Heterocyclic compounds for electronic devices

Abstract

The present invention relates to heterocyclic compounds, in particular heterocyclic compounds for use in electronic devices. The present invention also relates to a method for preparing the compounds of the present invention, and electronic devices containing the compounds.

Description

[0001] The present invention relates to heterocyclic compounds, in particular heterocyclic compounds for use in electronic devices. The present invention also relates to methods for preparing the compounds of the present invention, and electronic devices containing these compounds.

[0002] The construction of organic electroluminescent devices (OLEDs) in which organic semiconductors are used as functional materials is common knowledge in the art. The luminescent materials used are often phosphorescent organometallic complexes. For quantum mechanical reasons, up to four times the energy efficiency and power efficiency can be achieved using organometallic compounds as phosphorescent emitters. In general, there is still a need for improvements in OLEDs, especially in phosphorescent OLEDs, for example with regard to efficiency, operating voltage and lifetime.

[0003] The properties of organic electroluminescent devices are not only determined by the luminophore used. In particular, the other materials used, such as host and matrix materials, hole blocking materials, electron transport materials, hole transport materials, and electron or exciton blocking materials, are also particularly important here. Improvements in these materials can lead to significant improvements in electroluminescent devices.

[0004] According to the prior art, aromatic or heteroaromatic compounds, such as triarylamine derivatives or carbazole derivatives, are often used as matrix materials for phosphorescent compounds and as electron-transporting materials. In addition, triazine derivatives or pyrimidine derivatives are also used as matrix materials.

[0005] In general, in the case of these materials, for example when used as matrix materials, there is still a need for improvement, in particular with regard to the lifetime of the device, but also with regard to efficiency and operating voltage.

[0006] The problem addressed by the present invention was therefore to provide compounds which are suitable for use in organic electronic devices, in particular organic electroluminescent devices, and which, when used in such devices, lead to good device properties, and to provide corresponding electronic devices.

[0007] More particularly, the problem addressed by the present invention is to provide compounds which lead to a high lifetime, good efficiency and a low operating voltage.In particular, the nature of the matrix material also has a significant influence on the lifetime and efficiency of an organic electroluminescent device.

[0008] Another problem that can be considered to be solved by the present invention is to provide compounds suitable for use in phosphorescent or fluorescent OLEDs, in particular as matrix materials. A particular problem solved by the present invention is to provide matrix materials suitable for red, yellow and green phosphorescent OLEDs and also for blue phosphorescent OLEDs.

[0009] Furthermore, the compounds, in particular when they are used as matrix materials, as hole conductor materials or as electron-transport materials in organic electroluminescent devices, should lead to devices having excellent color purity.

[0010] Furthermore, the compounds should be processable in a very simple manner and, in particular, exhibit good solubility and film-forming properties. For example, the compounds should exhibit increased oxidation stability and an improved glass transition temperature.

[0011] Another object may be considered to be to provide electronic devices with excellent performance which are very cheap and of constant quality.

[0012] Furthermore, it should be possible to use or adapt the electronic device for many applications. More particularly, the performance of the electronic device should be maintained over a wide temperature range.

[0013] It has been found that, surprisingly, specific compounds described in detail below solve these problems. The use of said compounds leads to very good properties of organic electronic devices, in particular organic electroluminescent devices, in particular in terms of lifetime, color purity, efficiency and operating voltage. Therefore, the present invention provides electronic devices, in particular organic electroluminescent devices, comprising such compounds, and corresponding preferred embodiments.

[0014] Therefore, the present invention provides a compound comprising at least one structure of formula (I):

[0015]

[0016] The symbols used are as follows:

[0017] X is the same or different at each occurrence and is N or CR, preferably CR;

[0018] R a is the same or different in each occurrence and is: H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar a )2,N(R)2,C(=O)Ar a , C(=O)R 2 , P(=O)(Ar a )2,P(Ar a )2,B(Ar a )2,B(OR)2,Si(Ar a)3, Si(R)3, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted with one or more R groups, wherein one or more non-adjacent CH2 groups may be substituted with -RC=CR-, -C≡C-, Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, -O-, -Se-, -S-, C=Se, -C(=O)O-, -C(=O)NR -, C═NR, NR, P(═O)(R), SO or SO2, and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R groups, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups, or a combination of these systems; at the same time, two or more preferably adjacent R a The groups may form a ring system with each other or with the R group;

[0019] Ar a is an aromatic or heteroaromatic ring system which is identical or different at each occurrence and has 5 to 30 aromatic ring atoms and may be substituted by one or more non-aromatic R groups; at the same time, two Ar atoms bonded to the same silicon, nitrogen, phosphorus or boron atom a The groups may also be linked together by a single bond bridging group or a bridging group selected from B(R), C(R)2, Si(R)2, C=O, C=NR, C=C(R)2, O, S, Se, S=O, SO2, N(R), P(R) and P(=O)R;

[0020] R is the same or different at each occurrence and is: H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar)2, N(R 1 )2,C(=O)Ar,C(=O)R 1 ,P(=O)(Ar)2,P(Ar)2,B(Ar)2,B(OR 1 )2,Si(Ar)3,Si(R 1 )3, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 group-substituted, where one or more non-adjacent CH2 groups may be replaced by –R1 C=CR 1 -、-C≡C-、Si(R 1 )2、Ge(R 1 )2、Sn(R 1 )2. C=O, C=S, C=Se, -C(=O)O-, -C(=O)NR 1 -、C=NR 1 NR 1 ,P(=O)(R 1 ), -O-, -S-, -Se-, SO or SO2 replaced and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be replaced by one or more R 1 or having 5 to 60 aromatic ring atoms and may be substituted with one or more R 1 substituted aryloxy or heteroaryloxy groups, or having 5 to 60 aromatic ring atoms and which may be replaced by one or more R 1 substituted aralkyl or heteroaralkyl groups, or combinations of these systems; at the same time, two or more preferably adjacent R 1 The groups may form a ring system with each other;

[0021] Ar is identical or different at each occurrence and is a ring having 5 to 30 aromatic ring atoms and may be replaced by one or more non-aromatic R 1 At the same time, the two Ar groups bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom can also be connected by a single bond bridging group or a group selected from B(R 1 )、C(R 1 )2、Si(R 1 )2. C=O, C=NR 1 , C=C(R 1 )2, O, S, Se, S=O, SO2, N(R 1 )、P(R 1 ) and P(=O)R 1 The bridging bases are connected together;

[0022] R 1 is the same or different in each occurrence and is: H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar 1 )2,N(R 2 )2,C(=O)Ar 1 , C(=O)R 2 , P(=O)(Ar 1 )2,P(Ar 1 )2,B(Ar 1)2,B(OR 2 )2,Si(Ar 1 )3,Si(R 2 )3, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 )2、Ge(R 2 )2、Sn(R 2 )2. C=O, C=S, C=Se, C=NR 2 、-C(=O)O-、-C(=O)NR 2 -、NR 2 ,P(=O)(R 2 ), -O-, -S-, -Se-, SO or SO2 and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or having 5 to 40 aromatic ring atoms and in each case by one or more R 2 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 40 aromatic ring atoms and substituted by one or more R 2 an aryloxy or heteroaryloxy group substituted with a group, or having 5 to 40 aromatic ring atoms and which may be replaced by one or more R 2 substituted aralkyl or heteroaralkyl groups, or combinations of these systems; at the same time, two or more preferably adjacent R 1 The groups may form a ring system with each other;

[0023] Ar 1 is the same or different at each occurrence and has 5 to 30 aromatic ring atoms and may be replaced by one or more non-aromatic R 2 Aromatic or heteroaromatic ring system substituted with a group; at the same time, two Ar 1 The group may also be connected by a single bond bridge or selected from B(R 2 )、C(R 2 )2、Si(R 2 )2. C=O, C=NR 2 , C=C(R 2 )2, O, S, Se, S=O, SO2, N(R 2 )、P(R 2 ) and P(=O)R 2 The bridging bases are connected together;

[0024] R 2 is the same or different in each occurrence and is: H, D, F, Cl, Br, I, CN, B (OR 3 )2, NO2, C(=O)R 3 , CR 3 =C(R 3 )2,C(=O)OR 3 ,C(=O)N(R 3 )2,Si(R 3 )3, P(R 3 )2,B(R 3 )2,N(R 3 )2, NO2, P(=O)(R 3 )2, OSO2R 3 , OR 3 , S(=O)R 3 , S(=O)2R 3 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be replaced by one or more R 3 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 3 C=CR 3 -、-C≡C-、Si(R 3 )2、Ge(R 3 )2、Sn(R 3 )2. C=O, C=S, C=NR 3 、-C(=O)O-、-C(=O)NR 3 -、NR 3 ,P(=O)(R 3 ), -O-, -S-, -Se-, SO or SO2 and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or having 5 to 40 aromatic ring atoms and in each case by one or more R 3 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 40 aromatic ring atoms and substituted by one or more R 3 substituted aryloxy or heteroaryloxy groups, or combinations of these systems; at the same time, two or more preferably adjacent R 2 The substituents may also form a ring system with each other;

[0025] R 3are identical or different at each occurrence and are selected from: H, D, F, CN, aliphatic hydrocarbon radicals having 1 to 20 carbon atoms, and aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, one or more hydrogen atoms in said radicals or ring systems being replaceable by D, F, Cl, Br, I or CN and said radicals or ring systems being replaceable by one or more alkyl radicals each having 1 to 4 carbon atoms; at the same time, two or more preferably adjacent R 3 The substituents may form a ring system with each other.

[0026] The following situation is preferred: no more than one R a The group is OH, and if an R a If the group is OH, then the second R a The group is not F, Cl, Br, I or CN.

[0027] Adjacent carbon atoms in the sense of the present invention are carbon atoms that are directly bonded to each other. In addition, in the definition of groups, "adjacent groups" means that these groups are bonded to the same carbon atom or to adjacent carbon atoms. These definitions are particularly applicable to the terms "adjacent groups" and "adjacent substituents" accordingly.

[0028] Within the scope of the present description, the expression that two or more radicals together can form a ring should be understood to mean in particular that the two radicals are chemically bonded to one another with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0029]

[0030] However, in addition, the above terms should also be understood to mean that if one of the two groups is hydrogen, the second group is bound to the position to which the hydrogen atom is bonded, thereby forming a ring. This should be illustrated by the following scheme:

[0031]

[0032] The fused aryl group, fused aromatic ring system or fused heteroaromatic ring system in the sense of the present invention are groups in which two or more aromatic groups are fused to each other along a common limit, i.e., annulation, so that for example two carbon atoms belong to at least two aromatic or heteroaromatic rings, as in for example naphthalene. On the contrary, for example, fluorene is not a fused aryl group in the sense of the present invention, because the two aromatic groups in fluorene do not have a common limit. The corresponding definition is applicable to heteroaryl groups and fused ring systems, and the fused ring system can contain but need not also contain heteroatoms.

[0033] Aryl groups in the sense of the present invention contain 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms; heteroaryl groups according to the present invention contain 2 to 60 carbon atoms, preferably 2 to 40 carbon atoms, and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. Aryl groups 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 aryl or heteroaryl groups, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.

[0034] An aromatic ring system in the sense of the present invention contains 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, in the ring system. A heteroaromatic ring system in the sense of the present invention contains 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, and at least one heteroatom in the ring system, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system in the sense of the present invention is understood as meaning a system which does not necessarily contain only aryl or heteroaryl groups, but rather a plurality of aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of non-H atoms), for example carbon, nitrogen or oxygen atoms or carbonyl groups. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, stilbenes, etc. are also to be regarded as aromatic ring systems in the sense of the present invention, as are systems in which two or more aryl groups are interrupted, for example, by linear or cyclic alkyl groups or by silyl groups. In addition, systems in which two or more aryl or heteroaryl groups are directly bonded to one another, such as biphenyl, terphenyl, quaterphenyl or bipyridine, are likewise to be regarded as aromatic or heteroaromatic ring systems.

[0035] Cyclic alkyl, alkoxy or thioalkoxy groups in the sense of this invention are understood to mean monocyclic, bicyclic or polycyclic groups.

[0036] In the context of the present invention, C1- to C2-containing compounds in which individual hydrogen atoms or CH2 groups can also be replaced by the above-mentioned groups are present. 20-Alkyl groups are understood to mean, for example: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hexan-1-yl, 1,1-dimethyl-n-heptan-1-yl , 1,1-dimethyl-n-octyl, 1,1-dimethyl-n-decyl, 1,1-dimethyl-n-dodecyl, 1,1-dimethyl-n-tetradecyl, 1,1-dimethyl-n-hexadecyl, 1,1-dimethyl-n-octadecyl, 1,1-diethyl-n-hexyl, 1,1-diethyl-n-heptyl, 1,1-diethyl-n-octyl, 1,1-diethyl The alkynyl group is understood to mean, for example, ethynyl, propynyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. The alkynyl group is understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. 40 An -alkoxy group is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy.

[0037] An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, which in each case may also be substituted by the abovementioned radicals and which may be attached to the aromatic or heteroaromatic system via any desired position is understood to mean, for example, radicals derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, triphenylene, pyrene, lettuce, perylene, fluoranthene, benzofluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylylidene, terphenyl, biphenylylidene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydrophenanthrene, pyrene, pyrene, pyroxene ... Pyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, trimerized indene, isotrimerized indene, spirotrimerized indene, spiroisotrimerized 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.

[0038] In a preferred embodiment, the following situation may be preferred, that is, R aAt least one of the radicals, and preferably both, is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted in each case by one or more R radicals.

[0039] In another variant, it may be the case that R a At least one of the groups, and preferably both, is a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R groups.

[0040] In a preferred configuration, the compound of the present invention may contain at least one structure of formula (IIa), (IIb), (IIc) or (IId).

[0041]

[0042]

[0043] wherein p is 0 or 1, Y is B(R), C(R)2, Si(R)2, C=O, C=NR, C=C(R)2, O, S, Se, S=O, SO2, N(R), P(R) and P(=O)R, preferably B(R), C(R)2, Si(R)2, O, S, Se, S=O, SO2, N(R), P(R) and P(=O)R, and the symbols R and X used have the definitions given above, in particular for formula (I). If p=0, there is a bond between the aromatic or heteroaromatic rings shown.

[0044] It may be preferred that in formula (I), (IIa), (IIb), (IIc) or (IId) no more than two X groups in each ring are N; preferably at least one, more preferably at least two, of the X groups in each ring are selected from CH and CD.

[0045] Preferably, in formula (I), (IIa), (IIb), (IIc) or (IId), no more than four and preferably no more than two X groups are N; more preferably, all X groups are CR 1 , where X represents the CR 1 Preferably at most 4, more preferably at most 3 and especially preferably at most 2 of the radicals are not CH groups.

[0046] Preferably, the compounds of the present invention may comprise the structures of formula (IIIa), (IIIb), (IIIc) and / or (IIId).

[0047]

[0048]

[0049] wherein l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2, and m is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and the symbols R, Y and p used have the definitions given above, in particular for formula (I) and / or (II), wherein the sum of the indices l and m is preferably up to 6, particularly preferably up to 4, particularly preferably up to 2. If p=0, there is a bond between the aromatic rings shown.

[0050] It may also be the case that in the structures of formula (I), (IIc), (IId), (IIIc), and (IIId), R bonded to the fluorene bridging group is a or at least one of the R groups, preferably the R a or R groups, is a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, preferably 1 to 10 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, preferably 1 to 10 carbon atoms, which may be replaced by one or more R or R 1 The groups are substituted and preferably unsubstituted. Alkyl groups are preferred over alkoxy or thioalkoxy groups.

[0051] In addition, compounds having the following formula (I), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc) and / or (IIId) are preferred, wherein R a and / or at least one of the R radicals is, independently in each case, a straight-chain alkyl, alkoxy or thioalkoxy radical having 1 to 40 carbon atoms, preferably having 1 to 10 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy radical having 3 to 40 carbon atoms, preferably having 1 to 10 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, preferably having 5 to 24 aromatic ring atoms, particularly preferably having 5 to 18 aromatic ring atoms, which radical or ring system may be substituted by one or more R or R 1 The aromatic or heteroaromatic ring system is preferably substituted with 5 to 40 aromatic ring atoms, preferably with 5 to 24 aromatic ring atoms, particularly preferably with 5 to 18 aromatic ring atoms, which may be substituted with one or more R or R 1 The aryl or heteroaryl groups are preferably substituted with 5 to 40 aromatic ring atoms, preferably 5 to 24 aromatic ring atoms, and particularly preferably 5 to 18 aromatic ring atoms, which may be substituted with one or more R or R 1The radicals are substituted, very particularly preferably aryl radicals having 6 to 40 aromatic ring atoms, preferably having 5 to 24 aromatic ring atoms, particularly preferably having 5 to 18 aromatic ring atoms.

[0052] It may also be the case that the substituents R of the heteroaromatic ring systems of the formula (I), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc) and / or (IIId) do not form a fused aromatic or heteroaromatic ring system with the ring atoms of the heteroaromatic ring system, preferably do not form any fused ring system. This includes possible R groups that may be bonded to the R groups. 1 , R 2 , R 3 The substituents form a fused ring system. It is preferred that the substituents R in formula (I), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc) and / or (IIId) do not form any ring system with the ring atoms of the heteroaromatic ring system. This includes R groups that may be bonded to the R group. 1 , R 2 , R 3 The substituents form a ring system.

[0053] When two in particular can be selected from R a , R, R 1 , R 2 , R and / or R 3 When the groups of the ring system are formed with each other, the ring system may be a monocyclic or polycyclic aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system. In this case, the groups that together form the ring system may be adjacent, which means that these groups are bonded to the same carbon atom or to carbon atoms that are directly bonded to each other, or they may also be remote from each other.

[0054] In a preferred configuration, the compounds of the present invention can be represented by the structures of formula (I), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc) and / or (IIId). Therefore, preferred are compounds of formula (I), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc) and / or (IIId) structures. Preferably, the molecular weight of the compound comprising the structure of formula (I), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc) and / or (IIId) is not more than 5000 g / mole, preferably not more than 4000 g / mole, particularly preferably not more than 3000 g / mole, especially preferably not more than 2000 g / mole, and most preferably not more than 1200 g / mole.

[0055] In addition, preferred compounds of the present invention are characterized in that they are sublimable. These compounds generally have a molar mass of less than about 1200 g / mole.

[0056] In another preferred embodiment, it may be the following situation, that is, R in the structure shown above a and / or R is selected from the group consisting of phenyl, o-, m- or p-biphenyl, terphenyl, in particular branched terphenyl, quaterphenyl, in particular branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiophenyl, pyrenyl, triazine, imidazolyl, benzimidazolyl, benzo oxazolyl, benzothiazolyl, 1-, 2-, 3- or 4-carbazolyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl and / or terphenylidene, each of which, except for fluorenyl and carbazolyl, may be replaced by one or more R or R 1 The moiety is substituted, but preferably unsubstituted, particularly preferably spirobifluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene, terphenylidene moiety.

[0057] When X is CR or when the aromatic and / or heteroaromatic radical is substituted by substituents R, these substituents R are preferably selected from: H, D, F, CN, N(Ar)2, C(=O)Ar, P(=O)(Ar)2, straight-chain alkyl or alkoxy radicals having 1 to 10 carbon atoms or branched or cyclic alkyl or alkoxy radicals having 3 to 10 carbon atoms or alkenyl radicals having 2 to 10 carbon atoms, each of which may be substituted by one or more R 1 substituted with a radical, in which one or more non-adjacent CH2 groups may be replaced by O and in which one or more hydrogen atoms may be replaced by D or F, having 5 to 24 aromatic ring atoms and in each case by one or more R 1 A substituted, but preferably unsubstituted, aromatic or heteroaromatic ring system, or a substituted, but preferably unsubstituted aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms and which may be replaced by one or more R 1 At the same time, optionally, two substituents R bonded to the same carbon atom or to adjacent carbon atoms may form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more R 1 wherein Ar is identical or different on each occurrence and is an aromatic ring having 5 to 40 atoms and may be substituted by one or more R 1 Aromatic or heteroaromatic ring system substituted with 5 to 40 aromatic ring atoms and substituted with one or more R 1 substituted aryloxy radicals, or aryloxy radicals having 5 to 40 aromatic ring atoms and in each case being substituted by one or more R1 An aralkyl group substituted with a group, wherein two or more preferably adjacent R 1 The substituents may optionally form a monocyclic or polycyclic aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system, preferably a monocyclic or polycyclic aliphatic ring system, which may be substituted by one or more R 2 The symbol R 2 Ar may have the definitions given above, in particular for formula (I). Preferably, Ar is identical or different on each occurrence and is a radical having 5 to 24, preferably 5 to 12, aromatic ring atoms and may in each case be replaced by one or more R 2 The aryl or heteroaryl groups are substituted but preferably unsubstituted.

[0058] Examples of suitable Ar groups are selected from the group consisting of phenyl, o-, m- or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiophenyl, and 1-, 2-, 3- or 4-carbazolyl, each of which may be substituted by one or more R 1 The group is substituted, but is preferably unsubstituted.

[0059] More preferably, these substituents R are selected from: H, D, F, CN, N(Ar)2, straight-chain alkyl groups having 1 to 8 carbon atoms, preferably 1, 2, 3 or 4 carbon atoms, or branched or cyclic alkyl groups having 3 to 8 carbon atoms, preferably 3 or 4 carbon atoms, or alkenyl groups having 2 to 8 carbon atoms, preferably 2, 3 or 4 carbon atoms, each of which may be replaced by one or more R 1 substituted with, but preferably unsubstituted with, 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms and in each case may be replaced by one or more non-aromatic groups R 1 substituted, but preferably unsubstituted, aromatic or heteroaromatic ring system; at the same time, two substituents R bonded to the same carbon atom or to adjacent carbon atoms may optionally form a monocyclic or polycyclic aliphatic ring system, which may be substituted by one or more R 1 The group is substituted, but preferably unsubstituted, wherein Ar may have the above-mentioned definition.

[0060] Most preferably, the R substituents are selected from H and aromatic or heteroaromatic ring systems having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more non-aromatic R 1 The group is substituted, but is preferably unsubstituted.

[0061] It is preferred that the compound contains a hole transporting group, wherein R a One of the groups or one of the R groups comprises a hole transport group and is preferably a hole transport group.

[0062] In another embodiment, R a And / or one of the R groups is a group selected from the following: an arylamino group, preferably a diarylamino group or a triarylamino group, a heteroarylamino group, preferably a diheteroarylamino group or a triheteroarylamino group, a carbazole group, wherein the carbazole group is preferred. These groups can also be regarded as hole transport groups.

[0063] The case where the hole transport group comprises a group selected from the group consisting of formulae (H-1) to (H-3) and is preferably a group selected from the group consisting of formulae (H-1) to (H-3) may be preferred:

[0064]

[0065]

[0066] The dotted key indicates the connection location, and

[0067] Ar 2 ,Ar 3 ,Ar 4 Each independently is an aromatic ring system having 6 to 40 carbon atoms or a heteroaromatic ring system having 3 to 40 carbon atoms, each of which may be replaced by one or more R 1 Group substitution;

[0068] p is 0 or 1, and

[0069] W 1 is a key, C(R 1 )2、Si(R 1 )2. C=O、N-Ar 1 , BR 1 , PR 1 、POR 1 、SO、

[0070] SO2, Se, O or S, preferably C(R 1 2. N-Ar 1 , O or S, where the symbol Ar 1 and R 1 has the definitions given above, in particular for formula (I) and / or (II). Preferably, the presence of N-N bonds is excluded, so that, for example, in W 1 =NR or NAr, it is represented by p=1.

[0071] It may also be the case that the hole transport group comprises a group selected from the group consisting of formulae (H-4) to (H-26), and preferably a group selected from the group consisting of formulae (H-4) to (H-26):

[0072]

[0073]

[0074]

[0075] where Y 1 O, S, C (R 1 )2 or NAr 1 , dotted bonds indicate the connection positions, e is 0, 1, or 2, j is 0, 1, 2, or 3, h is 0, 1, 2, 3, or 4, p is 0 or 1, Ar 2 has the definitions given above, in particular for formula (H-1) or (H-2), and Ar 1 and R 1 has the definitions given above, in particular for formula (I) and / or (II).

[0076] Preferably, the presence of NN bonds is excluded, therefore, for example, in the case where Y=NAr in formulas (H-5), (H-6), (H-9), (H-12), (H-15), (H-18), (H-21), (H-24), (H-25) and (H-26), the label p is preferably 1.

[0077] Among the groups (H-1) to (H-26), preferred are carbazole groups, particularly the groups (H-4) to (H-26).

[0078] Preferably, Ar 2 The group may be combined with the aromatic or heteroaromatic group or Ar of formula (H-1) to (H-26) 2 The nitrogen atom to which the radical may be bonded forms complete conjugation.

[0079] In another preferred embodiment of the present invention, Ar 2 is an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having 6 to 12 carbon atoms, which may be replaced by one or more R 1 substituted, but preferably unsubstituted, wherein R 1 may have the definitions given above, in particular for formula (I). More preferably, Ar 2 is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which may be substituted by one or more R 1 substituted, but preferably unsubstituted, wherein R1 may have the definitions given above, in particular for formula (I).

[0080] Also preferably, the symbol Ar shown in formulas (H-1) to (H-26) 2 In particular, aryl or heteroaryl groups have 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, so that the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is bonded directly to the corresponding atom of the other group, i.e. via the atom of the aromatic or heteroaromatic group.

[0081] The compounds used as hole transport materials or host materials may also be the following: Ar shown in formulas (H-1) to (H-26): 2 The group contains an aromatic ring system with no more than two fused aromatic and / or heteroaromatic rings, preferably does not contain any fused aromatic or heteroaromatic ring system. Therefore, a naphthyl structure is preferred over anthracene structure. In addition, a fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structure is preferred over a naphthyl structure. Particularly preferred are structures without fusion, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0082] Suitable aromatic or heteroaromatic ring systems Ar 2 Examples of are selected from: o-, m- or p-phenylene, o-, m- or p-biphenylene, terphenylene, especially branched terphenylene, quaterphenylene, especially branched quaterphenylene, fluorene, spirobifluorene, dibenzofuranene, dibenzothiophene and carbazole, each of which may be substituted by one or more R 2 The group is substituted, but is preferably unsubstituted.

[0083] It is also possible that Ar shown in formulas (H-1) to (H-26) 2 In particular, the radical has not more than 1 nitrogen atom, preferably not more than 2 heteroatoms, particularly preferably not more than 1 heteroatom and especially preferably no heteroatoms.

[0084] In another preferred embodiment of the present invention, Ar 3 and / or Ar 4 is identical or different on each occurrence and is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably an aromatic ring system having 6 to 12 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 aromatic ring atoms, each of which may be replaced by one or more R 1 substituted, but preferably unsubstituted, wherein R 1 may have the definitions given above, in particular in formula (I) and / or (II). Suitable Ar 3 and / or Ar 4Examples of radicals are selected from the group consisting of phenyl, o-, m- or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiophenyl, and 1-, 2-, 3- or 4-carbazolyl, each of which may be substituted by one or more R 1 The group is substituted, but is preferably unsubstituted.

[0085] Preferably, R 1 The group does not have the same 1 The group may be bonded to an aryl or heteroaryl group Ar 1 ,Ar 2 ,Ar 3 and / or Ar 4 This includes the ring atoms that can be bonded to R 1 or R 2 Possible substituents R of the group 2 , R 3 A fused ring system is formed.

[0086] The following case may be preferred, that is, the compound contains an electron transporting group, wherein R a One of the groups or one of the R groups comprises an electron transporting group and is preferably an electron transporting group. Electron transporting groups are well known in the art and facilitate the ability of a compound to transport and / or conduct electrons.

[0087] Furthermore, compounds comprising at least one structure of Formula (I), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc), (IIId) or preferred embodiments thereof, wherein R a and / or the R group comprises at least one structure selected from pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and / or benzimidazole, with pyrimidine, triazine and quinazoline being particularly preferred.

[0088] In a preferred configuration of the present invention, it may be the following situation, that is, R a One of the groups or one of the R groups contains an electron transporting group which can be represented by formula (QL) and is preferably an electron transporting group which can be represented by formula (QL)

[0089]

[0090] Where L 1represents a bond or has 5 to 40, preferably 5 to 30 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group, and Q is an electron transporting group, wherein R 1 has the definitions given above, especially for formula (I).

[0091] Preferably, in particular, the Q group shown in formula (QL), or the electron transport group can be selected from the structures of formula (Q-1), (Q-2), (Q-3), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9) and / or (Q-10):

[0092]

[0093]

[0094] The dotted key indicates the connection position.

[0095] Q' is the same or different in each occurrence and is CR 1 or N, and

[0096] Q" is NR 1 , O or S;

[0097] where at least one Q' is N and

[0098] R 1 As defined above, especially in formula (I).

[0099] In addition, the Q group shown in formula (QL) or the electron transport group may preferably be selected from the structures of formula (Q-11), (Q-12), (Q-13), (Q-14) and / or (Q-15).

[0100]

[0101]

[0102] The symbol R 1 has the definitions given above, in particular for formula (I), X 1 Is N or CR 1 , and the dotted key indicates the connection location, where X 1 A nitrogen atom is preferred.

[0103] In another embodiment, the Q group or the electron transport group, especially shown in formula (QL), can be selected from the structures of formula (Q-16), (Q-17), (Q-18), (Q-19), (Q-20), (Q-21) and / or (Q-22):

[0104]

[0105]

[0106] The symbol R 1 With the definitions detailed above, especially for formula (I), the dashed bond marks the attachment position and m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, n is 0, 1, 2 or 3, preferably 0, 1 or 2, and o is 0, 1 or 2, preferably 1 or 2. Preferred here are the structures of formula (Q-16), (Q-17), (Q-18) and (Q-19).

[0107] In another embodiment, the Q group, or the electron transport group, particularly in formula (QL), may be selected from the structures of formula (Q-23), (Q-24) and / or (Q-25):

[0108]

[0109] The symbol R 1 has the meanings as described above, in particular for formula (I), and the dashed bond indicates the position of attachment.

[0110] In another embodiment, the Q group, or the electron transport group, particularly in formula (QL), may be selected from the structures of formula (Q-26), (Q-27), (Q-28), (Q-29) and / or (Q-30):

[0111]

[0112] The symbol Ar 1 and R 1 has the definitions given above, in particular for formula (I), X 1 Is N or CR 1 Preferably, in the structures of formula (Q-26), (Q-27) and (Q-28), exactly one X 1 It's a nitrogen atom.

[0113] Preferably, the Q group or the electron transport group, especially as shown in formula (QL), can be selected from the structures of formula (Q-31), (Q-32), (Q-33), (Q-34), (Q-35), (Q-36), (Q-37), (Q-38), (Q-39), (Q-40), (Q-41), (Q-42), (Q-43) and / or (Q-44).

[0114]

[0115]

[0116] The symbol Ar 1 and R 1 has the definitions described above, in particular for formula (I), the dashed bond marks the attachment position and m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, n is 0, 1, 2 or 3, preferably 0 or 1, n is 0, 1, 2 or 3, preferably 0, 1 or 2, and l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2.

[0117] Preferably, the symbol Ar 1 is an aryl or heteroaryl group, such that the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is directly, i.e., bonded through an atom of the aromatic or heteroaromatic group, to a corresponding atom of another group, e.g., a carbon or nitrogen atom of a group of formula (H-1) to (H-26) or (Q-16) to (Q-34) shown above.

[0118] In another preferred embodiment of the present invention, Ar 1 is identical or different on each occurrence and is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably an aromatic ring system having 6 to 12 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 aromatic ring atoms, which ring system may in each case be replaced by one or more R 2 substituted, but preferably unsubstituted, wherein R 2 may have the meanings given above, especially in formula (I). Suitable Ar 1 Examples of radicals are selected from the group consisting of phenyl, o-, m- or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiophenyl, and 1-, 2-, 3- or 4-carbazolyl, each of which may be substituted by one or more R 2 The group is substituted, but is preferably unsubstituted.

[0119] Advantageously, Ar in formula (H-1) to (H-26) or (Q-16) to (Q-34) 1 is a ring having 6 to 12 aromatic atoms and may be substituted by one or more R 2 A substituted, but preferably unsubstituted aromatic ring system, wherein R 2 may have the meanings as detailed above, especially for formula (I).

[0120] Preferably, R in formula (H-1) to (H-26) or (Q-1) to (Q-34) 1 The group does not have any heteroaryl group or the R 1The group is bonded to Ar 1 and / or Ar 2 The ring atoms of the group form a fused ring system. This includes 1 or R 2 Possible substituents R of the group 2 , R 3 A fused ring system is formed.

[0121] In a preferred configuration, it may be the case that at least one R in formula (I), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc) or (IIId) a Or the R group can be represented by the formula L 1 -Z represented by a group, wherein L 1 represents a bond or has 5 to 40, preferably 5 to 30 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a radical, Z is R 1 , Ar or formula Z a or Z b The group, where the symbols Ar and R 1 has the definitions given above, in particular for formula (I), and Z a or Z b yes

[0122]

[0123] wherein W is identical or different at each occurrence and is an aromatic ring having 5 to 30 atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system, nitrogen atom, boron atom, phosphorus atom or phosphine oxide group substituted by a radical, the dashed bond marks the position of attachment and the symbols Ar and R 1 has the definitions given above, especially for formula (I).

[0124] It may also be the case that at least one R in formula (I), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc) or (IIId) a or R groups, preferably all R a Or the R group may be represented by the formula R as detailed above and below 1 The group represented by the group.

[0125] Preferably, the compound of the present invention may comprise a structure of formula (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg), (IVh), (IVi), (IVj), (IVk), (IVl), (IVm), (IVn), (IVo), (IVp), (IVq), (IVr), (IVs), (IVt), (IVu), (IVv), (IVw), (IVx) or (IVy).

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135] wherein l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2, m is 0, 1, 2, 3, or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and n is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, and the symbol R used is 1 , L 1 and Z has the above, especially for formula (I) and / or (L 1 -Z), wherein the sum of the indices l, m and n is preferably at most 6, particularly preferably at most 4, particularly preferably at most 2.

[0136] It is also possible that in the structures of formulae (IVt) to (IVy), R bonded to the fluorene bridging group is 1 At least one of the groups, preferably the R 1 The group is a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, preferably 1 to 10 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, preferably 1 to 10 carbon atoms, which may be replaced by one or more R 2 The groups are substituted and preferably unsubstituted. Alkyl groups are preferred over alkoxy or thioalkoxy groups.

[0137] Preferably, the compound of the present invention may comprise a structure of formula (Va), (Vb), (Vc), (Vd), (Ve), (Vf), (Vg) or (Vh)

[0138]

[0139]

[0140]

[0141]

[0142] wherein m is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and n is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, and the symbol R used is 1 , L 1 and Z has the above, especially for formula (I) and / or (L 1 -Z), wherein the sum of the indices m and n is preferably at most 5, particularly preferably at most 3 and particularly preferably at most 1.

[0143] It is also possible that in the structure of formula (Vf), (Vg) or (Vh), R bonded to the fluorene bridging group is 1 At least one of the groups, preferably the R 1 The group is a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, preferably 1 to 10 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, preferably 1 to 10 carbon atoms, which may be replaced by one or more R 2 The groups are substituted and preferably unsubstituted. Alkyl groups are preferred over alkoxy or thioalkoxy groups.

[0144] Preferably, the compounds of the present invention may comprise the structures of formula (VIa), (VIb), (VIc), (VId), (VIe), (VIf), (VIg), (VIh), (VIi), (VIj), (VIk), (VIl), (VIm), (VIn), (VIo), (VIp), (VIq), (VIr), (VIs) and (VIt).

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151] wherein l is 1, 2, 3, 4 or 5, preferably 0, 1 or 2, m is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and n is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, and the symbol R used is 1 , L 1 and Z has the above, especially for formula (I) and / or (L 1 -Z), wherein the sum of the indices l, m and n is preferably at most 5, particularly preferably at most 3, particularly preferably at most 1.

[0152] It may also be the case that L in (IVa) to (IVy), (Va) to (Vh) or (VIa) to (VIt) 1 The -Z group is a hole transport group of formula (H-1) to (H-26) and / or an electron transport group of formula (QL), preferably formula (Q-1) to (Q-44).

[0153] It can also be the following situation, that is, formula L 1 The symbol Z in the structures of formulae (IVa) to (IVy), (Va) to (Vh) and / or (VIa) to (VIt) is selected from the group consisting of: 1 -90)

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160] The symbols used are as follows:

[0161] k is independently 0 or 1 at each occurrence;

[0162] i is independently 0, 1, or 2 at each occurrence;

[0163] j is independently 0, 1, 2, or 3 at each occurrence;

[0164] h is independently 0, 1, 2, 3, or 4 at each occurrence;

[0165] g is independently 0, 1, 2, 3, 4 or 5 at each occurrence; the dashed bond indicates the attachment position; and

[0166] Ar 1 , R 1 has the definitions given above, especially for formula (I).

[0167] Preferably, L 1 The group may be combined with the Q group or the Z group and the group in the formula (QL) or the group in the formula (L 1 -L in Z) 1 The atoms to which the groups are bonded form complete conjugation. Complete conjugation of the aromatic or heteroaromatic system is achieved as soon as a direct bond is formed between adjacent aromatic or heteroaromatic rings. Other connections between the aforementioned conjugated groups, for example via sulfur, nitrogen or oxygen atoms or carbonyl groups, are not detrimental to the conjugation. In the case of the fluorene system, the two aromatic rings are directly bonded, with the sp at position 9 being 3 -hybridized carbon atoms do prevent fusion of these rings, but conjugation is possible because the sp 3 -hybridized carbon atom is not necessarily located between the electron transporting Q group and the nitrogen atom. In contrast, in the case of the second spirobifluorene structure, if the Q group and L of formula (QL) 1 If the bond between the aromatic or heteroaromatic groups to which the group is bonded is through the same phenyl group in the spirobifluorene structure or through phenyl groups in the spirobifluorene structure that are directly bonded to each other and in one plane, then complete conjugation can be formed. 1 The bond between the aromatic or heteroaromatic group to which the group is bonded is through the sp at the 9-position in the second spirobifluorene structure. 3 If the -hybridized carbon atom is bonded to a different phenyl group, the conjugation is interrupted.

[0168] In another preferred embodiment of the present invention, L 1 is a bond or an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having 6 to 12 carbon atoms, which may be replaced by one or more R 1 substituted, but preferably unsubstituted, wherein R 1 may have the definitions given above, in particular for formula (I). More preferably, L 1 is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which may be substituted by one or more R 2 substituted, but preferably unsubstituted, wherein R2 may have the definitions given above, in particular for formula (I).

[0169] Also preferably, especially in formula (QL) or formula (L 1 -Z) shown in the symbol L 1 is identical or different on each occurrence and is a bond or an aryl or heteroaryl group having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, such that the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is directly bonded to the corresponding atom of the other group, i.e. bonded via an atom of the aromatic or heteroaromatic group.

[0170] Alternatively, the following may be the case, that is, in formula (QL) or formula (L 1 -Z) shown in L 1 The group contains an aromatic ring system with no more than two fused aromatic and / or heteroaromatic six-membered rings, preferably does not contain any fused aromatic or heteroaromatic ring system. Therefore, a naphthyl structure is preferred over anthracene structure. In addition, a fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structure is preferred over a naphthyl structure.

[0171] Particularly preferred are those having no condensed structures, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0172] Suitable aromatic or heteroaromatic ring systems L 1 Examples of are selected from: o-, m- or p-phenylene, o-, m- or p-biphenylene, terphenylene, especially branched terphenylene, quaterphenylene, especially branched quaterphenylene, fluorene, spirobifluorene, dibenzofuranene, dibenzothiophene and carbazole, each of which may be substituted by one or more R 1 The group is substituted, but is preferably unsubstituted.

[0173] It can also be the following situation, that is, in formula (QL) or formula (L 1 -Z) shown in L 1 In particular, the radical has not more than 1 nitrogen atom, preferably not more than 2 heteroatoms, particularly preferably not more than 1 heteroatom and more preferably no heteroatoms.

[0174] Preferred are compounds comprising at least one structure of formula (H-1) to (H-26), wherein Ar 2 The group is a bond or is selected from the formula (L 1 -1) to (L 1 -162), and / or compounds comprising the structures of formulae (IVa) to (IVy), (Va) to (Vh) and / or (VIa) to (VIp), wherein the structural unit L 1 -L in Z 1 The group is a bond or is selected from the formula (L1 -1) to (L 1 -162) groups, and / or compounds comprising the structure of formula (QL), wherein L 1 The group is a bond or is selected from the formula (L 1 -1) to (L 1 -162)

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185] wherein the dashed key in each case indicates the connection position, the label k is 0 or 1, the label l is 0, 1 or 2, the label j is independently 0, 1, 2 or 3 at each occurrence; the label h is independently 0, 1, 2, 3 or 4 at each occurrence, the label g is 0, 1, 2, 3, 4 or 5; the symbol Y 1 O, S or NR 1 , preferably O or S; and the symbol R 1 has the definitions given above, in particular for formula (I).

[0186] The following situation is preferred, that is, the formula (L 1 -1) to (L 1 The sum of the indices k, l, g, h and j in the structure of -163) is in each case at most 3, preferably at most 2, more preferably at most 1.

[0187] With the formula (QL) or (L 1 -Z) group comprises L 1 Group, the L 1 The group represents a bond or is selected from the formula (L 1 -163), (L 1 -1) to (L 1-78) and / or (L 1 -92) to (L 1 -162), preferably formula (L 1 -163), (L 1 -1) to (L 1 -54) and / or (L 1 -92) to (L 1 -162), especially preferably formula (L 1 -163), (L 1 -1) to (L 1 -29) and / or (L 1 -92) to (L 1 -162). Advantageously, in formula (L 1 -163), (L 1 -1) to (L 1 -78) and / or (L 1 -92) to (L 1 -162), preferably (L 1 -163), (L 1 -1) to (L 1 -54) and / or (L 1 -92) to (L 1 -162), the formula (L 1 -163), (L 1 -1) to (L 1 -29) and / or (L 1 -92) to (L 1 -162), the sum of the indices k, l, g, h and j may in each case be not greater than 3, preferably not greater than 2, more preferably not greater than 1.

[0188] Preferred compounds of the invention having groups of formula (H-1) to (H-26) contain Ar 2 Group, the Ar 2 The group is selected from the formula (L 1 -163), (L 1 -1) to (L 1 -78) and / or (L 1 -92) to (L 1 -162), preferably formula (L 1 -163), (L 1 -1) to (L 1 -54) and / or (L 1 -92) to (L 1 -162), especially preferably formula (L 1 -163), (L 1 -1) to (L1 -29) and / or (L 1 -92) to (L 1 -162). Advantageously, in formula (L 1 -163), (L 1 -1) to (L 1 -78) and / or (L 1 -92) to (L 1 -162), preferably (L 1 -163), (L 1 -1) to (L 1 -54) and / or (L 1 -92) to (L 1 -162), the formula (L 1 -163), (L 1 -1) to (L 1 -29) and / or (L 1 -92) to (L 1 -162), the sum of the indices k, l, g, h and j may in each case be not greater than 3, preferably not greater than 2, more preferably not greater than 1.

[0189] Preferably, the formula (L 1 -1) to (L 1 -163) 1 The group does not correspond to the R 1 The ring atoms of the aryl or heteroaryl groups to which the group is bonded form a fused aromatic or heteroaromatic ring system, preferably without forming any fused ring system. This includes the ring atoms of the aryl or heteroaryl groups to which the group may be bonded to R 1 or R 2 Possible substituents R of the group 2 , R 3 A fused ring system is formed.

[0190] It can also be the following situation, that is, Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 and / or R 1 The radical is selected from the group consisting of phenyl, o-, m- or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiophenyl, pyrenyl, triazine, imidazolyl, benzimidazolyl, benzo oxazolyl, benzothiazolyl, 1-, 2-, 3- or 4-carbazolyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl and / or terphenylidene, each of which may be replaced by one or more R 1 or R 2 The moiety may be substituted, but is preferably unsubstituted, particularly preferably phenyl, spirobifluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene, terphenylidene moiety.

[0191] It may also be the case that in the structures of Formula (I), (IIa), (IIb), (IIc), (IId), (IIIa), (IIIb), (IIIc), (IIId), (IVa) to (IVy), (Va) to (Vh) and / or (VIa) to (VIt), at least one R 1 or Ar 1 The group is selected from the formula (R 1 -1) to (R 1 -177), or in the structures of formulae (H-1) to (H-26), (Q-1) to (Q-44), (Z-1) to (Z-91), at least one Ar 1 or R 1 The group is selected from the formula (R 1 -1) to (R 1 -177)

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204] The symbols used are as follows:

[0205] Y 1 O, S or NR 2 , preferably O or S;

[0206] i is independently 0, 1, or 2 at each occurrence;

[0207] j is independently 0, 1, 2, or 3 at each occurrence;

[0208] h is independently 0, 1, 2, 3, or 4 at each occurrence;

[0209] g is independently 0, 1, 2, 3, 4, or 5 at each occurrence;

[0210] R 2 may have the definitions given above, in particular for formula (I) and / or (II), and

[0211] Dashed keys indicate connection locations.

[0212] In the above formula (R 1 -1) to (R 1 -177), preferably the structure of formula (R 1 -1) to (R 1 -64) and (R 1 -94) to (R 1 -177), particularly preferably a group of formula (R 1 -1) to (R 1 -64) and (R 1 -115) to (R 1 -177) group.

[0213] The following situation is preferred, that is, in the formula (R 1 -1) to (R 1 -177), the sum of the indices i, j, h and g is in each case not greater than 3, preferably not greater than 2, more preferably not greater than 1.

[0214] Preferably, the formula (R 1 -1) to (R 1 -177) 2 The group does not correspond to the R 2 The ring atoms of the aryl or heteroaryl groups to which the group is bonded form a fused aromatic or heteroaromatic ring system, preferably without forming any fused ring system. This includes the ring atoms of the aryl or heteroaryl groups to which the group may be bonded to the R 2 The group may have R 3 The substituents form a fused ring system.

[0215] When the compounds of the present invention are 1 or R2 When the group is substituted, especially in the case of its configuration as a host material, electron transport material or hole transport material, it is preferred when the group does not have any aryl or heteroaryl groups with more than two aromatic six-membered rings directly fused to each other. More preferably, the substituent does not have any aryl or heteroaryl groups with six-membered rings directly fused to each other at all. The reason for this preferred mode is that the triplet energy of such a structure is low. Fused aromatic groups with more than two aromatic six-membered rings directly fused to each other but still suitable according to the present invention are phenanthrene and terphenylene, because they also have a high triplet energy level.

[0216] In another preferred embodiment of the present invention, for example in the structure of formula (I) and the preferred embodiments of the structure or the structures citing these formulas, R 2 are identical or different on each occurrence and are selected from: H, D, an aliphatic hydrocarbon radical having 1 to 10 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, preferably 5 to 24 aromatic ring atoms, more preferably 5 to 13 aromatic ring atoms, which radical or ring system may be substituted by one or more alkyl radicals each having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0217] In another preferred embodiment of the present invention, for example in the structure of formula (I) and the preferred embodiments of the structure or the structures citing these formulas, R 3 are identical or different on each occurrence and are selected from: H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 10 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, preferably 5 to 24 aromatic ring atoms, more preferably 5 to 13 aromatic ring atoms, which radical or ring system may be substituted by one or more alkyl radicals each having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0218] Particularly preferred are compounds of the invention having the structures of formula (I) or (IIa) to (IId), wherein a total of not more than 4, preferably not more than 2, groups of the formula X are not CH or CD, wherein at least one R a or the R group comprises an electron transporting group, preferably a triazine group, more preferably a group of formula (QL) wherein Q is a group of formula (Q-23), or a group of formula (L) wherein Z is a group of formula (Z-48) 1 -Z) group, the compound has the following properties:

[0219]

[0220]

[0221] Also preferred are compounds of the invention having the structure of formula (IIIa), wherein p=0 and wherein the sum of the indices m is not greater than 3, preferably not greater than 2, particularly preferably 1, wherein at least one R is an electron transport group, preferably a triazine group, more preferably a group of formula (QL) wherein Q is a group of formula (Q-23), or a group of formula (L) wherein Z is a group of formula (Z-48). 1 -Z) group, the compound has the following properties:

[0222]

[0223] Particularly preferred are compounds of the invention having the structures of formula (IVa), (IVb), (IVc), preferably (IVa), or compounds having the structures of formula (Va), (Vb), (Ve), preferably (Vb), wherein the sum of the markers m and n is not greater than 3, preferably not greater than 2, and particularly preferably 0, wherein the group of formula (L1-Z) contains at least one electron transport group, preferably a triazine group, and more preferably wherein Z is a group of formula (Z-48) 1 -Z) group, the compound has the following properties:

[0224]

[0225] Examples of suitable compounds of the present invention are the following structures of Formulae 1 to 407 shown below:

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247] Preferred embodiments of the compounds of the present invention are described in detail in the examples, and these compounds can be used alone or in combination with other compounds for all purposes of the present invention.

[0248] As long as the conditions specified in the present invention are followed, the above preferred embodiments can be combined with each other as needed. In a particularly preferred embodiment of the present invention, the above preferred embodiments are adopted simultaneously.

[0249] The compounds according to the invention can in principle be prepared by various methods. However, the method described hereinafter has been found to be particularly suitable.

[0250] Therefore, the present invention also provides a method for preparing a compound comprising the structure of formula (I), wherein, in a coupling reaction, a compound comprising at least one nitrogen-containing heterocyclic group is linked to a compound comprising at least one aromatic or heteroaromatic group.

[0251] Suitable compounds containing at least one nitrogen-containing heterocyclic group are commercially available in many cases, and the starting compounds detailed in the examples can be obtained by known methods, which are therefore referred to.

[0252] Compounds containing at least one nitrogen-containing heterocyclic group can be reacted with other aryl or heteroaryl compounds by known coupling reactions, the necessary conditions for which are known to those skilled in the art, and the detailed description in the examples provides support for those skilled in the art to carry out these reactions.

[0253] Particularly suitable and preferred coupling reactions that all result in CC bond formation and / or CN bond formation are coupling reactions according to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA and HIYAMA. These reactions are well known and the examples will provide further instructions to those skilled in the art.

[0254] In all the synthetic schemes that follow, compounds with a small number of substituents are shown for the sake of structural simplicity. This does not exclude the presence of any desired additional substituents in the process.

[0255] The following schemes are exemplary implementations, and there is no intention that these will impose limitations. The constituent steps of each scheme can be combined with each other as needed.

[0256] Scenario 1:

[0257]

[0258] Scenario 2:

[0259]

[0260] Scenario 3:

[0261]

[0262] The symbols used in Schemes 1 to 3 are defined essentially the same as for Formula (I) or L 1 Those defined by -Z correspond, with numbering omitted for clarity.

[0263] The methods shown for synthesizing the compounds of the invention should be understood as examples. A person skilled in the art will be able to develop alternative synthetic routes within the scope of his general knowledge in the art.

[0264] The principles of the preparation methods detailed above are known in principle from the literature for similar compounds and can be easily adapted by a person skilled in the art for the preparation of the compounds according to the invention. Further information can be found in the examples.

[0265] By these methods, if necessary followed by purification, for example recrystallization or sublimation, high purities, preferably greater than 99% (by 1 H NMR and / or HPLC) of the compounds of the present invention comprising the structure of formula (I).

[0266] The compounds of the invention may also have suitable substituents, for example by relatively long alkyl groups (about 4 to 20 carbon atoms), especially branched alkyl groups, or optionally substituted aryl groups such as xylyl, The compounds of the present invention are substituted with a terphenyl or quaternary group, which group causes solubility in standard organic solvents, so that the compounds are soluble in toluene or xylene at room temperature, for example, in sufficient concentrations to process the compounds from solution. These soluble compounds have particularly good suitability for processing from solution, for example, by printing methods. In addition, it should be emphasized that the solubility of the compounds of the present invention comprising at least one structure of formula (I) in these solvents has been improved.

[0267] The compounds of the present invention can also be mixed with polymers. These compounds can also be covalently bonded to polymers. Compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boric acid or boric esters or reactive polymerizable groups such as olefins or oxetanes are particularly feasible. These can be used as monomers for making corresponding oligomers, dendritic macromolecules or polymers. Oligomerization or polymerization is preferably carried out by halogen functional groups or boronic acid functional groups or by polymerizable groups. It is also feasible to crosslink the polymer by such groups. The compounds of the present invention and polymers can be used in the form of crosslinked or uncrosslinked layers.

[0268] Therefore, the present invention also provides oligomers, polymers or dendrimers containing one or more structures of formula (I) or compounds of the present invention as described in detail above, wherein there are one or more bonds connecting the compounds of the present invention or structures of formula (I) to the polymers, oligomers or dendrimers. According to the connection of the structures of formula (I) or the compounds, they thus form side chains of the oligomers or polymers or are bonded within the main chain. The polymers, oligomers or dendrimers may be conjugated, partially conjugated or non-conjugated. The oligomers or polymers may be linear, branched or dendritic. With regard to the repeating units of the compounds of the present invention in the oligomers, dendrimers and polymers, the same preferences as above apply.

[0269] To prepare the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. Preference is given to copolymers in which the units of formula (I) or the preferred embodiments listed above and below are present in an amount of 0.01 mol % to 99.9 mol %, preferably 5 mol % to 90 mol %, more preferably 20 mol % to 80 mol %. Suitable and preferred comonomers forming the basic backbone of the polymer are selected from fluorene (for example according to EP 842208 or WO 2000 / 022026), spirobifluorene (for example according to EP 707020, EP 894107 or WO 2006 / 061181), p-phenylene (for example according to WO 92 / 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), 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 2004 / 070772 or WO 2004 / 113468), 2005 / 104264 or WO

[0270] 2007 / 017066) or a combination of these units. The polymers, oligomers and dendrimers may also contain other units, such as hole transport units, especially those based on triarylamines, and / or electron transport units.

[0271] Of particular interest are compounds of the invention characterized by a high glass transition temperature. In this regard, particular preference is given to compounds of the invention having a glass transition temperature of at least 70° C., more preferably at least 110° C., even more preferably at least 125° C., particularly preferably at least 150° C., determined according to DIN 51005 (2005-08 edition).

[0272] For processing the compounds of the invention from the liquid phase, for example by spin coating or by printing methods, formulations of the compounds of the invention are required. These formulations may 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, alkanes, 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, decalin, 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, hexamethylindan, or a mixture of these solvents.

[0273] Therefore, the present invention also provides a preparation comprising a compound of the present invention and at least one other compound. The other compound may be, for example, a solvent, in particular one of the above-mentioned solvents or a mixture of these solvents. Alternatively, the other compound may be at least one organic or inorganic compound, such as a luminescent compound, in particular a phosphorescent dopant, and / or other matrix material, which is also used in electronic devices. The other compound may also be polymeric.

[0274] Therefore, the present invention further provides a composition comprising a compound of the present invention and at least one other organic functional material. The functional material is generally an organic or inorganic material introduced between the anode and the cathode. Preferably, the organic functional material is selected from: a fluorescent luminescent body, a phosphorescent luminescent body, a multi-foot luminescent body, a luminescent body exhibiting TADF (thermally activated delayed fluorescence), a host material, an electron transport material, an electron injection material, a hole transport material, a hole injection material, an electron blocking material, a hole blocking material, a wide bandgap material, and an n-type dopant.

[0275] In one particular aspect of the invention, the compounds according to the invention can be employed as matrix materials, especially for phosphorescent emitters, and in many cases in combination with other matrix materials.

[0276] The present invention therefore also relates to a composition comprising at least one compound comprising the structure of formula (I) or of the preferred embodiments listed above and below and at least one further matrix material.

[0277] The invention also provides a composition comprising at least one compound having at least one structure of (I) or the preferred embodiments listed above and below and at least one wide bandgap material, a wide bandgap material being understood as a material within the meaning of the disclosure of US Pat. No. 7,294,849. These systems exhibit particularly advantageous performance data in electroluminescent devices.

[0278] Preferably, the further compound may have a band gap of 2.5 eV or higher, preferably 3.0 eV or higher, very preferably 3.5 eV or higher.One way to calculate the band gap is by the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

[0279] The molecular orbitals of the material, especially the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), their energy levels, and the energy of the lowest triplet state T1 and the energy of the lowest excited singlet state S1 are determined by quantum chemical calculations. In order to calculate organic substances, the geometry is first optimized by the "ground state / semi-empirical / default spin / AM1 / charge 0 / spin singlet" method. Subsequently, energy calculations are performed on the basis of the optimized geometry. This is performed using the "TD-SFC / DFT / default spin / B3PW91" method and the "6-31G (d)" basis set (charge 0, spin singlet). The HOMO energy level HEh and the LUMO energy level LEh are derived from energy calculations in Hartree units. This is used to determine the HOMO and LUMO energy levels in electron volts as follows, calibrated by cyclic voltammetry measurements:

[0280] HOMO(eV)=((HEh*27.212)-0.9899) / 1.1206

[0281] LUMO(eV)=((LEh*27.212)-2.0041) / 1.385

[0282] In the sense of this application, these values ​​are to be regarded as the HOMO and LUMO energy levels of the material.

[0283] The lowest triplet state T1 is defined as the energy of the triplet state with the lowest energy, which is clear from the described quantum chemical calculations.

[0284] The lowest excited singlet state S1 is defined as the energy of the excited singlet state with the lowest energy, which is clear from the described quantum chemical calculations.

[0285] The method described herein is independent of the software package used and always gives the same results. Examples of programs frequently used for this purpose are "Gaussian09W" (Gaussian Corporation) and Q-Chem 4.1 (Q-Chem Corporation).

[0286] The present invention furthermore relates to a composition comprising at least one compound comprising the structure of the formula (I) or of the preferred embodiments listed above and below and at least one phosphorescent emitter, the term "phosphorescent emitter" also being understood to mean a phosphorescent dopant.

[0287] The term "doping agent" in a system comprising a matrix material and a doping agent is understood to mean the component with the smaller proportion in the mixture. Correspondingly, the term "matrix material" in a system comprising a matrix material and a doping agent is understood to mean the component with the larger proportion in the mixture.

[0288] Preferred phosphorescent dopants for use in matrix systems, preferably mixed-matrix systems, are the preferred phosphorescent dopants specified below.

[0289] The term "phosphorescent dopant" generally includes compounds that emit light via a spin-forbidden transition, for example, from an excited triplet state or a state with a higher spin quantum number, such as a quintet state.

[0290] Suitable phosphorescent compounds (=triplet emitters) are especially compounds which, when suitably excited, emit light preferably in the visible region and which also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially a metal with this atomic number. Preferably used phosphorescent emitters are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium or platinum. In the sense of the present invention, all emitting compounds containing the abovementioned metals are regarded as phosphorescent compounds.

[0291] Examples of the above-mentioned emitters can be found in the following applications: WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626, WO 2011 / 066898, WO 2011 / 157339, WO 2012 / 007086, WO 2014 / 008982, WO 2014 / 023377, WO 2014 / 094961, WO 2014 / 094960, WO 2016 / 124304, WO 2016 / 015815, WO 2016 / 000803, WO 2015117718, WO 2015104045, and WO 2015036074. In general, all phosphorescent complexes which are used in phosphorescent OLEDs according to the prior art and are known to those skilled in the art in the field of organic electroluminescence are suitable, and the skilled person will be able to use other phosphorescent complexes without inventive step.

[0292] Specific examples of phosphorescent dopants are listed in the following table:

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304] In a particular aspect of the present invention, the compounds of the present invention can be used as hole blocking materials, preferably in a hole blocking layer, in which case the compounds of the present invention used as hole blocking materials comprise at least one electron transporting group. In a preferred embodiment, the compounds of the present invention used as hole blocking materials comprise less hole transporting groups than electron transporting groups, more preferably no hole transporting groups.

[0305] It may also be the case that the compound of the present invention is used as an electron or exciton blocking material, preferably in an electron or exciton blocking layer, in which case the compound of the present invention used as an electron or exciton blocking material comprises at least one hole transporting group. In a preferred embodiment, the compound of the present invention used as an electron or exciton blocking material comprises less electron transporting groups than hole transporting groups, more preferably no electron transporting groups, as shown above and below by R a Or an electron transport group defined by formula (QL) of the R group.

[0306] The above-mentioned compounds comprising the structure of formula (I) or the preferred embodiments detailed above can preferably be used as active components in electronic devices. An electronic device is understood to mean any device comprising an anode, a cathode and at least one layer between the anode and the cathode, the layer comprising at least one organic compound or organometallic compound. The electronic device of the present invention therefore comprises an anode, a cathode and at least one intermediate layer, the intermediate layer containing at least one compound comprising the structure of formula (I). Preferred electronic devices are selected from the group consisting of organic electroluminescent devices (OLED, PLED), organic integrated circuits (O-IC), organic field effect transistors (O-FET), organic thin film transistors (O-TFT), organic light emitting transistors (O-LET), organic solar cells (O-SC), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQD), organic electrosensors, light emitting electrochemical cells (LEC), organic laser diodes (O-lasers) and organic plasma light emitting devices (DM Koller et al., Nature Photonics 2008, 1-4), preferably organic electroluminescent devices (OLED, PLED), especially phosphorescent OLEDs, which contain at least one compound comprising a structure of formula (I) in at least one layer. Particularly preferred are organic electroluminescent devices. Active components are usually organic or inorganic materials introduced between anode and cathode, such as charge injection, charge transport or charge blocking materials, but in particular luminescent materials and matrix materials.

[0307] A preferred embodiment of the present invention is an organic electroluminescent device. The organic electroluminescent device comprises a cathode, an anode, and at least one luminescent layer. In addition to these layers, it may also comprise other layers, such as one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers and / or organic or inorganic p / n junctions in each case. At the same time, one or more hole transport layers may be p-type doped, such as with metal oxides such as MoO3 or WO3 or doped with (per) fluorinated electron-poor aromatic systems, and / or one or more electron transport layers are n-type doped. Intermediate layers may also be introduced between two luminescent layers, which intermediate layers have, for example, exciton blocking functions and / or control the charge balance in the electroluminescent device. However, it should be noted that each of these layers does not necessarily need to exist.

[0308] In this case, the organic electroluminescent device may contain one emitting layer, or it may contain a plurality of emitting layers. If a plurality of emitting layers are present, these emitting layers preferably have a plurality of emitting peaks generally between 380 nm and 750 nm, so that the overall result is white emitting light; in other words, a plurality of emitting compounds that can fluoresce or phosphoresce are used in the emitting layer. Particularly preferred are three-layer systems, in which the three layers exhibit blue, green and orange or red emission (for the basic structure, see, for example, WO 2005 / 011013); or systems with more than three emitting layers. The system may also be a mixed system in which one or more layers fluoresce and one or more other layers phosphoresce.

[0309] In a preferred embodiment of the present invention, the organic electroluminescent device contains a compound of the present invention comprising the structure of formula (I) or the preferred embodiment described in detail above as a matrix material in one or more emitting layers, preferably as an electron-conducting matrix material, preferably in combination with other matrix materials, preferably hole-conducting matrix materials. The emitting layer comprises at least one emitting compound. In another preferred embodiment, the other matrix material is a compound with a large band gap, which does not participate to a significant extent in the transport of holes and electrons in the layer, even if it participates. In another preferred embodiment of the present invention, the compound of the present invention comprising the structure of formula (I) or the preferred embodiment described in detail above is present as a matrix material in one or more emitting layers, preferably as a hole-conducting matrix material, preferably in combination with other matrix materials, preferably electron-conducting matrix materials.

[0310] Suitable matrix materials which can be used in combination with the compounds of formula (I) or according to the preferred embodiments are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triarylamines, in particular monoamines, for example according to WO 2014 / 015935, carbazole derivatives, for example CBP (N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851, indolocarbazole derivatives, for example according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, for example according to WO 2010 / 136109 and WO 2011 / 000455, azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, for example according to WO 2007 / 137725, silanes, for example according to WO 005 / 111172, borazolidines or boric acid 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 EP 652273 or WO 2009 / 062578, siladiazolidine or siladiazolidine derivatives, for example according to WO 2010 / 054729, phosphodiazolidine derivatives, for example according to WO 2010 / 054730, bridged carbazole derivatives, for example according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107, WO 2011 / 088877 or WO 2012 / 143080, terphenylidene derivatives, for example according to WO 2012 / 048781, lactams, for example according to WO 2011 / 116865, WO 2011 / 137951 or WO 2013 / 064206, or 4-spirocarbazole derivatives, for example according to WO 2014 / 094963 or the as yet unpublished application EP 14002104.9. Other phosphorescent emitters which emit at a shorter wavelength than the actual emitter may also be present as cohosts in the mixture.

[0311] Preferred co-host materials are triarylamine derivatives, especially monoamines, indenocarbazole derivatives, 4-spirocarbazole derivatives, lactams, and carbazole derivatives.

[0312] Preferred triarylamine derivatives used as co-host materials with the compounds of the present invention are selected from the compounds of the following formula (TA-1):

[0313]

[0314] Among them, Ar 1 are identical or different at each occurrence and have 6 to 40 carbon atoms and may be replaced in each case by one or more R 2 Aromatic or heteroaromatic ring system substituted with 5 to 60 aromatic ring atoms and substituted with one or more R 2 substituted aryloxy radicals, or having 5 to 60 aromatic ring atoms and in each case being substituted by one or more R 2 A substituted aralkyl group wherein two or more adjacent R 2 The substituents may optionally form a monocyclic or polycyclic aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system, preferably a monocyclic or polycyclic aliphatic ring system, which may be substituted by one or more R 3 The symbol R 2 has the meanings given above, in particular for formula (I). Preferably, Ar 1 is identical or different on each occurrence and is a radical having 5 to 24, preferably 5 to 12, aromatic ring atoms and which can be replaced in each case by one or more R 2 The aryl or heteroaryl groups are substituted but preferably unsubstituted.

[0315] Suitable Ar 1 Examples of radicals are selected from the group consisting of phenyl, o-, m- or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiophenyl, and 1-, 2-, 3- or 4-carbazolyl, each of which may be substituted by one or more R 2 The group is substituted, but is preferably unsubstituted.

[0316] Preferably, Ar 1 The group is the same or different at each occurrence and is selected from the above R 1 -1 to R 1 -177 group, more preferably R 1 -1 to R 1 -64.

[0317] In a preferred embodiment of the compound of formula (TA-1), at least one Ar 1The group is selected from biphenyl groups, which may be o-, m- or p-biphenyl groups. In another preferred embodiment of the compound of formula (TA-1), at least one Ar 1 The group is selected from a fluorene group or a spirobifluorene group, wherein these groups can each be bonded to the nitrogen atom at the 1, 2, 3 or 4 position. In another preferred embodiment of the compound of formula (TA-1), at least one Ar 1 The group is selected from a benzylidene or biphenyl group, wherein the group is an ortho-, meta- or para-bonded group, substituted by a dibenzofuran group, a dibenzothiophene group or a carbazole group, especially a dibenzofuran group, wherein the dibenzofuran or dibenzothiophene group is bonded to the benzylidene or biphenyl group via the 1, 2, 3 or 4 position, and wherein the carbazole group is bonded to the benzylidene or biphenyl group via the 1, 2, 3 or 4 position or via a nitrogen atom.

[0318] In a particularly preferred embodiment of the compound of formula (TA-1), one Ar 1 The group is selected from fluorene or spirobifluorene groups, especially 4-fluorene or 4-spirobifluorene groups, and one Ar 1 The group is selected from a biphenyl group, especially a p-biphenyl group, or a fluorene group, especially a 2-fluorene group, and the third Ar 1 The radical is selected from a p-phenylene group or a p-biphenylene group substituted by a dibenzofuran group, especially a 4-dibenzofuran group, or a carbazole group, especially an N-carbazole group or a 3-carbazole group.

[0319] In a preferred embodiment, the co-host material is a carbazole compound, and it is particularly preferred when the carbazole compound is a biscarbazole or triscarbazole compound, and it is very particularly preferred when the carbazole compound is selected from the compounds of the following structures:

[0320]

[0321]

[0322]

[0323] Preferred indenocarbazole derivatives used as co-host materials together with the compounds of the present invention are selected from the compounds of the following formula (TA-2):

[0324]

[0325] Among them, Ar 1 and R 1 has the meanings given above, in particular for formula (I) and / or (TA-1). 1 A preferred embodiment of the group is the above structure R 1 -1 to R1 -177, more preferably R 1 -1 to R 1 -64.

[0326] A preferred embodiment of the compound of formula (TA-2) is a compound of the following formula (TA-2a):

[0327]

[0328] Among them, Ar 1 and R 1 has the meanings given above, in particular for formula (I) and / or (TA-1). The two R bonded to the indene carbon atom 1 The radicals here are preferably identical or different and are alkyl radicals having 1 to 4 carbon atoms, in particular methyl radicals, or aromatic ring systems having 6 to 12 carbon atoms, in particular phenyl radicals. More preferably, the two R 1 It is also preferred that R bonded to the indenocarbazole basic skeleton in formula (TA-2a) 1 The substituent is H or a carbazole group which can be bonded to the indenocarbazole basic skeleton via the 1, 2, 3 or 4 position or via the nitrogen atom, in particular via the 3 position.

[0329] Other preferred indenocarbazoles as co-hosts are those disclosed in WO 2010 / 136109 and WO 2013 / 041176.

[0330] Preferred 4-spirocarbazole derivatives used as co-host materials together with the compounds of the present invention are selected from the compounds of the following formula (TA-3):

[0331]

[0332] Among them, Ar 1 and R 1 has the meanings given above, in particular for formula (I), (II) and / or (Q-1). 1 A preferred embodiment of the group is the above structure R 1 -1 to R 1 -177, more preferably R 1 -1 to R 1 -64.

[0333] A preferred embodiment of the compound of formula (TA-3) is a compound of the following formula (TA-3a):

[0334]

[0335] Among them, Ar 1 and R 1has the meanings given above, in particular for formula (I), (II) and / or (Q-1). 1 A preferred embodiment of the group is the above structure R 1 -1 to R 1 -177, more preferably R 1 -1 to R 1 -64.

[0336] Preferred co-host materials are also those which contain carbazole groups in addition to triazine groups, particularly preferably when the two groups are bridged via dibenzofuran or dibenzothiophene. Very particularly preferred co-host materials having triazine-dibenzofuran / dibenzothiophene-carbazole structural units are disclosed in WO 2015 / 169412.

[0337] Preferred lactams used as co-host materials with the compounds of the present invention are selected from compounds of the following formula (LAC-1):

[0338]

[0339] Where R 1 has the meanings as described above, in particular for formula (I).

[0340] A preferred embodiment of the compound of formula (LAC-1) is the compound of the following formula (LAC-1a):

[0341]

[0342] Where R 1 has the meanings given above, in particular for formula (I). 1 is preferably identical or different on each occurrence and is H or has 5 to 40 aromatic ring atoms and may be replaced by one or more R 2 Aromatic or heteroaromatic ring system substituted with a radical, wherein R 2 may have the definitions given above, in particular for formula (I). Most preferably, R 1 The substituents are selected from H and aromatic or heteroaromatic ring systems having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, and which may in each case be replaced by one or more non-aromatic R 2 The group is substituted, but preferably is unsubstituted. Suitable R 1Examples of substituents are selected from the group consisting of phenyl, o-, m- or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothiophenyl, and 1-, 2-, 3- or 4-carbazolyl, each of which may be substituted by one or more R 2 The group is substituted, but preferably is unsubstituted. Suitable R 1 The structure is the same as above for R-1 to R-177, more preferably R 1 -1 to R 1 -The same structure as described in -64.

[0343] It is also preferred to use a plurality of different matrix materials as a mixture, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material. It is also preferred to use a mixture of a charge-transporting matrix material and an electrically inert matrix material which, even if it participates in charge transport, does not participate to a significant level, as described, for example, in WO 2010 / 108579.

[0344] Preference is also given to using a mixture of two or more triplet emitters together with a matrix. In this case, the triplet emitter with a shorter-wave emission spectrum serves as a co-matrix for the triplet emitter with a longer-wave emission spectrum.

[0345] More preferably, in a preferred embodiment, the compounds of the present invention comprising the structure of formula (I) can be used as a matrix material in the light-emitting layer of an organic electronic device, especially an organic electroluminescent device, such as an OLED or OLEC. In this case, the matrix material containing the compound comprising the structure of formula (I) or the preferred embodiments listed above and below is present in combination with one or more dopants, preferably phosphorescent dopants, in the electronic device.

[0346] In this case, the proportion of the matrix material in the 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 a fluorescent emitting layer, and between 85.0 and 97.0% by volume for a phosphorescent emitting layer.

[0347] 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 light-emitting layer, and between 3.0% and 15.0% by volume for the phosphorescent light-emitting layer.

[0348] The light-emitting layer of the organic electroluminescent device may also comprise a system containing a plurality of matrix materials (mixed matrix system) and / or a plurality of dopants. Also in this case, the dopants are usually those materials with a smaller proportion in the system, and the matrix materials are those materials with a larger proportion in the system. However, in individual cases, the proportion of a single matrix material in the system may be less than the proportion of a single dopant.

[0349] In another preferred embodiment of the present invention, the compound comprising the structure of the preferred embodiment of formula (I) or the context 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. Preferably, in this case, one of the two materials is a material with hole transport properties, and the other material is a material with electron transport properties. However, the desired electron transport and hole transport properties of the mixed matrix component can also be mainly or completely merged in a single mixed matrix component, in which case other mixed matrix components perform other functions. The two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, most preferably 1:4 to 1:1. Preferably, a mixed matrix system is used in a phosphorescent organic electroluminescent device. A source of more detailed information about mixed matrix systems is application WO 2010 / 108579.

[0350] The invention further provides an electronic device, preferably an organic electroluminescent device, comprising one or more compounds according to the invention and / or at least one oligomer, polymer or dendrimer according to the invention as hole-conducting compound in one or more hole-conducting layers.

[0351] In a preferred embodiment of the invention, the organic electroluminescent device contains a compound according to the invention comprising the formula (I) or the structure of the preferred embodiments detailed above and / or at least one oligomer, polymer or dendrimer according to the invention as electron-conducting compound in the electron-conducting layer.

[0352] The present invention also provides an electronic device, preferably an organic electroluminescent device, which contains one or more compounds of the present invention and / or at least one oligomer, polymer or dendrimer of the present invention in one or more electron transport layers, preferably in combination with a material having a high dielectric constant such as an alkali metal or alkaline earth metal fluoride, and the corresponding oxide or carbonate (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.) or an organic alkali metal complex such as Liq (lithium quinolate), particularly preferably an organic alkali metal complex, preferably Liq and a compound of the present invention and / or an oligomer, polymer or dendrimer of the present invention. The two different materials described here can be present in the electron transport layer in a ratio of 1:50 to 50:1, preferably 1:10 to 10:1, more preferably 1:4 to 4:1, and most preferably 1:2 to 2:1.

[0353] The invention further provides an electronic device, preferably an organic electroluminescent device, which comprises one or more compounds according to the invention and / or at least one oligomer, polymer or dendrimer according to the invention as matrix material in the emitting layer, preferably in combination with a phosphorescent emitter.

[0354] Preferred cathodes are metals, metal alloys or multilayer structures with low work functions, which are composed of various metals such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). In addition, alloys composed of alkali metals or alkaline earth metals and silver are suitable, such as alloys composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, other metals such as Ag with relatively high work functions can also be used, in which case combinations of the metals such as Mg / Ag, Ca / Ag or Ba / Ag are usually used. A thin intermediate layer of a material with a high dielectric constant can also be preferably introduced between a metal cathode and an organic semiconductor. Examples of useful materials for this purpose are fluorides of alkali metals or alkaline earth metals, and corresponding oxides or carbonates (e.g. LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Also useful for this purpose are organic alkali metal complexes such as Liq (lithium quinoline). The layer thickness of this layer is preferably between 0.5 nm and 5 nm.

[0355] Preferred anodes are materials with a high work function. Preferably, the anode has a work function of greater than 4.5 eV relative to vacuum. Firstly, metals with a high redox potential, such as Ag, Pt or Au, are suitable for this purpose. Secondly, metal / metal oxide electrodes (such as Al / Ni / NiO x 、Al / PtO x). For some applications, at least one of the electrodes must be transparent or partially transparent in order to enable irradiation of organic materials (O-SC) or emission of light (OLED / PLED, O-laser). Preferred anode materials here are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive doped organic materials, in particular conductive doped polymers, such as PEDOT, PANI or derivatives of these polymers. It is also preferred when a p-doped hole transport material is applied to the anode as a hole injection layer, in which case suitable p-type dopants are metal oxides, for example, MoO3 or WO3 or (per) fluorinated electron-poor aromatic systems. Other suitable p-type dopants are HAT-CN (hexacyanohexaazatriphenylene) or the compound NPD9 from Novaled. Such a layer simplifies hole injection in materials with a low HOMO, i.e. a HOMO that is large in magnitude.

[0356] In the other layers, generally any materials as used in the prior art for said layers can be used, and a person skilled in the art will be able to combine any of these materials with the materials of the invention in an electronic device without inventive step.

[0357] Since the lifetime of such components is severely shortened in the presence of water and / or air, the components are structured accordingly (depending on the application), provided with contact connections and finally hermetically sealed.

[0358] Also preferred is an electronic device, in particular an organic electroluminescent device, characterized in that one or more layers are applied by a sublimation process. In this case, the sublimation reaction is carried out in a vacuum sublimation system at a temperature of typically less than 10 -5 mbar, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of 10 mbar. The initial pressure can also be even lower or even higher, for example less than 10 -7 millibar.

[0359] Likewise preferred is an electronic device, in particular an organic electroluminescent device, characterized in that one or more layers are applied by the OVPD (organic vapor phase deposition) method or by sublimation with the aid of a carrier gas. -5 The material is applied at a pressure between mbar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jet) method, in which the material is applied directly through a nozzle and thereby structured (eg MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0360] Also preferred are electronic devices, especially organic electroluminescent devices, as described below, characterized in that one or more layers are produced from solution, for example by spin coating, or by any printing method, such as screen printing, flexographic printing, offset printing or nozzle printing, but more preferably LITI (light-induced thermal imaging, thermal transfer) or inkjet printing. For this purpose, soluble compounds are required, which are obtained, for example, by appropriate substitution.

[0361] Electronic devices, especially organic electroluminescent devices, can also be manufactured as hybrid systems by applying one or more layers from a solution and applying one or more other layers by vapor deposition. For example, a light-emitting layer comprising a compound of the invention having a structure of formula (I) and a matrix material can be applied from a solution, and a hole blocking layer and / or an electron transport layer can be applied thereto by vapor deposition under reduced pressure.

[0362] These methods are generally known to those skilled in the art and can be applied without difficulty to electronic devices, especially organic electroluminescent devices, comprising compounds of the present invention having a structure comprising formula (I) or the preferred embodiments detailed above.

[0363] It is noteworthy that the electronic device of the present invention, especially the organic electroluminescent device, is superior to the prior art in one or more of the following surprising advantages:

[0364] 1. Electronic devices, especially organic electroluminescent devices, comprising compounds, oligomers, polymers or dendrimers having a structure of formula (I) or of the preferred embodiments listed above and below, especially as host materials or as electron-conducting materials and / or hole-conducting materials, have very good lifetimes. In this case, these compounds especially produce low roll-off, i.e. the power efficiency of the device decreases less at high brightness.

[0365] 2. An electronic device, especially an organic electroluminescent device, comprising a compound, oligomer, polymer or dendrimer having a structure of formula (I) or the preferred embodiments listed above and below as an electron-conducting material, a hole-conducting material and / or a host material, having excellent efficiency. In this case, the compound, oligomer, polymer or dendrimer of the present invention having a structure of formula (I) or the preferred embodiments listed above and below, when used in an electronic device, produces a low operating voltage.

[0366] 3. The compounds, oligomers, polymers or dendrimers of the invention having the structure of formula (I) or the preferred embodiments listed above and below show high stability and longevity.

[0367] 4. With compounds, oligomers, polymers or dendrimers having the structure of formula (I) or the preferred embodiments listed above and below, the formation of light loss channels in electronic devices, especially organic electroluminescent devices, can be avoided. As a result, these devices are characterized by high PL efficiency of the emitter and the resulting high EL efficiency, and excellent energy transfer from the host to the dopant.

[0368] 5. The use of compounds, oligomers, polymers or dendrimers having the structure of the formula (I) or of the preferred embodiments listed above and below in layers of electronic devices, especially organic electroluminescent devices, leads to high mobility of the electron-conducting structures.

[0369] 6. Compounds, oligomers, polymers or dendrimers having the structure of formula (I) or the preferred embodiments listed above and below are characterized by excellent thermal stability and good sublimation properties for compounds with a molar mass of less than about 1200 g / mole.

[0370] 7. The compound, oligomer, polymer or dendrimer having the structure of formula (I) or the preferred embodiments listed above and below has excellent glass film forming properties.

[0371] 8. The compounds, oligomers, polymers or dendrimers having the structure of formula (I) or the preferred embodiments listed above and below form good films from solution.

[0372] 9. The compounds, oligomers, polymers or dendrimers comprising the structure of formula (I) or of the preferred embodiments listed above and below have a surprisingly high triplet energy level T1.

[0373] These aforementioned advantages are not accompanied by degradation of other electronic properties.

[0374] The compounds and mixtures according to the invention are suitable for use in electronic devices. An electronic device is understood here to mean a device which comprises at least one layer which contains at least one organic compound. However, the component may also comprise inorganic materials or layers which are formed completely from inorganic materials.

[0375] The present invention therefore also provides for the use of the compounds or mixtures according to the invention in electronic devices, especially in organic electroluminescent devices.

[0376] The present invention further provides the use of the compounds of the present invention and / or the oligomers, polymers or dendrimers of the present invention as host materials, electron transport materials and / or hole transport materials of phosphorescent emitters in organic devices, preferably as host materials of red or green phosphorescent compounds or as electron transport materials in organic electroluminescent devices with fluorescent emitters.

[0377] The invention further provides the use of a compound according to the invention and / or an oligomer, polymer or dendrimer according to the invention as part of an electron transport layer in an electronic device, in particular in combination with a material having a high dielectric constant.

[0378] The present invention further provides an electronic device comprising at least one of the compounds or mixtures of the present invention described in detail above. In this case, the preferred embodiments described above for the compounds also apply to the electronic device. More preferably, the electronic device is selected from: organic electroluminescent devices (OLED, PLED), organic integrated circuits (O-IC), organic field effect transistors (O-FET), organic thin film transistors (O-TFT), organic light emitting transistors (O-LET), organic solar cells (O-SC), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQD), organic electrical sensors, light emitting electrochemical cells (LEC), organic laser diodes (O-lasers) and organic plasma light emitting devices (DM Koller et al., Nature Photonics (Nature Photonics) 2008, 1-4), preferably organic electroluminescent devices (OLED, PLED), especially phosphorescent OLEDs.

[0379] In another embodiment of the invention, the organic electroluminescent device according to the invention does not contain any separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, which means that the light-emitting layer is directly adjacent to the hole injection layer or the anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051. In addition, metal complexes identical or similar to the metal complexes in the light-emitting layer can be used as hole transport or hole injection materials directly adjacent to the light-emitting layer, as described, for example, in WO 2009 / 030981.

[0380] In other layers of the organic electroluminescent device of the present invention, any material can be used as commonly used in the prior art. Therefore, those skilled in the art can use any material known for organic electroluminescent devices in combination with formula (I) or the compounds of the present invention according to a preferred embodiment without creative effort.

[0381] The compounds of the invention generally have very good properties when used in organic electroluminescent devices. In particular, when the compounds of the invention are used in organic electroluminescent devices, the lifetime is significantly better compared to similar compounds of the prior art. At the same time, other properties of the organic electroluminescent device, in particular efficiency and voltage, are also better or at least comparable.

[0382] It should be noted that variations of the embodiments described in the present invention are covered by the scope of the present invention. Unless explicitly excluded, any feature disclosed in the present invention can be replaced with an alternative feature serving the same purpose or an equivalent or similar purpose. Therefore, unless otherwise specified, any feature disclosed in the present invention should be considered as an example of a generic series or as an equivalent or similar feature.

[0383] All features of the present invention can be combined with each other in any way, unless specific features and / or steps are mutually exclusive. This is especially true for the preferred features of the present invention. Similarly, features of non-essential combinations can be used separately (without combination).

[0384] It should also be noted that many features, especially those of the preferred embodiments of the invention, should be considered creative in themselves, rather than just as some embodiments of the invention. For these features, independent protection may be sought, supplementing any currently claimed invention or replacing it.

[0385] The technical teachings disclosed in the present invention can be extracted and combined with other examples.

[0386] The following examples illustrate the present invention in more detail without any intention to limit the present invention thereto.

[0387] A person skilled in the art will be able, using the detailed information given, to produce other electronic devices of the invention without inventive step and thus to implement the invention within the entire scope of the claims. Example

[0388] Unless otherwise stated, the following syntheses were carried out in dry solvents under a protective gas atmosphere. The reactants can be sourced from ALDRICH. The numbers of the reactants known from the literature (some of which are indicated in square brackets) are the corresponding CAS numbers.

[0389] Synthesis example

[0390]

[0391] Synthesis example

[0392] a) 1-Bromo-4b,9-diazaindeno[1,2-a]inden-10-one

[0393]

[0394] In a 2 l flask, 89.0 g (754 mmol; 1.50 eq.) benzimidazole [CAS 51-17-2], 102 g (502 mmol; 1.00 eq.) 2-bromo-6-fluorobenzaldehyde [CAS 360575-28-6] and 108 g (778 mmol; 1.55 eq.) potassium carbonate [CAS 584-08-7] are suspended in 1500 ml DMSO [CAS 67-68-5]. The reaction mixture is stirred at 105 ° C. with introduction of air for 18 hours. After cooling to room temperature, the reaction mixture is poured into 2.5 l of ice water. The precipitated solid is filtered off and washed with ethyl acetate [CAS 141-78-6]. 43.3 g (144.7 mmol, 29% of theory) of the product are obtained as an orange solid.

[0395] In a similar manner, the following compounds can be obtained:

[0396]

[0397] b) 10-(4'-chlorobiphenyl-2-yl)-10H-4b,9-diazaindeno[1,2-a]inden-10-ol

[0398]

[0399] In a 1 l flask, under protective gas, 20.9 g (78.2 mmol; 1.07 eq) of 2-bromo-4'-chlorobiphenyl [CAS 179526-95-5] were dissolved in 50 ml of dry THF [CAS 109-99-9] and cooled to -78°C. Then 30.7 ml (2.5 mol / l; 76.7 mmol; 1.05 eq) of n-butyllithium [CAS 109-72-8] were added dropwise and the mixture was stirred for a further 2 hours. To this mixture was added dropwise a suspension of 16.1 g (73.0 mmol, 1.00 eq) of 4b,9-diazaindeno[1,2-a]inden-10-one [CAS 138479-49-9] in 370 ml of dry THF [CAS 109-99-9]. The resulting mixture was gradually warmed to room temperature and stirred for a further 18 hours. The reaction was quenched by adding 300 ml of water and the resulting phase was separated. After extraction of the aqueous phase with ethyl acetate (3×150 ml) [CAS 141-78-6], the combined organic phases were washed with water (2×150 ml). Removal of the solvent under reduced pressure yielded a crude product which was finally dissolved in dichloromethane [CAS 75-09-2] and precipitated by adding heptane. After filtration, 25.3 g (61.8 mmol; 85%) of the product were obtained as a brown filter residue.

[0400] In a similar manner, the following compounds can be obtained:

[0401]

[0402]

[0403] c) 2-Chlorospiro[fluorene-9,11'-indolo[1,2-a]benzimidazole]

[0404]

[0405] In a 500 ml flask, 24.9 g (60.9 mmol; 1.00 eq) of 10-(4'-chlorobiphenyl-2-yl)-10H-4b,9-diazaindeno[1,2-a]inden-10-ol and 116 g (609 mmol; 10.0 eq) of toluenesulfonic acid monohydrate [CAS6192-52-5] were suspended in 290 ml of toluene [CAS 108-88-3] and the mixture was stirred at 115 ° C for 72 hours. When the conversion was complete, the mixture was cooled to room temperature and the reaction solution was concentrated. The crude product was dissolved in ethyl acetate (500 ml) [CAS141-78-6] and washed with water (2×250 ml). After filtration through silica gel and precipitation with heptane, 19.1 g (80%, 48.8 mmol) of the product was obtained in the form of a beige solid.

[0406] In a similar manner, the following compounds can be obtained:

[0407]

[0408]

[0409] d) 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[fluorene-9,11'-indolo[1,2-a]benzimidazole]

[0410]

[0411] In a 1 l flask, under protective gas, 18.6 g (47.5 mmol; 1.00 eq) of 2-chlorospiro[fluorene-9,11'-indolo[1,2-a]benzimidazole] and 14.5 g (57 mmol, 1.20 eq) of bis(pinacolato)diborane [CAS 73183-34-3] were dissolved in 450 ml of dry distilled water. 10.2 g (105 mmol, 2.20 eq.) of potassium acetate [CAS 127-08-2] and 1.76 g (2.38 mmol, 5 mol%) of trans-dichlorobis(tricyclohexylphosphine)palladium(II) complex [CAS 29934-17-6] were subsequently added and the mixture was heated to 90° C. overnight. After the reaction was complete, the mixture was diluted with 300 ml of toluene [CAS 108-88-3] and extracted with water. The solvent was removed on a rotary evaporator and the solid obtained was dried. 17.9 g of the product (37.1 mmol, 78% of theory) were obtained without further purification.

[0412] In a similar manner, the following compounds can be obtained:

[0413]

[0414]

[0415] e) 10,10-dimethyl-1,8-diazatetracyclo[7.7.0.0 2,7 .0 11,16 ] Hexadecene-2,4,6,8,11(16),12,14-heptaene

[0416]

[0417] Under an inertized atmosphere, 147 g (774 mmol, 4.00 eq) of titanium (IV) chloride [CAS 7550-45-0] and dichloromethane [CAS 75-09-2] were first loaded at -40 ° C. Then 387 ml (2 mol / l, 774 mmol, 4.00 eq) of dimethyl zinc solution [CAS 544-97-8] were added at a rate such that the temperature did not exceed -35 ° C. Subsequently, 42.6 g (193.6 mmol, 1.00 eq) of 4b, 9-diazaindeno [1,2-a] inden-10-one were added. The resulting solution was gradually warmed to room temperature and quenched by adding ethanol and then water. Phase separation was performed and the organic phase was concentrated to a solid. The crude product was repeatedly recrystallized from a mixture of heptane [CAS 142-82-5] and ethyl acetate [CAS 141-78-6]. This gave 5.03 g (21.3 mmol, 11% of theory) of product.

[0418] f) 5-bromo-10,10-dimethyl-1,8-diazatetracyclo[7.7.0.0 2,7 .0 11,16 ] Hexadecene-2,4,6,8,11(16),12,14-heptaene

[0419]

[0420] Under protective gas, 4.83 g (20.6 mmol, 1.00 eq) of 3-[3'-(4,6-diphenyl-1,3,5-triazine-2-yl)-[1,1'-biphenyl]-3-yl]-9-(terphenylidene-2-yl)-9H-carbazole are suspended in 30 ml of dry DMF [CAS 68-12-2] and cooled to 0° C. 4.03 g (22.7 mmol, 1.1 eq) of NBS [CAS 128-08-5] are then added and the reaction mixture is stirred for 16 hours, during which it is allowed to warm to room temperature. The reaction is quenched by adding 150 ml of water and stirring for 30 minutes. After filtering and drying, 5.48 g (17.5 mmol; 85% of theory) of product are obtained.

[0421] g) N-(9,9-dimethylfluoren-4-yl)-N-(4-phenylphenyl)spiro[fluorene-9,11'-indolo[1,2-a]benzimidazol-2-amine

[0422]

[0423] An initial charge of 15.2 g (38.9 mmol; 1.00 eq.) 2-chlorospiro[fluorene-9,11′-indolo[1,2-a]benzimidazole], 14.5 g (39.3 mmol; 1.01 eq.) biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-4-yl)amine [CAS 1421789-16-3] and 4.96 g (42.7 mmol; 1.10 eq.) sodium tert-amylate [CAS 14593-46-5] in 200 ml of toluene [CAS 108-88-3] was inerted in an argon stream for 30 minutes. Then 479 mg (1.17 mmol; 3 mol%) of dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)phosphine (SPhos) [CAS 657408-07-6], 262 mg (1.17 mmol; 3 mol%) of palladium acetate [CAS 3375-31-3] were added and the mixture was heated to reflux for 18 hours. After the conversion was complete and cooled to room temperature, 500 ml of water were added to the reaction mixture. After phase separation and extraction of the aqueous phase with toluene [CAS 108-88-3], the combined organic phases were concentrated and heptane was added. The precipitated solid was separated. Purification by Soxhlet extraction, recrystallization and vacuum sublimation gave the desired product (6.63 g; 9.26 mmol; 24% of theory).

[0424] In a similar manner, the following compounds can be obtained:

[0425]

[0426]

[0427]

[0428] h) 2-[9-phenyl-6-(9-phenylcarbazole-3-yl)carbazole-3-yl]spiro[fluorene-9,11'-indolo[1,2-a]benzimidazole]

[0429]

[0430] 6.36 g (16.3 mmol; 1.00 eq) of 2-chlorospiro[fluorene-9,11′-indolo[1,2-a]benzimidazole], 11.4 g (18.7 mmol; 1.15 eq) of 9,9′-diphenyl-6-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-9H,9′H-[3,3′]bicarbazole [CAS1572537-61-1] and 7.49 g (32.5 mmol; 2.00 eq) of tripotassium phosphate [CAS14593-46-5] were suspended in 210 ml of toluene [CAS108-88-3] and 20 ml of water. To this suspension are added 334 mg (814 μmol; 5 mol %) of dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)phosphine (SPhos) [CAS 657408-07-6], 183 mg (814 μmol; 5 mol %) of palladium acetate [CAS 3375-31-3], and the reaction mixture is heated under reflux for 16 hours. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 150 ml of water and then concentrated to dryness. The residue is recrystallized from toluene and finally sublimed under high vacuum. The yield is 4.70 g (5.60 mmol, 34% of theory).

[0431] In a similar manner, the following compounds can be obtained:

[0432]

[0433]

[0434]

[0435] i) 2-(4,6-diphenyl-1,3,5-triazine-2-yl)spiro[fluorene-9,11'-indolo[1,2-a]benzimidazole]

[0436]

[0437] 10.8 g (22.4 mmol; 1.20 eq) of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[fluorene-9,11'-indolo[1,2-a]benzimidazole], 5.00 g (18.7 mmol; 1.00 eq) of 2-chloro-4,6-diphenyl-[1,3,5]triazine and 8.58 g (39.2 mmol; 2.10 eq) of tripotassium phosphate [CAS14593-46-5] were suspended in 45 ml of toluene [CAS108-88-3], 45 ml of distilled water, and ... tripotassium phosphate [CAS14593-46-5] were suspended in 45 ml of toluene [CAS108-88-3], 45 ml of distilled water, and 10.8 g (22.4 mmol; 1.20 eq) of alkane [CAS 123-91-1] and 45 ml of water. To this suspension are added 383 mg (934 micromol; 5 mol%) of dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)phosphine (SPhos) [CAS 657408-07-6], 210 mg (934 micromol; 5 mol%) of palladium acetate [CAS 3375-31-3] and the reaction mixture is heated under reflux for 16 hours. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 500 ml of water and then concentrated to dryness. The residue is recrystallized from toluene [CAS 108-88-3] and finally sublimed under high vacuum. The yield is 5.32 g (9.05 mmol, 48% of theory).

[0438] In a similar manner, the following compounds can be obtained:

[0439]

[0440]

[0441] OLED Manufacturing

[0442] The following Examples E1 to E12 (see Table 1) illustrate the use of the materials according to the invention in OLEDs.

[0443] Pretreatment of Examples E1-E12: Glass plates coated with structured ITO (indium tin oxide) with a thickness of 50 nm were treated with oxygen plasma and then with argon plasma before coating. These plasma-treated glass plates formed the substrates to which the OLEDs were applied.

[0444] An OLED essentially has the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emissive layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm. The exact structure of the OLED can be found in Table 1. Table 2 shows the materials required for the manufacture of the OLED. Table 3 lists the data of the OLED.

[0445] 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) added to the matrix material by coevaporation in a specific volume ratio. Details given in the form of EG1:IC2:TEG1 (49%:44%:7%) mean that the material EG1 is present in the layer in a volume ratio of 49%, IC2 in a proportion of 44% and TEG1 in a proportion of 7%. Similarly, the electron transport layer can also consist of a mixture of two materials.

[0446] The OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum, the current efficiency (CE, measured in cd / A), the external quantum efficiency (EQE, measured in %), which was calculated as a function of the brightness from the current-voltage-brightness characteristic showing Lambertian radiation characteristics, and the lifetime were determined. The electroluminescence spectrum was measured at 1000 cd / m 2 The CIE 1931 x and y color coordinates are calculated from the brightness of the color. The parameter U1000 in Table 3 refers to 1000 cd / m 2 The voltage required for the brightness is 1000cd / m 2 The current efficiency and external quantum efficiency achieved.

[0447] The lifetime LD is defined as the time after which the brightness decreases from the initial brightness to a certain proportion L1 during operation at a constant current density j0. The number L1=80% in Table 3 means that the lifetime reported in the LD column corresponds to the time after which the brightness decreases to 80% of its initial value.

[0448] Use of the compounds of the present invention as electron transport materials

[0449] The materials of the present invention can be used in the electron transport layer (ETL) of OLEDs. Compound EG1 of the present invention can be used as an electron transport material in fluorescent blue OLEDs in Examples E1, E2, E5 and E6. In addition, the materials of the present invention can be successfully used in hole blocking layers (HBL). This was demonstrated in Experiments E3, E4, E7 and E8.

[0450] Use of the compounds of the invention as matrix materials in phosphorescent OLEDs

[0451] The materials according to the invention can be used in the emission layer of phosphorescent OLEDs, for example green OLEDs. The compounds EG1 to EG4 according to the invention can be used as matrix materials in the emission layer in Examples E9 to E12.

[0452] Table 1: Structure of OLED

[0453]

[0454]

[0455] Table 2: Structural formulas of materials used in OLEDs

[0456]

[0457]

[0458] Table 3: OLED data

[0459]

[0460]

[0461] Thermal stability

[0462] The compound EG1 of the present invention shows a significant increase in thermal stability compared to the literature compound ST3. This stability was determined by heat treating the two materials at 350°C for 7 days in a vacuum glass ampoule. The analytical determination of purity (HPLC) showed the following results:

[0463]

Claims

1. A compound comprising at least one structure of formula (IIIa) or (IIId): The symbols used are as follows: R a are the same or different at each occurrence and are: a straight-chain alkyl group having 1 to 10 carbon atoms; R is the same or different at each occurrence and is: N(Ar)2, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, wherein the heteroatom in the heteroaromatic ring system is N, wherein each of the aromatic or heteroaromatic ring systems may be replaced by one or more R 1 Group substitution; Ar is identical or different at each occurrence and is a ring having 6 to 12 aromatic ring atoms and may be replaced by one or more non-aromatic R 1 The aromatic ring system may be substituted with one or more non-aromatic R 1 4-fluorenyl substituted with a group; R 1 are identical or different on each occurrence and are: H, D, a straight-chain alkyl radical having 1 to 10 carbon atoms or which may be replaced in each case by one or more R 2 The following radicals substituted with radicals: phenyl, o-, m- or p-biphenyl, pyridyl, pyrimidyl, triazinyl; R 2 are identical or different on each occurrence and are: H, D, a straight-chain alkyl radical having 1 to 10 carbon atoms or which may be replaced in each case by one or more R 3 phenyl substituted with a radical; R 3 is the same or different at each occurrence and is selected from: H or D; m is the same or different at each occurrence and is 0 or 1, but not all m are 0 in the structure of formula (IIIa) or (IIId); and p is 0, ie there is a bond between the two aromatic ring systems in the structure of formula (IIIa).

2. The compound according to claim 1, characterized in that The compound comprises a hole transport group, wherein one of the R groups is a hole transport group, and the hole transport group is a group of formula (H-1): The dotted key indicates the connection position. Ar 2 is independently an aromatic ring system having 6 to 40 carbon atoms, each of which may be replaced by one or more R 1 Group substitution; Ar 3 ,Ar 4 Each independently is an aromatic ring system having 6 to 12 aromatic ring atoms or a 4-fluorenyl group, wherein the aromatic ring system and the 4-fluorenyl group may be substituted by one or more non-aromatic R 1 group substitution; and p is 0.

3. The compound according to claim 1, characterized in that The compound is selected from the following compounds:

4. A composition comprising at least one compound according to any one of claims 1 to 3 and at least one other compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, multipod emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole conduction materials, hole injection materials, electron blocking materials and hole blocking materials.

5. A formulation comprising at least one compound according to any one of claims 1 to 3 or a composition according to claim 4, and at least one solvent.

6. Use of the compound according to any one of claims 1 to 3 or the composition according to claim 4 as a host material, a hole transport material or an electron transport material in an electronic device.

7. The method for preparing a compound according to any one of claims 1 to 3, characterized in that: In the coupling reaction, a compound comprising at least one nitrogen-containing heterocyclic group is linked to a compound comprising at least one aromatic or heteroaromatic group.

8. An electronic device comprising at least one compound according to any one of claims 1 to 3 or a composition according to claim 4, wherein the electronic device is selected from an organic electroluminescent device, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light emitting electrochemical cell and an organic laser diode.

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