Electronic Device Materials

Abstract

To provide an aromatic compound that is suitable for use in electronic devices and includes a group selected from an amino group, a crosslinked amino group and a carbazole group.SOLUTION: Provided herein is a compound of the following formula (II-A).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present application relates to aromatic compounds containing groups selected from amino groups, bridging amino groups and carbazole groups according to formulae (I) and (II) as defined below. These compounds are suitable for use in electronic devices.

[0002] Electronic devices in the context of this application are understood to mean so-called organic electronic devices that contain organic semiconductor materials as functional materials. More specifically, they are understood to mean OLEDs (organic electroluminescent devices). The term OLED is understood to mean an electronic device that has one or more layers that contain organic compounds and emits light when a voltage is applied. The general principles of the construction and function of OLEDs are known to those skilled in the art.

[0003] In electronic devices, and in particular in OLEDs, there is a strong interest in improving performance data, especially lifetime, efficiency and operating voltage, aspects of which no fully satisfactory solutions have yet been found.

[0004] In addition, materials with high glass transition temperatures, low tendency to crystallize, and high refractive index are sought, especially for use in the hole transport layer of OLEDs.

[0005] The performance data of electronic devices is largely determined by the light-emitting layer and the layer having hole transport function. There is a need for new compounds for use in these layers, in particular hole transport compounds, and also compounds that can function as matrix materials in the light-emitting layer, in particular for phosphorescent emitters.

[0006] A wide variety of aromatic compounds containing groups selected from amino groups, bridging amino groups and carbazole groups are known in the prior art as hole transport materials and / or matrix materials in electronic devices.

[0007] However, there remains a need for alternative compounds suitable for use in electronic devices. Improvements are also needed with respect to performance data in electronic device use, particularly with respect to lifetime, operating voltage and efficiency.

[0008] It has now been found that certain compounds from the above-mentioned structural classes are very suitable for use in electronic devices, especially for use in OLEDs, and especially for use as hole transport material and matrix material for phosphorescent emitters in OLEDs.The compounds preferably lead to long device life, high efficiency and low operating voltage.More preferably, the compounds have low tendency to crystallize, high glass transition temperature and high refractive index.

[0009] The present application relates to a compound represented by the following formula (I) or (II):

[0010] [ka]

[0011] wherein the variables occurring are as follows: Z 1 are the same or different in each case, and CR 1 and C.R. 3 Selected from; Ar 1 has 6 to 20 aromatic ring atoms and one or more R 3 an aryl group optionally substituted by a radical, or an aryl group having 5 to 20 aromatic ring atoms and one or more R 3 an optionally substituted heteroaryl group; Ar 2 are the same or different in each occurrence and have 6 to 40 aromatic ring atoms; 5 Aromatic ring systems, optionally substituted by radicals, having 5 to 40 aromatic ring atoms and one or more R 5 a heteroaromatic ring system optionally substituted by a radical; Ar 3 has 6 to 20 aromatic ring atoms and one or more R 2 an aryl group optionally substituted by a radical, or an aryl group having 5 to 20 aromatic ring atoms and one or more R 2 an optionally substituted heteroaryl group; X 1 are the same or different in each case, -C(R 4 ) 2 -, -C(R 4 ) 2 -C(R 4 ) 2 -, -CR 4 =CR 4 -, -Si(R 4 ) 2 -, NR 4 is a divalent radical selected from O and S; Ar L has 6 to 40 aromatic ring atoms and one or more R 5 Aromatic ring systems, optionally substituted by radicals, having 5 to 40 aromatic ring atoms and one or more R 5 a heteroaromatic ring system optionally substituted by a radical; E is a single bond or C(R 5 ) 2 , Si(R 5 ) 2 , N(R 5 ), O, and S; R 0 has H, D, 6 to 40 aromatic ring atoms, and one or more R 6 Aromatic ring systems, optionally substituted by radicals, having 5 to 40 aromatic ring atoms and one or more R 6 a heteroaromatic ring system optionally substituted by a radical; R 1 are the same or different in each occurrence and have 6 to 40 aromatic ring atoms; 6 Aromatic ring systems, optionally substituted by radicals, having 5 to 40 aromatic ring atoms and one or more R 6a heteroaromatic ring system optionally substituted by a radical; R 2 are the same or different in each case and are H, D, F, CN, Si(R 6 ) 3 , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; 0 The radicals may be linked to each other or to form a ring; the mentioned alkyl, alkoxy, alkenyl and alkynyl groups, and the mentioned aromatic and heteroaromatic ring systems, may each be one or more R 6 may be substituted by one or more CH 2 The group is -R 6 C=CR 6 -, -C≡C-, Si(R 6 ) 2 , C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 ), -O-, -S-, SO or SO 2 may be replaced by; R 3 , R 4 , R 5 are the same or different in each case, H, D, F, C(=O)R 6 , CN, Si(R 6 ) 3 , N(R 6 ) 2 , P(=O)(R 6 ) 2 , OR 6 , S(=O)R 6 , S(=O) 2 R 6, a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; 3 or R 4 or R 5 The radicals may be linked to each other or to form a ring; the mentioned alkyl, alkoxy, alkenyl and alkynyl groups, and the mentioned aromatic and heteroaromatic ring systems, may each be one or more R 6 may be substituted by one or more CH 2 The group is -R 6 C=CR 6 -, -C≡C-, Si(R 6 ) 2 , C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 ), -O-, -S-, SO or SO 2 may be replaced by; R 6 are the same or different in each case, H, D, F, C(=O)R 7 , CN, Si(R 7 ) 3 , N(R 7 ) 2 , P(=O)(R 7 ) 2 , OR 7 , S(=O)R 7 , S(=O) 2 R 7, a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; 6 The radicals may be linked to each other or to form a ring; the mentioned alkyl, alkoxy, alkenyl and alkynyl groups, and the mentioned aromatic and heteroaromatic ring systems, may each be one or more R 7 may be substituted by one or more CH 2 The group is -R 7 C=CR 7 -, -C≡C-, Si(R 7 ) 2 , C=O, C=NR 7 , -C(=O)O-, -C(=O)NR 7 -, NR 7 , P(=O)(R 7 ), -O-, -S-, SO or SO 2 may be replaced by; R 7 are the same or different and are selected from H, D, F, CN, an alkyl or alkoxy group having 1 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; 7 the radicals may be bonded to each other or may form rings; the alkyl, alkoxy, alkenyl and alkynyl groups, the aromatic and heteroaromatic ring systems mentioned may be substituted by F or CN; k is 0, 1, 2 or 3, where, when k=0, Ar L The group is absent and the nitrogen atom (N) of the group of formula serves as the point of attachment; m is 0 or 1, where when m=0, the E group is absent and Ar 2the groups are not bonded to each other; wherein all positions shown as unsubstituted in formulas (I) and (II) are each independently R 3 may be substituted with a radical; In the formula (I) and in the formula (II), in each case CR 1 At least one Z 1 (group exists) The present invention provides a compound of the formula:

[0012] The circle drawn around the six-membered ring in formulae (I) and (II) means that the six-membered ring in question has aromatic character.

[0013] The following definitions are applicable to chemical groups used in this application. These are applicable unless some more detailed definition is given.

[0014] An aryl group in the context of the present invention is understood to mean either a single aromatic ring, i.e. benzene, or a condensed aromatic polycycle, such as naphthalene, phenanthrene or anthracene. A condensed aromatic polycycle in the context of the present application consists of two or more single aromatic rings condensed together. Fusion between rings is understood here to mean that the rings share at least one edge with each other. An aryl group in the context of the present invention contains 6 to 40 aromatic ring atoms, none of which are heteroatoms.

[0015] A heteroaryl group in the context of the present invention is understood to mean either a single heteroaromatic ring, such as pyridine, pyrimidine or thiophene, or a fused heteroaromatic polycycle, such as quinoline or carbazole. A fused heteroaromatic polycycle in the context of the present application consists of two or more single aromatic or heteroaromatic rings fused together, where at least one of the aromatic and heteroaromatic rings is a heteroaromatic ring. Fusion between rings is understood here to mean that the rings share at least one edge with each other. A heteroaryl group in the context of the present invention contains 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms of the heteroaryl group are preferably selected from N, O and S.

[0016] The aryl or heteroaryl groups, each of which may be substituted by the abovementioned radicals, are especially benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, triphenylene, fluoranthene, benzoanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, Pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazineimidazole, quinoxalineimidazole, oxazole, benzoxazole, naphtho Oxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1, This is understood to mean groups derived from 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.

[0017] An aromatic ring system in the context of the present invention is a system that does not necessarily contain only aryl groups, but may additionally contain one or more non-aromatic rings fused to at least one aryl group. These non-aromatic rings contain only carbon atoms as ring atoms. Examples of groups encompassed by this definition are tetrahydronaphthalene, fluorene and spirobifluorene. In addition, the term "aromatic ring system" includes systems consisting of two or more aromatic ring systems bonded together via single bonds, such as biphenyl, terphenyl, 7-phenyl-2-fluorenyl, quaterphenyl and 3,5-diphenyl-1-phenyl. Aromatic ring systems in the context of the present invention contain 6 to 40 carbon atoms and do not contain heteroatoms in the ring system. The definition of "aromatic ring system" does not include heteroaryl groups.

[0018] Heteroaromatic ring systems meet the above definition of aromatic ring systems, except that they must contain at least one heteroatom as a ring atom. As in the case of aromatic ring systems, heteroaromatic ring systems need not contain only aryl and heteroaryl groups, but may in addition contain one or more non-aromatic rings fused to at least one aryl or heteroaryl group. The non-aromatic ring may contain only carbon atoms as ring atoms or may additionally contain one or more heteroatoms, where the heteroatoms are preferably selected from N, O and S. An example of such a heteroaromatic ring system is benzopyranyl. In addition, the term "heteroaromatic ring system" is understood to mean a system consisting of two or more aromatic or heteroaromatic ring systems bonded to each other via single bonds, such as 4,6-diphenyl-2-triazinyl. Heteroaromatic ring systems in the context of the present invention contain 5 to 40 ring atoms selected from carbon and heteroatoms, where at least one of the ring atoms is a heteroatom. The heteroatoms of the heteroaromatic ring system are preferably selected from N, O and S.

[0019] Thus, the terms "heteroaromatic ring system" and "aromatic ring system" as defined herein differ from each other in that an aromatic ring system cannot have a heteroatom as a ring atom, while a heteroaromatic ring system must have at least one heteroatom as a ring atom, which may be present as a ring atom of a non-aromatic heterocycle or as a ring atom of an aromatic heterocycle.

[0020] According to the above definitions, any aryl group is encompassed by the term "aromatic ring system", and any heteroaryl group is encompassed by the term "heteroaromatic ring system".

[0021] An aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms is understood to mean, in particular, radicals derived from the radicals mentioned above under the aryl and heteroaryl radicals, and from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, indenocarbazole or a combination of these radicals.

[0022] In the context of the present invention, linear alkyl groups having 1 to 20 carbon atoms, as well as branched or cyclic alkyl groups having 3 to 20 carbon atoms, and alkenyl or alkynyl groups having 2 to 40 carbon atoms are each independently selected from the group consisting of an individual hydrogen atom or a CH 2The radicals may be substituted by the radicals mentioned above in the definition of the radicals, and are preferably understood to mean the methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl radicals.

[0023] An alkoxy or thioalkyl group having 1 to 20 carbon atoms is substituted with individual hydrogen atoms or CH 2The radicals may be replaced by the radicals mentioned above in the definition of the radicals, preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, This is understood to mean n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

[0024] The expression that two or more radicals may together form a ring is in the context of this application to be understood as meaning, inter alia, that the two radicals are bonded to one another by a chemical bond, but in addition to this, the above expression is also to be understood as meaning that, if one of the two radicals is hydrogen, the second radical is bonded to the position to which the hydrogen atom is bonded to form a ring.

[0025] The compounds of formulae (I) and (II) preferably contain only one triarylamino group. More preferably, they contain only one amino group. A triarylamino group is understood to mean an amino group to which three groups selected from aromatic and heteroaromatic ring systems are attached.

[0026] Preferably, one or two Z 1 The base is CR 1 and other Z 1 The base is CR 3 More preferably, one Z 1 The base is CR 1 and the other two Z 1 The base is CR 3 It is.

[0027] Preferably, Ar 1 has 6 to 14 aromatic ring atoms and one or more R 3 is an aryl group optionally substituted by a radical; more preferably, Ar 1 is one or more R 3 It is a benzene group which may be substituted by a radical.

[0028] Preferably, Ar 3 has 6 to 14 aromatic ring atoms and one or more R 2 is an aryl group optionally substituted by a radical; more preferably, Ar 3 is one or more R 2 It is a benzene group which may be substituted by a radical.

[0029] Preferably, X 1 are the same in each occurrence. Preferably, X in each occurrence 1 is C(R 4 ) 2 or Si(R 4 ) 2 and more preferably C(R 4 ) 2 It is.

[0030] Ar L The group preferably has 6 to 20 aromatic ring atoms and contains one or more R 5 Aromatic ring systems, optionally substituted by radicals, having 5 to 20 aromatic ring atoms and one or more R 5 Heteroaromatic ring systems, optionally substituted by radicals, are particularly preferred. LThe radicals are selected from divalent radicals derived from benzene, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which is selected from one or more R 5 It may be substituted by a radical. Most preferably, it is Ar L In each case, one or more R 5 Ar is a divalent group derived from benzene which may be substituted by a radical. L The groups may be selected to be the same or different in each occurrence.

[0031] Preferably, k is selected from 0 or 1; more preferably, k is 0.

[0032] Preferred -(Ar L ) k The - group has the formula:

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] wherein the dotted line represents the bond to the remainder of formula (I) or (II). Matches

[0039] Ar bonded directly to nitrogen atom 2 The group is preferably an aromatic ring system.

[0040] Preferably, Ar 2 The radicals are in each case the same or different and are selected from monovalent radicals derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, especially 9,9′-dimethylfluorene and 9,9′-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, where the monovalent radicals are each selected from one or more R 5 Alternatively, Ar 2 The radicals may preferably be selected, the same or different in each case, from a combination of radicals derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, especially 9,9′-dimethylfluorene and 9,9′-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, where the radicals are each one or more of R 5 It may be substituted by a radical.

[0041] Particularly preferred is Ar 2The radicals are in each case the same or different and are selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9′-dimethylfluorenyl and 9,9′-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, in which the mentioned radicals are each selected from one or more R 5 It may be substituted by a radical.

[0042] Particularly preferred is Ar 2 The group has the formula:

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049]

change

[0050]

change

[0051]

change

[0052]

change

[0053]

change

[0054]

change

[0055]

change

[0056]

change

[0057]

change

[0058]

change

[0059] wherein the groups are each R 5 The bond shown with a dashed line represents the bond to the amine nitrogen atom. is selected from.

[0060] In each case, two different Ar 2 Preferably the group is attached to the amine nitrogen atom.

[0061] The E group is preferably a single bond or C(R 4 ) 2 group, and more preferably a single bond.

[0062] Preferably, m=0, such that there are no E groups.

[0063] In an equally preferred alternative embodiment, Ar 2 m=1, such that the Ar groups are bonded to each other via the E group. 2 The groups are preferably selected from phenyl and fluorenyl, each of which may be selected from one or more R 5 In addition, in this case, two Ar 2 The E groups that connect the Ar groups together are 2 Based on Ar 2 Preferably, the E group is attached at the ortho position relative to the bond to the amine nitrogen of the Ar 2 Together with the group, E is C(R 5 ) 2 , Si(R 5 ) 2 , N.R. 5 , O and S, it preferably forms a 6-membered ring, and when E is a single bond it preferably forms a 5-membered ring.

[0064] Units when m=1

[0065] [ka]

[0066] A preferred embodiment of the present invention is the group illustrated below:

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] wherein the groups are each R 5 radicals, preferably unsubstituted at unoccupied positions, and the dashed bond represents the bond to the remainder of the formula. It is.

[0071] Base when m=0

[0072] [ka]

[0073] A preferred embodiment of the present invention is the group illustrated below:

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] wherein the groups are each R 5 radicals, preferably unsubstituted at unoccupied positions, and the dashed bond represents the bond to the remainder of the formula. It is.

[0081] R 0 is preferably H.

[0082] R 1 are preferably in each case the same or different and are selected from monovalent radicals derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, especially 9,9′-dimethylfluorene and 9,9′-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, where the monovalent radicals are each selected from one or more R 6 The group may be substituted with a radical. 6 If radicals are present, one or two R 6 The radical is N(R 7 ) 2 Preferably, where R 7is selected from aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms. Particularly preferred R 1 The group is phenyl, one or two -N(R 7 ) 2 and selected from phenyl, biphenyl, N-linked carbazolyl, C-linked carbazolyl, naphthyl, dibenzofuranyl, and dibenzothiophenyl, each of which is selected from one or more R 6 It may be substituted by a radical, but is preferably unsubstituted.

[0083] R 2 are preferably in each occurrence the same or different and selected from H, D, a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms, wherein said alkyl group and said aromatic ring system and heteroaromatic ring system each comprise one or more R 6 More preferably, R 2 is H.

[0084] R 3 are preferably in each case the same or different and are H, D, F, CN, Si(R 6 ) 3 , a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system each comprise one or more R 6 may be substituted by a radical; one or more of the CH 2 The groups are -C≡C-, -R 6 C=CR 6 -, Si(R 6 ) 2 , C=O, C=NR 6 , -NR6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 More preferably, R 3 is H.

[0085] R 4 , R 5 are preferably in each case the same or different and are H, D, F, CN, Si(R 6 ) 3 , N(R 6 ) 2 , a linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system each comprise one or more R 6 may be substituted by a radical; one or more of the CH 2 The groups are -C≡C-, -R 6 C=CR 6 -, Si(R 6 ) 2 , C=O, C=NR 6 , -NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 - may be replaced by

[0086] X 1 =C(R 4 ) 2 R attached to the group 4 The radicals are preferably selected from alkyl groups having 1 to 20 carbon atoms, aromatic ring systems having 6 to 20 aromatic ring atoms and heteroaromatic ring systems having 5 to 20 aromatic ring atoms; wherein said alkyl groups, said aromatic ring systems and said heteroaromatic ring systems each comprise one or more R 6 In a preferred embodiment, X 1 =C(R 4 ) 2 Two R in the group 4The radical is X 1 =C(R 4 ) 2 The carbon atoms of the groups are taken together to form a ring such that they are spiro atoms. In this case, the ring formed is preferably a cycloalkyl ring or a ring of the following structure:

[0087] [ka]

[0088] (In the formula, the bond shown by the dotted line is X 1 (shows the bond from the group to the rest of the compound) It is.

[0089] Preferably, R 6 are the same or different in each case and are H, D, F, CN, Si(R 7 ) 3 , N(R 7 ) 2 , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl and alkoxy groups, the aromatic ring systems, and the heteroaromatic ring systems each comprise one or more R 7 may be substituted by one or more CH radicals in the alkyl or alkoxy group mentioned. 2 The groups are -C≡C-, -R 7 C=CR 7 -, Si(R 7 ) 2 , C=O, C=NR 7 , -NR 7 -, -O-, -S-, -C(=O)O- or -C(=O)NR 7 - may be replaced by

[0090] A preferred embodiment of formula (I) is represented by the following formula:

[0091] [ka]

[0092] (In the formula, all positions shown as unsubstituted on the benzene ring are R 3 may be substituted with a radical) Matches

[0093] Preferably, in formulae (IA) and (IB), the group

[0094] [ka]

[0095] is in each case attached at the para position relative to the bond to the adjacent benzene group, which is represented by the formulae (IAa) and (IBa):

[0096] [ka]

[0097] (In the formula, all positions shown as unsubstituted on the benzene ring are R 3 may be substituted with a radical) Corresponds to.

[0098] A preferred embodiment of formula (II) is the following formula:

[0099] [ka]

[0100] (In the formula, all positions shown as unsubstituted on the benzene ring are R 3 may be substituted with a radical) Matches

[0101] Further preferred embodiments of formula (I) are represented by the following formula:

[0102] [ka]

[0103] (wherein the occurring variables are as defined above; R 0 and R 3 is preferably H) More preferably, in these formulas, k=0 and m=0, and Ar 1 is one or more R 3 It is a phenyl group which may be substituted by a radical.

[0104] Preferred embodiments of formula (IA) and (IB) are represented by the following formula:

[0105] [ka]

[0106] (wherein the occurring variables are as defined above). Preferably, in these formulas, k=0 and m=0. More preferably, in these formulas, R 3 and R 0 is H. Preferably, in formulae (IA-1), (IA-2) and (IB-1), the group

[0107] [ka]

[0108] is attached in each case para to the bond to the adjacent benzene group, which has the formula:

[0109] [ka]

[0110] (wherein the occurring variables are as defined above). Corresponds to.

[0111] Preferred embodiments of formulae (IA-1), (IA-2) and (IB-1) are represented by the following formula:

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119] (wherein the occurring variables are as defined above; R 0 and R 3 is preferably H) In formulae (IA-1-3), (IA-1-4), (IA-2-3), (IA-2-4), (IB-1-3) and (IB-1-4), E is preferably a single bond and C(R 4) 2 More preferably, E is a single bond. L is preferably one or more R 5 A phenyl group which may be substituted by a radical. Preferably, in the above formula,

[0120] [ka]

[0121] When present, a group selected from is in each instance attached at the para position relative to the bond to the adjacent benzene group.

[0122] Among the above formulae, the formulae (IA-1-1), (IA-1-2), (IA-2-1), (IA-2-2), (IB-1-1) and (IB-1-2) are particularly preferred, among which (IA-1-1) and (IA-1-2) are particularly preferred, among which (IA-1-2) is very particularly preferred. Correspondingly, very particularly preferred formulae are the following embodiments of the formulae (IA-1-1) and (IA-1-2):

[0123] [ka]

[0124] where formula (IA-1-2-a) is most preferred.

[0125] A preferred embodiment of formula (II-A) is represented by the following formula:

[0126] [ka]

[0127] (wherein the occurring variables are as defined above; R 2 and R 3 is preferably H) In formulae (II-A-1) and (II-A-3), E is preferably a single bond and C(R 4 ) 2 More preferably, E is a single bond. L is preferably one or more R 5 A phenyl group which may be substituted by a radical. Among the above formulae, formula (II-A-4) is particularly preferred.

[0128] Preferred compounds according to the invention are illustrated below:

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] [ka]

[0133] [ka]

[0134] [ka]

[0135] [ka]

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] The compounds of formula (I) and (II) can be prepared by known organic reactions, notably the Suzuki reaction, the Hartwig-Buchwald reaction, and the cyclization reaction.

[0142] In a preferred method (Scheme 1), starting with a benzene compound bearing two reactive groups X and two carboxylic ester groups, two successive Suzuki couplings prepare an intermediate in which a central benzene group is attached on one side to a benzene group bearing an amino group A and on the other side to a benzene group bearing an aromatic Ar substituent, the aromatic substituent being in the ortho or meta position relative to the bond between the two benzene groups.

[0143] The carboxylate groups of this compound are then converted to tertiary alkoxy groups by reaction with metal alkyl compounds, preferably lithium alkyl compounds or Grignard alkyl compounds, which cyclize to form rings under the action of an acid, resulting in the compounds of formula (I).

[0144] [ka]

[0145] In an alternative preferred method (Scheme 2), starting from a benzene compound bearing two reactive groups X and two carboxylic acid ester groups, two successive Suzuki couplings are carried out to prepare an intermediate having a central benzene group to which is attached on one side a benzene group bearing a reactive group X and on the other side a benzene group bearing an aromatic substituent Ar, the aromatic substituent being in the ortho or meta position relative to the bond between the two benzene groups.

[0146] The carboxylic acid ester group of this compound is then converted to a tertiary alkoxy group by reaction with a metal alkyl compound, preferably a lithium alkyl compound or a Grignard alkyl compound. These tertiary alkoxy groups cyclize to form a ring under the action of an acid. Finally, an amino group is introduced by Buchwald coupling or a diarylaminoaryl or diarylaminoheteroaryl group is introduced by Suzuki reaction to obtain a compound of formula (I).

[0147] [ka]

[0148] In an alternative preferred method (Scheme 3), starting from a benzene compound bearing two reactive groups X and two carboxylic acid ester groups, two successive Suzuki couplings are carried out to prepare an intermediate having a central benzene group attached on one side to a benzene group bearing a reactive group X and on the other side to a benzene group bearing an amino group A. The reactive group X is in the ortho or meta position relative to the bond between the two benzene groups.

[0149] The carboxylate group of this compound is then converted to a tertiary alkoxy group by reaction with a metal alkyl compound, preferably a lithium alkyl compound or a Grignard alkyl compound. These tertiary alkoxy groups cyclize to form a ring under the action of an acid. Finally, the aromatic substituent Ar is introduced by a Suzuki reaction, resulting in the compound of formula (I).

[0150] [ka]

[0151] A preferred method for preparing compounds of formula (II) is shown in Scheme 4 below. In this case, starting from a benzene compound with two reactive groups X and two carboxylic acid ester groups, two successive Suzuki couplings are carried out to prepare an intermediate with a central benzene group to which a benzene group is attached on one side and a benzene group carrying two reactive X groups is attached on the other side. At least one of the two reactive groups X is in the ortho or meta position with respect to the bond between the two benzene groups. The carboxylic acid ester group of this compound is then converted to a tertiary alkoxy group by reaction with a metal alkyl compound, preferably a lithium alkyl compound or a Grignard alkyl compound. These tertiary alkoxy groups cyclize to form a ring under the action of an acid. An amino group is then introduced by Buchwald coupling or a diarylaminoaryl or diarylaminoheteroaryl group is introduced by Suzuki reaction. Finally, an aromatic substituent Ar is introduced by Suzuki reaction, resulting in a compound of formula (II).

[0152] [ka]

[0153] Thus, the present application further provides a method for preparing a compound of formula (I) or (II), the method being characterized in that a benzene compound having two carboxylic ester groups and at least one reactive group is reacted with a benzene compound containing a boronic acid group and at least one group selected from a reactive group X and an aromatic or heteroaromatic group Ar, wherein the boronic acid group and the at least one group selected from the X and Ar groups are in the ortho or meta position relative to each other on the benzene ring.

[0154] Preferably, the X group is selected from Cl, Br, I, mesylate and tosylate. Preferably, the reaction of a benzene compound having two carboxylic ester groups and two reactive groups with a benzene compound containing a boronic acid group and a group selected from a reactive group X and an aromatic or heteroaromatic group Ar is a Suzuki reaction.

[0155] The above compounds, especially those substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acids or boronic esters, can find use as monomers for preparing the corresponding oligomers, dendrimers or polymers. Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boronic acids, boronic esters, amines, alkenyl or alkynyl groups with terminal CC double or triple bonds, oxiranes, oxetanes, groups involved in cycloadditions, such as 1,3-dipolar cycloadditions, such as dienes or azides, carboxylic acid derivatives, alcohols and silanes.

[0156] Thus, the present invention further provides an oligomer, polymer or dendrimer containing one or more compounds of formula (I) or (II), wherein the bond(s) to the polymer, oligomer or dendrimer is / are selected from the group consisting of R 1 , R 2, R 3 , R 4 or R 5 may be located at any desired position substituted by. Depending on the bond of the compound, the compound becomes part of the side chain or part of the main chain of the oligomer or polymer. An oligomer in the context of the present invention is understood to mean a compound formed from at least three monomer units. A polymer in the context of the present invention is understood to mean a compound formed from at least 10 monomer units. A polymer, oligomer or dendrimer of the present invention may be conjugated, partially conjugated or non-conjugated. An oligomer or polymer of the present invention may be linear, branched or dendritic. In structures with linear bonds, the units of formula (I) or (II) may be bonded directly to each other or may be bonded to each other via a divalent group, for example via a substituted or unsubstituted alkylene group, via a heteroatom or via a divalent aromatic or heteroaromatic group. In branched and dendritic structures, for example, three or more units of formula (I) or (II) may be bonded via a trivalent or higher group, for example via a trivalent or higher aromatic or heteroaromatic group, to form a branched or dendritic oligomer or polymer.

[0157] For repeat units of formula (I) or (II) in oligomers, dendrimers and polymers the same preferences apply as stated for compounds of formula (I) or (II).

[0158] To prepare oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with further monomers.Suitable preferred comonomers are selected from fluorene, spirobifluorene, paraphenylene, carbazole, thiophene, dihydrophenanthrene, cis- and trans-indenofluorene, ketone, phenanthrene, or two or more of these units.Polymers, oligomers and dendrimers typically contain further units, such as luminescent (fluorescent or phosphorescent) units, such as vinyltriarylamine or phosphorescent metal complexes, and / or charge transport units, especially those based on triarylamine.

[0159] The polymers and oligomers of the present invention are generally prepared by polymerization of one or more monomers, at least one of which leads to repeat units of formula (I) or (II) in the polymer. Suitable polymerization reactions are known to those skilled in the art and described in the literature. Particularly suitable and preferred polymerization reactions leading to the formation of CC or CN bonds are Suzuki polymerization, Yamamoto polymerization, Stille polymerization and Hartwig-Buchwald polymerization.

[0160] Processing the compounds of the invention from a liquid phase, for example by spin-coating or printing methods, requires formulations of the compounds of the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, the use of mixtures of two or more solvents may be preferred. Suitable preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanoate, cyclohexanol ... The solvents include, for example, benzene, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or mixtures of these solvents.

[0161] Thus, the present invention further provides a formulation, especially a solution, dispersion or emulsion, comprising at least one compound of formula (I) or (II) and at least one solvent, preferably an organic solvent. The methods by which such solutions can be prepared are known to those skilled in the art.

[0162] The compounds of the present invention are suitable for use in electronic devices, especially organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds are used in different functions and layers.

[0163] Thus, the present invention further provides the use of a compound of formula (I) or (II) in an electronic device, preferably selected from the group consisting of organic integrated circuits (OICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic light emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field quenching devices (OFQDs), organic light emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), more preferably organic electroluminescent devices (OLEDs).

[0164] As already mentioned above, the present invention further provides an electronic device comprising at least one compound of formula (I) or (II), said electronic device being preferably selected from the devices mentioned above.

[0165] The electronic device is more preferably an organic electroluminescent device (OLED) comprising an anode, a cathode, and at least one light-emitting layer, characterized in that at least one organic layer, which may be a light-emitting layer, a hole-transporting layer or another layer, comprises at least one compound of formula (I) or (II).

[0166] Besides the cathode, the anode and the light-emitting layer, the organic electroluminescent device may further comprise further layers, which in each case are selected, for example, from one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers, charge generation layers and / or organic or inorganic p / n junctions.

[0167] The layer order of an organic electroluminescent device comprising a compound of formula (I) or (II) is preferably as follows: anode-hole injection layer-hole transport layer-optional further hole transport layer(s)-optional electron blocking layer-light emitting layer-optional hole blocking layer-electron transport layer-electron injection layer-cathode. In addition, further layers may be present in the OLED.

[0168] The organic electroluminescent device of the present invention may contain two or more emitting layers. More preferably, these emitting layers in this case have several emission maxima at 380 nm to 750 nm, which together produce a white light emission; in other words, various emitting compounds that can fluoresce or phosphoresce and emit blue, green, yellow, orange or red light are used in the emitting layers. Particularly preferred are three-layer systems, i.e. systems with three emitting layers, where the three layers show blue, green and orange or red emission. The compound of the present invention is preferably present here in the hole transport layer, the hole injection layer, the electron blocking layer and / or the emitting layer, more preferably as a matrix material in the emitting layer and / or in the electron blocking layer.

[0169] According to the present invention, it is preferred when the compound of formula (I) or (II) is used in an electronic device comprising one or more phosphorescent compounds. In this case, the compound may be present in different layers, preferably in the hole transport layer, the electron blocking layer, the hole injection layer and / or the light emitting layer. More preferably, the compound is present in the electron blocking layer or in combination with the phosphorescent compound in the light emitting layer. In the latter case, the phosphorescent compound is preferably selected from red or green phosphorescent compounds. Most preferably, the compound is present in the electron blocking layer.

[0170] The term "phosphorescent compound" includes compounds in which emission occurs due to a spin-forbidden transition, typically from, for example, an excited triplet state or a state having a higher spin quantum number, such as a quintet state.

[0171] Suitable phosphorescent compounds (= triplet emitters) are especially compounds which, when appropriately excited, preferably emit light in the visible range and further 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. As phosphorescent compounds, it is preferred to use compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium, platinum or copper. In the context of the present invention, all luminescent iridium, platinum or copper complexes are considered to be phosphorescent compounds.

[0172] Generally, all phosphorescent complexes are suitable as those used in phosphorescent OLEDs according to the prior art and known to those skilled in the art in the field of organic electroluminescent devices.Those skilled in the art can also use other phosphorescent complexes in combination with the compound of formula (I) or (II) in organic electroluminescent devices without exerting their original inventive ability.Further examples are given in the following table:

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] [ka]

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] In a preferred embodiment of the present invention, the compound of formula (I) or (II) is used as a hole transport material. In that case, the compound is preferably present in a hole transport layer. The preferred embodiments of the hole transport layer are a hole transport layer, an electron blocking layer and a hole injection layer. When the compound of formula (I) or (II) is present in a hole transport layer, the latter is preferably an electron blocking layer. It is preferably directly adjacent to the light emitting layer on the anode side.

[0185] The hole transport layer according to the present invention is a layer having a hole transport function between the anode and the light emitting layer, more specifically, a hole transport layer which is neither a hole injection layer nor an electron blocking layer.

[0186] The hole injection layer and the electron blocking layer are understood to be specific embodiments of the hole transport layer in the context of this application. The hole injection layer is a hole transport layer that is directly adjacent to the anode or separated from the anode by a single coating of the anode when there are multiple hole transport layers between the anode and the light emitting layer. The electron blocking layer is a hole transport layer that is directly adjacent to the light emitting layer on the anode side when there are multiple hole transport layers between the anode and the light emitting layer. Preferably, the OLED of the present invention comprises two, three or four hole transport layers between the anode and the light emitting layer, at least one of which preferably contains a compound of formula (I) or (II), more preferably only one or two of which contain a compound of formula (I) or (II).

[0187] When the compound of formula (I) or (II) is used as a hole transport material in the hole transport layer, hole injection layer or electron blocking layer, the compound can be used as a pure material, i.e., in the proportion of 100%, in the hole transport layer, or can be used in combination with one or more additional compounds.In that case, in a preferred embodiment, the organic layer that comprises the compound of formula (I) or (II) additionally contains one or more p-dopants.The p-dopants used according to the present invention are preferably organic electron acceptor compounds that can oxidize one or more of the other compounds in the mixture.

[0188] Particularly preferred p-dopants are quinodimethane compounds, azaindenofluorenediones, azaphenalenes, azatriphenylenes, I 2 , metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or metal of the third main group, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd and Pt with ligands containing at least one oxygen atom as binding site. As dopants further transition metal oxides are preferred, preferably oxides of rhenium, molybdenum and tungsten, more preferably oxides of Re. 2 O 7 , MoO 3 , WO 3 and ReO 3It is.

[0189] The p-dopant is preferably substantially uniformly distributed in the p-doped layer, which can be achieved, for example, by co-evaporation of the p-dopant and a hole transport material matrix.

[0190] Preferred p-dopants are especially the following compounds:

[0191] [ka]

[0192] In a further preferred embodiment of the present invention, the compounds of formula (I) or (II) are used in combination with a hexaazatriphenylene derivative as hole transport material in an OLED, where it is particularly preferred to use the hexaazatriphenylene derivative in a separate layer.

[0193] In a preferred embodiment of the present invention, the compounds of formula (I) or (II) are used as matrix materials in the light-emitting layer in combination with one or more light-emitting compounds, preferably phosphorescent compounds, which are preferably selected from red phosphorescent and green phosphorescent compounds.

[0194] In this case, the ratio of the matrix material in the light-emitting layer is 50.0% to 99.9% by volume, preferably 80.0% to 99.5% by volume, and more preferably 85.0% to 97.0% by volume.

[0195] Correspondingly, the proportion of the luminescent compound is between 0.1% and 50.0% by volume, preferably between 0.5% and 20.0% by volume, more preferably between 3.0% and 15.0% by volume.

[0196] The light-emitting layer of an organic electroluminescent device may comprise a system comprising multiple matrix materials (mixed matrix systems) and / or multiple light-emitting compounds. Again, the light-emitting compound is generally the lower proportion of the system and the matrix material is the higher proportion of the system. However, in individual cases the proportion of a single matrix material in the system may be lower than the proportion of a single light-emitting compound.

[0197] The compounds of formula (I) or (II) are preferably used as components of a mixed matrix system for phosphorescent emitters. 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. The compounds of formula (I) or (II) are preferably matrix materials with hole transport properties. Correspondingly, the compounds of formula (I) or (II) are used as matrix materials for phosphorescent emitters in the emitting layer of an OLED, and a second matrix compound with electron transport properties is present in the emitting layer. The two different matrix materials may 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.

[0198] However, the desired electron-transporting and hole-transporting properties of the mixed matrix component may be primarily or completely possessed by a single mixed matrix component, with additional mixed matrix component(s) performing other functions.

[0199] The mixed matrix system may comprise one or more light-emitting compounds, preferably one or more phosphorescent light-emitting compounds. Generally, the mixed matrix system is preferably used in phosphorescent organic electroluminescent devices.

[0200] Particularly suitable matrix materials which can be used as matrix components in mixed matrix systems in combination with the compounds of the invention are selected from the preferred matrix materials defined below for the phosphorescent compounds, especially those which have electron transporting properties.

[0201] Preferred embodiments of different functional materials in electronic devices are listed below.

[0202] Preferred fluorescent compounds are selected from the class of arylamines. Arylamines or aromatic amines in the context of the present invention are understood to mean compounds containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, more preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. Aromatic anthracenamines are understood to mean compounds in which a diarylamino group is directly bonded to an anthracene group, preferably in the 9-position. Aromatic anthracenediamines are understood to mean compounds in which two diarylamino groups are directly bonded to an anthracene group, preferably in the 9- and 10-positions. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are similarly defined, in which the diarylamino group is directly bonded to the pyrene, preferably in the 1- or 1- and 6-positions. Further preferred luminescent compounds are indenofluorene amines or diamines, benzoindenofluorene amines or diamines, and dibenzoindenofluorene amines or diamines, as well as indenofluorene derivatives with fused aryl groups.Also preferred are pyrenearylamines, benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives substituted with furan or thiophene units.

[0203] Useful matrix materials, preferably for fluorescent compounds, include materials from various substance classes. Preferred matrix materials are selected from the classes of oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobifluorene or dinaphthylanthracene), especially oligoarylenes containing fused aromatic groups, oligoarylenevinylenes (e.g. DPVBi or spiro-DPVBi), polypodal metal complexes, hole-conducting compounds, electron-conducting compounds, especially ketones, phosphine oxides and sulfur oxides, atropisomers, boronic acid derivatives or benzanthracene. Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides and sulfoxides. Very particularly preferred matrix materials are selected from the class of oligoarylenes, which include anthracene, benzoanthracene, benzophenanthrene and / or pyrene or atropisomers of these compounds. Oligoarylenes in the context of the present invention are of course understood to mean compounds in which at least three aryl or arylene groups are bonded to one another.

[0204] Preferred matrix materials for the phosphorescent compounds are, in addition to the compounds of formula (I) or (II), aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, silanes, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasilol or tetraazasilol derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives and lactams.

[0205] Suitable charge transporting materials that can be used in the hole-injecting or hole-transporting or electron-blocking layers or in the electron-transporting layer of the electronic device of the present invention are, in addition to the compounds of formula (I) or (II), for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials as used for these layers according to the prior art.

[0206] Preferred materials for the hole transport layer of an OLED are the following materials:

[0207] [ka]

[0208] [ka]

[0209] [ka]

[0210] Preferably, the OLED of the present invention comprises two or more different hole transport layers.The compound of formula (I) or (II) here may be used in one or more or all of the hole transport layers.In a preferred embodiment, the compound of formula (I) or (II) is used in only one or only two of the hole transport layers, and other compounds, preferably aromatic amine compounds, are used in the additional hole transport layers present. In addition to the compounds of formula (I) or (II), further compounds which are preferably used in the hole-transporting layer of the OLED of the present invention are especially indenofluorene amine derivatives, amine derivatives, hexaazatriphenylene derivatives, amine derivatives containing fused aromatic systems, monobenzoindenofluorene amines, dibenzoindenofluorene amines, spirobifluorene amines, fluorene amines, spirodibenzopyran amines, dihydroacridine derivatives, spirodibenzofurans and spirodibenzothiophenes, phenanthrene diarylamines, spirotribenzotropolones, spirobifluorenes with metaphenyldiamine groups, spirobisacridines, xanthene diarylamines, and 9,10-dihydroanthracene spiro compounds with diarylamino groups.

[0211] The material used in the electron transport layer may be any material that is used as an electron transport material in electron transport layers according to the prior art. Particularly suitable are aluminum complexes such as Alq 3 , zirconium complexes, such as Zrq 4 , lithium complexes, such as Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives and phosphine oxide derivatives. The compounds shown in the table below are particularly preferred:

[0212] [ka]

[0213] [ka]

[0214] Preferred cathodes for electronic devices are metals, metal alloys or multilayer structures made up of different metals, such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.) with a low work function. In addition, alloys made up of alkali metals or alkaline earth metals and silver, such as alloys made up of magnesium and silver, are also suitable. In the case of multilayer structures, in addition to the metals mentioned, it is also possible to use further metals with a relatively high work function, such as Ag or Al, in which case metal combinations such as Ca / Ag, Mg / Ag or Ba / Ag are commonly used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between the metallic cathode and the organic semiconductor. Examples of materials useful for this purpose are alkali metal or alkaline earth metal fluorides as well as the corresponding oxides or carbonates (e.g. LiF, Li 2 O, BaF 2 , MgO, NaF, CsF, Cs 2 CO 3 It is also possible to use lithium quinolinate (LiQ) for this purpose. The layer thickness of this layer is preferably 0.5 to 5 nm.

[0215] Preferred anodes are materials with a high work function. Preferably, the anode has a work function of more than 4.5 eV vs. vacuum. Firstly, metals with high redox potentials are suitable for this purpose, for example Ag, Pt or Au. Secondly, metal / metal oxide electrodes (e.g. Al / Ni / NiO x , Al / PtO x) may be preferred. Depending on the application, at least one of the electrodes must be transparent or partially transparent to allow either irradiation (organic solar cell) or light emission (OLED, O-LASER) of the organic material. Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Furthermore, conductive doped organic materials, especially conductive doped polymers, are preferred. In addition, the anode may consist of two or more layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0216] The device is then appropriately structured (depending on the application), the contacts are connected and finally sealed to eliminate the damaging effects of water and air.

[0217] In a preferred embodiment, the electronic device is characterized in that one or more layers are coated by a sublimation process, in which the material is deposited in a vacuum sublimation system at 10 -5 Less than mbar, preferably less than 10 -6 It is applied by evaporation at an initial pressure of less than 10 mbar. However, in this case, the initial pressure can be lowered, for example to 10 -7 It is also possible to go below mbar.

[0218] Likewise preferred are electronic devices characterized in that one or more layers are coated by the OVPD (organic vapor phase deposition) method or with the aid of carrier gas sublimation. In this case, the material is preferably 10 -5 It is applied at a pressure of between mbar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly by a nozzle and thus structured (eg MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0219] In addition, electronic devices are preferred, 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, nozzle printing or offset printing, but more preferably by LITI (Light Induced Thermal Imaging, Thermal Transfer Printing) or inkjet printing. For this purpose, soluble compounds of formula (I) or (II) are required. High solubility can be achieved by suitable substitution of the compounds.

[0220] More preferably, the electronic devices of the present invention are fabricated by applying one or more layers from solution and applying one or more layers by a sublimation process.

[0221] According to the present invention, electronic devices comprising one or more compounds of formula (I) or (II) can be used as light sources for lighting applications, as light sources for medical and / or cosmetic applications, in display devices.

[0222] [example] A) Synthesis example Example 1-1: Synthesis of Compound 1-1 and Variants of the Invention

[0223] [ka]

[0224] Intermediate I-1 22 g of the boronic acid ester derivative 0-1 (34.8 mmol) and 11.7 g of the bromochlorodicarboxylic acid ester derivative (34.8 mmol) are suspended in 200 ml of toluene, 100 ml of ethanol, and 50 ml of water. 7.4 g of sodium carbonate is added. The reaction solution is degassed and then purified with N 2 Then, 0.6 g (0.51 mmol) of Pd(Ph 3 P) 4 The reaction mixture is heated to boiling under a protective atmosphere for 16 hours. The mixture is then partitioned between toluene and water, the organic phase is washed three times with water and sodium 2 SO4 It is dried on a sieve and concentrated by rotary evaporation. The remaining residue is extracted by stirring in heptane. The yield is 23 g (87% of theory). Intermediate II-1 6.3 g of (2-phenylphenyl)boronic acid (31.6 mmol) and 23 g of the chlorine derivative I-1 (30 mmol) are suspended in 260 ml of toluene and 100 ml of water. 8.3 g of potassium carbonate are added to it. The solution is degassed and then cooled with N 2 Then, 276 mg (0.3 mmol) of Pd 2 (dba) 3 and 250 mg of SPhos (0.3 mmol) are added. The reaction mixture is heated to boiling under a protective atmosphere for 12 h. The mixture is then partitioned between toluene and water, the organic phase is washed three times with water and 2 SO 4 The crude product is dried over silica gel with toluene and concentrated by rotary evaporation. The remaining residue is then recrystallized from EtOH. The yield is 20.7 g (80% of theory).

[0225] In a similar manner, the following compounds are prepared:

[0226] [ka]

[0227] [ka]

[0228] [ka]

[0229] [ka]

[0230] [ka]

[0231] Compound 1-1 15.0 g (17.4 mmol) of intermediate II-1 is dissolved in 150 ml of dry THF in a sintered flask. The solution is then cooled to 37° C. for 24 hours. 2 The clear solution is cooled to -5°C and then 35 ml (105 mmol) of a 3M solution of methylmagnesium chloride are added. The reaction mixture is gradually warmed to room temperature and then quenched with ammonium chloride. The mixture is subsequently partitioned between ethyl acetate and water, the organic phase is washed three times with water and then quenched with Na 2 SO 4 The mixture is dried on a lid and concentrated by rotary evaporation. The solution concentrated by rotary evaporation is dissolved in toluene and 8 g of Amberlyst 15 are added. The mixture is heated to 110° C. and kept at this temperature for 4 hours. During this time a white solid precipitates. The mixture is then cooled to room temperature and the precipitated solid is suction filtered and washed with heptane. The residue is dried under reduced pressure at 40° C. After filtering the crude product through silica gel with heptane:ethyl acetate 1:1, 13 g (90% of theory) of product are obtained. Finally, the material is sublimed under high vacuum. The purity is 99.9%.

[0232] In a similar manner, the following compounds are prepared:

[0233] [ka]

[0234] [ka]

[0235] [ka]

[0236] [ka]

[0237] Compound 2-1

[0238] [ka]

[0239] Dissolve 5.95 g of bis-p-tolylamine (30.2 mmol) and 15 g of intermediate III-1 (30.2 mmol) in 300 ml of toluene. Degas the solution and purify with N 2 Then, 0.28 g (0.302 mmol) of Pd 2 (dba) 3 and 0.6 ml of (tBu) 3 A 1M solution of P is added to it, followed by 4.3 g of sodium tert-butoxide (45.3 mol). The reaction mixture is heated to boiling under a protective atmosphere for 6 hours. The mixture is subsequently partitioned between toluene and water, the organic phase is washed three times with water and Na 2 SO 4 The mixture is dried over hexane and concentrated by rotary evaporation. The crude product is filtered through silica gel with toluene, and the remaining residue is recrystallized from heptane / toluene. The yield is 14.3 g (72% of theory). Finally, the material is sublimed under high vacuum. The purity is 99.9%.

[0240] In a similar manner, the following compounds are prepared:

[0241] [ka]

[0242] [ka]

[0243] [ka]

[0244] Compound 3-1

[0245] [ka]

[0246] 17.1 g (28.51 mmol) of pinacol boronic acid ester derivative IV-1 and 12 g (28.51 mmol) of intermediate III-1 are suspended in 350 ml of toluene and 4.1 g of sodium tert-butoxide (42.8 mmol). 0.26 g (0.285 mmol) of Pd 2 (dba) 2 is added to this suspension and the reaction mixture is heated under reflux for 12 hours. After cooling, the organic phase is removed, filtered through silica gel, washed 3 times with 80 ml of water and then concentrated to dryness. The crude product is filtered through silica gel with toluene and the remaining residue is recrystallized from heptane / toluene. The yield is 18 g (75% of theory). Finally, the material is sublimed under high vacuum. The purity is 99.9%.

[0247] In a similar manner, the following compounds are prepared:

[0248] [ka]

[0249] [ka]

[0250] [ka]

[0251] B) Device example 1) General manufacturing method of OLED and characterization of OLED A glass plaque coated with a 50 nm thick structured ITO (indium tin oxide) is the substrate onto which the OLED is applied.

[0252] An OLED basically has the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emissive layer (EML) / electron transport layer (ETL) / electron injection layer (EIL), and finally a cathode. The cathode is formed by a 100 nm thick layer of aluminum. The exact structure of an OLED can be found in the table that follows. The materials required for the manufacture of an OLED are given in the table below.

[0253] All materials are applied by thermal evaporation in a vacuum chamber. In this case, the emissive layer consists of at least one matrix material (host material) and emissive dopants (emitters) that are added to the matrix material(s) in a certain volumetric percentage by co-evaporation. Here, details given in the form IC1:EG1:TEG1 (55%:35%:10%) mean that the material IC1 is present in the layer in a volumetric percentage of 55%, EG1 in a percentage of 35% and TEG1 in a percentage of 10%.

[0254] Similarly, the electron transport layer and hole injection layer are made of a mixture of two materials. The structures of the materials used in the OLED are shown in Table 1.

[0255] The OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, the external quantum efficiency (EQE, measured in %) as a function of luminance calculated from the current-voltage-luminance characteristic assuming Lambertian emission characteristics, and the lifetime are determined. The parameter EQE@10 mA / cm 2 is 10mA / cm 2 The parameter U@10mA / cm 2 is 10mA / cm 2 Refers to the operating voltage at LT80@60mA / cm 2 is 60mA / cm 2 It is defined as the time it takes for the capacitance to drop to 80% of its initial value without the use of an acceleration factor when operated at a current density of 100 kPa. 2) Use of the compounds of the present invention in HIL and HTL of blue fluorescent devices An OLED having the following structure is fabricated:

[0256] [Table 1]

[0257] This gives very good results in terms of OLED performance data: EQE@10mA / cm 2 is about 7.5%, and the operating voltage U@10mA / cm 2 is about 4V, and the lifespan is LT80@60mA / cm 2 has exceeded 300 hours. 3) Use of the compounds of the present invention in the EBL of green phosphorescent emitting devices An OLED having the following structure is fabricated:

[0258] [Table 2]

[0259] This gives very good results in terms of OLED performance data in all cases: EQE@10mA / cm 2 is about 14% in all cases, and the operating voltage U@10mA / cm 2 is about 4V in all cases, and the lifetime LT80@60mA / cm 2 is greater than 300 hours in all cases. 4) Comparison of OLED performance data between the compound HTM-1 of the present invention and the comparative compound RefHTM An inventive OLED I6 is prepared having the same structure as OLED I1 described in 2), the only difference being the presence of compound HTM-1 in the HIL and HTL of the OLED instead of compound HTM-2.

[0260] For comparison, an OLED C1 was prepared which has the same structure as the inventive OLED I6, the only difference being that the compound RefHTM is present in the HIL and HTL of the OLED instead of the compound HTM-1.

[0261] In the case of the OLED I6 of the present invention, a clear improvement in the EQE value and a slight decrease in the operating voltage were observed compared to the comparative OLED C1. 2 is greater than 300 hours in both cases. The values ​​obtained are shown in the table below:

[0262] [Table 3]

[0263] [Table 4-1]

[0264] [Table 4-2]

Claims

1. The following formula (II-A): 【Chemistry 1】 wherein the variables occurring are as follows: Z １ are the same or different in each case, and CR １ and C.R. ３ Selected from: Ar ２ are the same or different in each occurrence and have 6 to 40 aromatic ring atoms; ５ an aromatic ring system optionally substituted by a radical, and having 5 to 40 aromatic ring atoms and one or more R ５ a heteroaromatic ring system optionally substituted by a radical; Ar Ｌ has 6 to 40 aromatic ring atoms and one or more R ５ an aromatic ring system optionally substituted by a radical, and having 5 to 40 aromatic ring atoms and one or more R ５ a heteroaromatic ring system optionally substituted by a radical; E is a single bond or C(R ５ ) ２ , Si(R ５ ) ２ , N(R ５ ), O, and S; R １ are the same or different in each occurrence and have 6 to 40 aromatic ring atoms; ６ an aromatic ring system optionally substituted by a radical, and having 5 to 40 aromatic ring atoms and one or more R ６ a heteroaromatic ring system optionally substituted by a radical; R ２ are the same or different in each case and are H, D, F, CN, Si(R ６ ) ３ , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; ２ The radicals may be bonded to each other or to form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups mentioned, and the aromatic and heteroaromatic ring systems mentioned, may each be one or more R ６ may be substituted by one or more of the above-mentioned alkyl, alkoxy, alkenyl and alkynyl groups. ２ The group is -R ６ C=CR ６ -, -C≡C-, Si(R ６ ) ２ , C=O, C=NR ６ , -C(=O)O-, -C(=O)NR ６ -, N.R. ６ , P(=O)(R ６ ), —O—, —S—, SO or SO ２ may be replaced by; R ３ , R ４ , R ５ are the same or different in each occurrence, H, D, F, C(=O)R ６ , CN, Si(R ６ ) ３ , N(R ６ ) ２ , P(=O)(R ６ ) ２ , OR ６ , S(=O)R ６ , S(=O) ２ R ６ , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; ３ Or R ４ Or R ５ The radicals may be bonded to each other or to form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups mentioned, and the aromatic and heteroaromatic ring systems mentioned, may each be one or more R ６ may be substituted by one or more of the above-mentioned alkyl, alkoxy, alkenyl and alkynyl groups. ２ The group is -R ６ C=CR ６ -, -C≡C-, Si(R ６ ) ２ , C=O, C=NR ６ , -C(=O)O-, -C(=O)NR ６ -, N.R. ６ , P(=O)(R ６ ), —O—, —S—, SO or SO ２ may be replaced by; R ６ are the same or different in each occurrence, H, D, F, C(=O)R ７ , CN, Si(R ７ ) ３ , N(R ７ ) ２ , P(=O)(R ７ ) ２ , OR ７ , S(=O)R ７ , S(=O) ２ R ７ , a linear alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; ６ The radicals may be bonded to each other or to form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups mentioned, and the aromatic and heteroaromatic ring systems mentioned, may each be one or more R ７ may be substituted by one or more of the above-mentioned alkyl, alkoxy, alkenyl and alkynyl groups. ２ The group is -R ７ C=CR ７ -, -C≡C-, Si(R ７ ) ２ , C=O, C=NR ７ , -C(=O)O-, -C(=O)NR ７ -, N.R. ７ , P(=O)(R ７ ), —O—, —S—, SO or SO ２ may be replaced by; R ７ are the same or different in each occurrence and are selected from H, D, F, CN, an alkyl or alkoxy group having 1 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; ７ the radicals may be bonded to each other or may form rings; the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic and heteroaromatic ring systems mentioned may be substituted by F or CN; k is 0, 1, 2 or 3, where when k=0, the Ar Ｌ The group is absent and the nitrogen atom (N) of the group of formula constitutes the point of attachment; m is 0 or 1, where when m=0, the E group is absent and the Ar ２ the groups are not bonded to each other; In formula (II-A), all positions shown as unsubstituted are each R ３ may be substituted with a radical; In formula (II-A), CR １ At least one Z １ groups are present; The compound of formula (II-A) contains only one triarylamino group. Compound.

2. In the formula (II-A), one or two Z １ The group is in each case CR １ And other Z １ The group is CR ３ The compound according to claim 1, characterized in that

3. 3. The compound according to claim 1, wherein k is 0.

4. k is not 0, -(Ar Ｌ ) ｋ - is of the formula: 【Chemistry 2-1】 【Chemistry 2-2】 【Chemistry 2-3】 【Chemistry 2-4】 in which the dotted lines in each case represent a bond to the remainder of formula (II-A) above.

3. A compound according to claim 1 or 2, characterized in that it meets one of the following criteria:

5. Ar ２ are the same or different in each occurrence and are selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, wherein each of the mentioned groups is selected from one or more of R ５ The compound according to any one of claims 1 to 4, which may be substituted by a radical.

6. In formula (II-A), 【Chemistry 3】 The radical has in each case the formula 【Chemistry 4-1】 【Chemistry 4-2】 【Chemistry 4-3】 【Chemistry 4-4】 【Chemistry 4-5】 【Chemistry 4-6】 wherein the groups are each represented by R ５ The bond shown with a dashed line represents the bond to the remainder of formula (II-A) above. The compound according to any one of claims 1 to 5, characterized in that it is selected from

7. 7. The compound according to claim 6, characterized in that said group is unsubstituted at said unoccupied position and the bond shown with a dashed line represents the bond to the remainder of formula (II-A).

8. R １ are the same or different in each occurrence and are selected from monovalent radicals derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine, and triazine, wherein the monovalent radicals each are selected from one or more R ６ The compound according to any one of claims 1 to 7, which may be substituted by a radical.

9. R ２ and R ３ The compound according to any one of claims 1 to 8, characterized in that is H.

10. A process for preparing a compound of formula (II-A) according to any one of claims 1 to 9, characterized in that a benzene compound having two carboxylic ester groups and at least one reactive group is reacted with a benzene compound containing a boronic acid group and at least one group selected from a reactive group X and an aromatic or heteroaromatic Ar group, wherein the boronic acid group and the at least one group selected from X and Ar groups are in the ortho or meta position relative to each other on the benzene ring.

11. A formulation comprising at least one compound according to any one of claims 1 to 9 and at least one solvent.

12. An electronic device comprising at least one compound according to any one of claims 1 to 9.

13. 13. The electronic device of claim 12, characterized in that it is an organic electroluminescent device comprising an anode, a cathode and at least one light-emitting layer, and that the compound is present in a hole-transporting layer of the device.

14. 14. The organic electroluminescent device of claim 13, wherein the compound is present in an electron blocking layer of the device.

15. Use of a compound according to any one of claims 1 to 9 in an electronic device.

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