to I12 and comparative examples C1 and C2, data of various OLEDs are presented. The substrate used is a glass plate coated with structured ITO (indium tin oxide) with a thickness of 50 nm. The OLED basically has the following layer structure: substrate / p-doped hole transport layer A' (HIL1) / hole transport layer A (HTL) / p-doped hole transport layer B (HIL2) / hole transport layer C (EBL) / luminescent layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) and finally cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm. The materials required for the manufacture of OLEDs are shown in Table 1, and the structures of the various electronic devices manufactured are shown in Table 2.

[0307] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emitting layer always consists of at least one matrix material (host material) and a luminescent dopant (emitter) which is added to the matrix material or materials in a specific volume ratio by coevaporation. Details given in this form of H1:SEB (5%) mean here that the material H1 is present in the layer in a proportion of 95% by volume, while SEB is present in the layer in a proportion of 5% by volume. In an analogous manner, the electron transport layer or the hole injection layer can also consist of a mixture of two materials.

[0308] The OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in percent) were determined, which was calculated as a function of the brightness from the current-voltage-luminance characteristic (IUL characteristic) which exhibits Lambertian emission properties, as well as the lifetime. 2 The electroluminescence spectrum was determined at a brightness of 10 mA / cm and the CIE 1931 x and y color coordinates were calculated from them. 2 The EQE below refers to the EQE at 10mA / cm 2 The external quantum efficiency at a current density of 60 mA / cm2. The LD80 at 60 mA / cm2 is the initial brightness of the LED at 60 mA / cm 2 The lifetime before the constant current drops to 80% of the starting intensity.

[0309]

[0310]

[0311] Table 2: Structure of OLED

[0312]

[0313] OLED Example 1

[0314] A reference sample C1 emitting blue fluorescence was manufactured and compared with samples I1 to I7 of the present invention. 2 At a current density of 60 mA / cm, the reference sample C1 has an external quantum efficiency of 6.2% and a lifetime of 120 hours (at 60 mA / cm 2 By comparison, samples I1 (7.5%, 160 hours), I2 (7.8%, 250 hours), I3 (7.6%, 210 hours), I4 (7.4%, 200 hours), I5 (8.0%, 235 hours), I6 (7.7%, 270 hours) and I7 (7.1%, 260 hours) of the present invention have both the LD80 under 10 mA / cm 2 Better external quantum efficiency and longer lifetime at current density (60mA / cm 2 LD80 below).

[0315] OLED Example 2

[0316] A green phosphorescent reference sample C2 was manufactured and compared with samples I8 to I12 of the present invention. 2 At a current density of 20 mA / cm, the reference sample C2 has an external quantum efficiency of 11.7% and a lifetime of 80 hours (at 20 mA / cm 2 By comparison, samples I8 (17.2%, 135 hours), I9 (18.7%, 110 hours), I10 (17.4%, 145 hours), I11 (19.0%, 105 hours) and I12 (20.2%, 160 hours) of the present invention have both LD80 at 2 mA / cm 2 Better external quantum efficiency and longer lifetime at current density (20 mA / cm 2 LD80 below).

Claims

1. A compound of formula (1-5a-1) or (1-5a-2) The symbols that appear are as follows: Ar 2 Equal to formula (A-2): wherein the structure may be represented by one or more R 3 group substitution; R 1 are the same or different in each case and are H or D; R 3 are identical or different in each case and are H, D, F and an alkyl radical having 1 to 20 carbon atoms.

2. The compound according to claim 1, characterized in that R 3 are identically or differently selected from H and D.

3. The compound according to claim 1 or 2, characterized in that R 1 H and R 3 For H.

4. The compound according to claim 1 or 2, characterized in that The compound has a structure according to one of the following formulae:

5. A compound, characterized in that The compound conforms to formula (1-3c), (1-3f) or (1-5c), in: R 1 are identical or different in each case and are H, D, or a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms; R 3 are identical or different in each case and are H, D, F and an alkyl group having 1 to 20 carbon atoms; and in: R 2 According to formula (A-1), The structure of formula (A-1) may be replaced by one or more R 3 group substitution; and Ar 1 and Ar 2 is equal to formula (A-2), wherein the structure may be represented by one or more R 3 group substitution; and Ar 3 is a ring having 6 aromatic atoms and may be substituted by one or more R 3 Aromatic ring systems substituted with radicals.

6. The compound according to claim 5, characterized in that R 1 are, identically or differently, H or D or methyl, and R 3 Identically or differently H or D.

7. The compound according to claim 5 or 6, characterized in that R 1 are the same or different H or methyl, and R 3 For H.

8. The compound according to claim 5 or 6, characterized in that The compound has a structure according to one of the following formulae:

9. A method for preparing the compound according to any one of claims 1 to 8, characterized in that: The basic skeleton of formula (1-5a-1), (1-5a-2), (1-3c), (1-3f) or (1-5c) is constructed by one or more coupling reactions.

10. An oligomer or polymer, comprising one or more compounds according to any one of claims 1 to 8, characterized in that: The bond to the oligomer or polymer is located in the formula (1-5a-1), (1-5a-2), (1-3c), (1-3f) or (1-5c) where R 1 Substitute at any desired position.

11. The oligomer or polymer of claim 10, wherein the polymer is a dendrimer.

12. A formulation comprising at least one compound according to any one of claims 1 to 8 or at least one polymer or oligomer according to claim 10 and at least one solvent.

13. The formulation of claim 12, wherein the polymer is a dendrimer.

14. An electronic device comprising at least one compound according to any one of claims 1 to 8 or at least one polymer or oligomer according to claim 10.

15. The electronic device of claim 14, wherein the polymer is a dendrimer.

16. The electronic device according to claim 14, characterized in that: The electronic device is selected from the group consisting of organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quenching devices, light emitting electrochemical cells, organic laser diodes and organic electroluminescent devices.

17. The electronic device according to claim 16, wherein the electronic device is selected from an organic electroluminescent device, characterized in that: The compound according to any one of claims 1 to 8 or the polymer or oligomer according to claim 10 is used in one or more of the following functions: - used as hole transport material in a hole transport or hole injection layer, - used as hole injection material, - used as hole blocking materials, - a light emitter used as a fluorescent light-emitting layer, - used as a matrix material in a light-emitting layer, - used as electron blocking material, - Materials used as intermediate layers.

18. The electronic device of claim 17, wherein the polymer is a dendrimer.

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