Materials for electronic devices

Abstract

To provide organic electroluminescent devices having improved lifetime, efficiency, and operating voltage.SOLUTION: There are provided a compound of lower formula (I-B), a method for preparing the compound, and an electronic device containing the compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present application relates to aromatic compounds containing a group selected from an amino group, a crosslinked amino group, and a carbazole group, represented by the following defined formulas (I) and (II). These compounds are suitable for use in electronic devices.

[0002] The electronic devices related to the present application are understood to mean so-called organic electronic devices containing an organic semiconductor material as a functional material. More specifically, these are understood to mean OLEDs (organic electroluminescent devices). The term OLED is understood to mean an electronic device having one or more layers containing an organic compound and emitting light when a voltage is applied. The general principles of the structure and function of OLEDs are known to those skilled in the art.

[0003] In electronic devices, especially OLEDs, there is a strong interest in improving performance data, especially lifetime, efficiency, and operating voltage. In these aspects, a fully satisfactory solution has not yet been found.

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

[0005] Greatly influencing the performance data of electronic devices are the light-emitting layer and the layer having a hole transport function. There is also a need for novel compounds for use in these layers, especially hole transport compounds, and compounds that can function as a matrix material, especially for phosphorescent emitters, in the light-emitting layer.

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

[0007] However, alternative compounds suitable for use in electronic devices are still needed. Improvements are also needed with respect to performance data in the use of electronic devices, particularly with respect to lifetime, operating voltage and efficiency.

[0008] Certain compounds from the class of structures described above have now been found to be extremely suitable for use in electronic devices, particularly for use in OLEDs, especially for use as hole transport materials in OLEDs and as matrix materials for phosphorescent emitters. The compounds preferably lead to long device lifetimes, high efficiency and low operating voltage. More preferably, the compounds have a low tendency to crystallize, a high glass transition temperature and a high refractive index.

[0009] This application relates to the following formula (I) or (II):

[0010]

Chemical formula

[0011] (wherein the variable groups that appear are as follows: Z 1 is the same or different in each case and is selected from CR 1 and CR 3 ; Ar 1 has 6 to 20 aromatic ring atoms and is an aryl group optionally substituted by one or more R 3 radicals, or has 5 to 20 aromatic ring atoms and is a heteroaryl group optionally substituted by one or more R 3 radicals; Ar 2 is the same or different in each case and is selected from an aromatic ring system having 6 to 40 aromatic ring atoms and optionally substituted by one or more R 5 radicals, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms and optionally substituted by one or more R 5 radicals; Ar 3 has 6 to 20 aromatic ring atoms and is an aryl group optionally substituted by one or more R 2 radicals, or has 5 to 20 aromatic ring atoms and is a heteroaryl group optionally substituted by one or more R 2 radicals; X 1 is, in each case, the same or different and is a divalent group selected from -C(R 4 ) 2 -, -C(R 4 ) 2 -C(R 4 ) 2 -, -CR 4 =CR 4 -, -Si(R 4 ) 2 -, NR 4 , O and S; Ar L has 6 to 40 aromatic ring atoms and is an aromatic ring system optionally substituted by one or more R 5 radicals, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms and optionally substituted by one or more R 5 radicals; E is a single bond or a divalent group selected from C(R 5 ) 2 , Si(R 5 ) 2 , N(R 5 ), O, and S; R 0 is H, D, an aromatic ring system having 6 to 40 aromatic ring atoms and optionally substituted by one or more R 6 radicals, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms and optionally substituted by one or more R 6 radicals; R 1 is, in each case, the same or different and has 6 to 40 aromatic ring atoms and is an aromatic ring system optionally substituted by one or more R 6 radicals, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms and optionally substituted by one or more R 6Selected from heteroaromatic ring systems which may be substituted by radicals; R 2 is, in each case, the same or different and is selected from 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; where two or more R 0 radicals may be bonded to each other or may form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups mentioned, and the aromatic ring systems and heteroaromatic ring systems mentioned may each be substituted by one or more R 6 radicals; one or more CH 2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -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 ; R 3 、R 4 、R 5 is, in each case, the same or different and is selected from 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, selected from; where two or more R 3 or R 4 or R 5 radicals may be bonded to each other or may form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups mentioned, and the aromatic ring system and heteroaromatic ring system mentioned, may each be substituted by one or more R 6 radicals; one or more CH 2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -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 ; R 6 is, in each case, the same or different, 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, wherein two or more R 6 radicals may be bonded to each other or may form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups mentioned, and the aromatic ring system and heteroaromatic ring system mentioned, may each be substituted by one or more R 7 radicals; one or more CH 2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by -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 ; R 7 is in each case the same or different and is 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; where two or more R 7 radicals may be bonded to each other or may form a ring; the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring system and heteroaromatic ring system mentioned may be substituted by F or CN; k is 0, 1, 2 or 3, where when k = 0, the Ar L group is absent and the nitrogen atom (N) of the group of the formula constitutes the bonding position; m is 0 or 1, where when m = 0, the E group is absent and Ar 2The groups are not bonded to each other; Here, in formulas (I) and (II), all of the positions shown as unsubstituted may each be substituted by an R 3 radical; In formulas (I) and (II), in each case, at least one Z 1 group which is CR 1 is present); to provide a compound of.

[0012] The circles drawn in the six-membered rings of formulas (I) and (II) mean that the respective six-membered rings are aromatic.

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

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

[0015] The heteroaryl group according to 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. The fused heteroaromatic polycycle according to the present application consists of two or more single aromatic or heteroaromatic rings fused to each other, where at least one of the aromatic and heteroaromatic rings is a heteroaromatic ring. The fusion between the rings is here understood to mean that the rings share at least one edge with each other. The heteroaryl group according to the present invention contains 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom of the heteroaryl group is preferably selected from N, O and S.

[0016] An aryl or heteroaryl group, each of which may be substituted by the above radicals, especially means a group derived from 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, naphthimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalineimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarbazole, 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.

[0017] The aromatic ring system related to the present invention does not necessarily contain only aryl groups, and in addition, it may be a system containing one or more non-aromatic rings condensed to at least one aryl group. These non-aromatic rings contain only carbon atoms as ring atoms. Examples of groups included in this definition are tetrahydronaphthalene, fluorene, and spirobifluorene. In addition, the term "aromatic ring system" refers to a system composed of two or more aromatic ring systems bonded to each other via a single bond, such as biphenyl, terphenyl, 7-phenyl-2-fluorenyl, quarterphenyl, and 3,5-diphenyl-1-phenyl. The aromatic ring system related to the present invention contains 6 to 40 carbon atoms and does not contain heteroatoms in the ring system. The definition of "aromatic ring system" does not include heteroaryl groups.

[0018] The heteroaromatic ring system conforms to the above definition of the aromatic ring system, except that it must contain at least one heteroatom as a ring atom. Similar to the case of the aromatic ring system, the heteroaromatic ring system does not necessarily contain only aryl groups and heteroaryl groups, and in addition, it may contain one or more non-aromatic rings condensed to at least one aryl or heteroaryl group. The non-aromatic ring may contain only carbon atoms as ring atoms, or in addition, it may 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 composed of two or more aromatic or heteroaromatic ring systems bonded to each other via a single bond, such as 4,6-diphenyl-2-triazinyl. The heteroaromatic ring system related to the present invention contains 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] Accordingly, the terms "heteroaromatic ring system" and "aromatic ring system" as defined in the present application are different 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. This heteroatom may be present as a ring atom of a non-aromatic heterocyclic ring or as a ring atom of an aromatic heterocyclic ring.

[0020] According to the above definition, any aryl group is included in the term "aromatic ring system", and any heteroaryl group is included in 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, a group derived from the groups mentioned above under aryl groups and heteroaryl groups, and from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, torquene, isotorquene, spirotorquene, spiroisotorquene, indenocarbazole or a combination of these groups.

[0022] For the present invention, a linear alkyl group having 1 to 20 carbon atoms, and a branched or cyclic alkyl group having 3 to 20 carbon atoms, and an alkenyl or alkynyl group having 2 to 40 carbon atoms are each a hydrogen atom or CH 2The group may be substituted by the groups mentioned earlier in the definition of the radical, preferably 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 radical is understood.

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

[0024] With respect to the present application, the expression that two or more radicals may together form a ring is of course understood to mean, in particular, that two radicals are bonded to each other by a chemical bond. However, in addition to this, the above expression is of course also understood to mean that when one of the two radicals is hydrogen, the second radical is bonded to the position where the hydrogen atom is bonded to form a ring.

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

[0026] Preferably, one or two Z 1 groups are CR 1 and the other Z 1 groups are CR 3 More preferably, one Z 1 group is CR 1 and the other two Z 1 groups are CR 3 .

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

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

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

[0030] The Ar L group preferably has 6 to 20 aromatic ring atoms and is selected from an aromatic ring system optionally substituted by one or more R 5 radicals and a heteroaromatic ring system having 5 to 20 aromatic ring atoms and optionally substituted by one or more R 5 radicals. Particularly preferred Ar LThe group is selected from divalent groups derived from benzene, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene, and carbazole, each of which may be substituted by one or more R 5 radicals. Most preferably, Ar L is, in each case, a divalent group derived from benzene which may be substituted by one or more R 5 radicals. The Ar L groups may be selected identically or differently in each case.

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

[0032] Preferred -(Ar L ) k - groups are of the following formula:

[0033]

Chemical formula

[0034]

Chemical formula

[0035]

Chemical formula

[0036]

Chemical formula

[0037]

Chemical formula

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

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

[0040] Preferably, the Ar 2 groups are the same or different in each case and are selected from monovalent groups 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 groups may each be substituted by one or more R 5 radicals. Alternatively, the Ar 2 groups are preferably the same or different in each case and may be selected from combinations of groups 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 groups may each be substituted by one or more R 5 radicals.

[0041] Particularly preferred Ar 2The groups are the same or different in each case and are selected from phenyl, biphenyl, terphenyl, quarterphenyl, 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, where the groups mentioned may each be substituted by one or more R 5 radicals.

[0042] Particularly preferred Ar 2 groups are of the following formula:

[0043]

Chemical formula

[0044]

Chemical formula

[0045]

Chemical formula

[0046]

Chemical formula

[0047]

Chemical formula

[0048]

Chemical formula

[0049]

Chem.

[0050]

Chem.

[0051]

Chem.

[0052]

Chem.

[0053]

Chem.

[0054]

Chem.

[0055]

Chem.

[0056]

Chem.

[0057]

Chem.

[0058]

Chem.

[0059] (In the formula, all the groups are each R at all non-occupied positions 5 and may be substituted by a radical, and the bond represented by a broken line represents a bond to an amine nitrogen atom.) is selected from

[0060] In each case, two different Ar 2 groups are preferably bonded to the amine nitrogen atom.

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

[0062] Preferably, m = 0 so that the E group is absent.

[0063] In a similarly preferred alternative embodiment, m = 1 such that the Ar 2 groups are bonded to each other via the E group. In this case, the Ar 2 groups are preferably selected from phenyl and fluorenyl, each of which may be substituted by one or more R 5 radicals. In addition, in this case, the E group bonding the two Ar 2 groups to each other is preferably bonded to the Ar 2 group at the ortho position with respect to the bond of the Ar 2 group to the amine nitrogen. In addition, the E group, together with the Ar 2 group, preferably forms a 6-membered ring when E is C(R 5 ) 2 , Si(R 5 ) 2 , NR 5 , O and S, and a 5-membered ring when E is a single bond.

[0064] The unit when m = 1

[0065]

Chemical formula

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

[0067]

Chemical formula

[0068]

Chemical formula

[0069]

Chemical formula

[0070] (In the formula, the groups may each be substituted by R radicals at their unoccupied positions, preferably unsubstituted at the unoccupied positions, and the bond shown by the dashed line represents the bond to the rest of the formula) 5 is as follows. is.

[0071] The group when m = 0

[0072]

Chemical formula

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

[0074]

Chemical formula

[0075]

Chemical formula

[0076]

Chemical formula

[0077] [Chemical formula]

[0078] [Chemical formula]

[0079] [Chemical formula]

[0080] (In the formula, the groups may each be substituted by R radicals at their unoccupied positions, preferably unsubstituted at the unoccupied positions, and the bond shown by the dashed line represents a bond to the rest of the formula) 5 [and is as follows] >.

[0081] R 0 is preferably H.

[0082] R 1 is preferably the same or different in each case and is selected from monovalent groups 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 group may each be substituted by one or more R 6 radicals. When R radicals are present in the group, one or two R 6 radicals are preferably N(R 6 ), 7 where R 2 is preferably 7is selected from an aromatic ring system having 6 to 40 aromatic ring atoms and a heteroaromatic ring system having 5 to 40 aromatic ring atoms. Particularly preferred R 1 groups are phenyl, phenyl substituted by one or two -N(R 7 ) 2 groups, biphenyl, N-bonded carbazolyl, C-bonded carbazolyl, naphthyl, dibenzofuranyl and dibenzothiophenyl, each of which may be substituted by one or more R 6 radicals and is preferably unsubstituted.

[0083] R 2 is preferably the same or different in each case and is 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, where the alkyl group and the aromatic ring system and heteroaromatic ring system may each be substituted by one or more R 6 radicals. More preferably, R 2 is H.

[0084] R 3 is preferably the same or different in each case and is selected from 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; where the alkyl group mentioned, the aromatic ring system mentioned and the heteroaromatic ring system mentioned may each be substituted by one or more R 6 radicals; one or more CH 2 groups in the alkyl group mentioned 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 may be replaced by. More preferably, R 3 is H.

[0085] R 4 、R 5 are preferably the same or different in each case and are selected from 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 mentioned, the aromatic ring system mentioned and the heteroaromatic ring system mentioned may each be substituted by one or more R 6 radicals; one or more CH 2 groups in the alkyl group mentioned may be -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 radicals attached to the group are preferably selected from an alkyl group having 1 to 20 carbon atoms, an aromatic ring system having 6 to 20 aromatic ring atoms and a heteroaromatic ring system having 5 to 20 aromatic ring atoms; wherein the alkyl group, the aromatic ring system and the heteroaromatic ring system may each be substituted by one or more R 4 radicals. In a preferred embodiment, two R 6 in the X 1 =C(R 4 ) 2 group 4The radical is X 1 =C(R 4 ) 2 groups are joined together to form a ring such that the carbon atom of the =C(R

[0087]

Chemical formula

[0088] (wherein the bond indicated by the dotted line represents the bond from the X 1 group to the remainder of the compound) is as follows.

[0089] Preferably, each R 6 is the same or different in each case and is selected from 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 mentioned, the aromatic ring system mentioned, and the heteroaromatic ring system mentioned may each be substituted by one or more R 7 radicals; one or more CH 2 groups in the alkyl or alkoxy group mentioned may be replaced by -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 -.

[0090] Preferred embodiments of formula (I) are the following formulas:

[0091] [Chemical formula]

[0092] (In the formula, all positions shown as unsubstituted on the benzene ring may each be substituted by an R 3 radical). corresponds to.

[0093] Preferably, in formulas (I-A) and (I-B), the group

[0094] [Chemical formula]

[0095] is, in each case, bonded para to the bond to the adjacent benzene group, which is represented by formulas (I-A-a) and (I-B-a):

[0096] [Chemical formula]

[0097] (In the formula, all positions shown as unsubstituted on the benzene ring may each be substituted by an R 3 radical). corresponds to.

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

[0099] [Chemical formula]

[0100] (In the formula, all positions shown as unsubstituted on the benzene ring may each be substituted by an R 3 radical). corresponds to.

[0101] A further preferred embodiment of formula (I) is the following formula:

[0102]

Chem.

[0103] (wherein the variable groups that appear are as defined above, and R 0 and R 3 are preferably H) corresponds. More preferably, in these formulas, k = 0 and m = 0, and Ar 1 is a phenyl group which may be substituted by one or more R 3 radicals.)

[0104] Preferred embodiments of formulas (I-A) and (I-B) are the following formulas:

[0105]

Chem.

[0106] (wherein the variable groups that appear are as defined above) correspond. Preferably, in these formulas, k = 0 and m = 0. More preferably, in these formulas, R 3 and R 0 are H. Preferably, in formulas (I-A-1), (I-A-2) and (I-B-1), the group

[0107]

Chem.

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

[0109]

Chem.

[0110] (wherein the variable groups appearing are as defined above) corresponds to

[0111] Preferred embodiments of formulas (I-A-1), (I-A-2) and (I-B-1) are the following formulas:

[0112]

Chemical formula

[0113]

Chemical formula

[0114]

Chemical formula

[0115]

Chemical formula

[0116]

Chemical formula

[0117]

Chemical formula

[0118]

Chemical formula

[0119] (wherein the variable groups appearing are as defined above, and R 0 and R 3 are preferably H) is. In formulas (I-A-1-3), (I-A-1-4), (I-A-2-3), (I-A-2-4), (I-B-1-3) and (I-B-1-4), E is preferably a single bond and C(R 4) 2 selected from; more preferably, E is a single bond. Ar in formulas (I-A-1-1), (I-A-1-3), (I-A-1-7), (I-A-2-1), (I-A-2-3), (I-B-1-1), (I-B-1-3) and (I-B-1-7) L is preferably a phenyl group which may be substituted by one or more R 5 radicals. Preferably, in the above formulas, the following groups

[0120]

Chemical formula

[0121] selected from the groups, when present, are attached in the para position with respect to the bond to the adjacent benzene group in each case.

[0122] Among the above formulas, formulas (I-A-1-1), (I-A-1-2), (I-A-2-1), (I-A-2-2), (I-B-1-1) and (I-B-1-2) are particularly preferred, among which (I-A-1-1) and (I-A-1-2) are preferred, and among which (I-A-1-2) is very particularly preferred. Correspondingly, very particularly preferred formulas are the following embodiments of formulas (I-A-1-1) and (I-A-1-2):

[0123]

Chemical formula

[0124] wherein formula (I-A-1-2-a) is the most preferred.

[0125] Preferred embodiments of formula (II-A) are the following formulas:

[0126]

Chemical formula

[0127] (wherein the variable groups that appear are as defined above, and R 2 and R 3 are preferably H) corresponds. In formulas (II-A-1) and (II-A-3), E is preferably a single bond and C(R 4 ) 2 selected from; more preferably, E is a single bond. Ar L in formulas (II-A-1) and (II-A-2) is preferably a phenyl group which may be substituted by one or more R 5 radicals. Among the above formulas, formula (II-A-4) is particularly preferred.

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

[0129]

Chemical formula

[0130]

Chemical formula

[0131]

Chemical formula

[0132]

Chemical formula

[0133]

Chemical formula

[0134]

Chemical formula

[0135]

Chemical formula

[0136] [Chemical]

[0137] [Chemical]

[0138] [Chemical]

[0139] [Chemical]

[0140] [Chemical]

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

[0142] In a preferred method (Scheme 1), starting from a benzene compound having two reactive groups X and two carboxylic acid ester groups, a benzene group having an amino group A is bonded to one side of the central benzene group and a benzene group having an aromatic Ar substituent is bonded to the other side through two consecutive Suzuki couplings to prepare an intermediate. The aromatic substituent is in the ortho or meta position with respect to the bond between the two benzene groups.

[0143] Subsequently, the carboxylic acid ester group of this compound is 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 under the action of an acid to form a ring, and as a result, the compound of formula (I) is obtained.

[0144]

Chemical formula

[0145] In an alternative preferred method (Scheme 2), starting from a benzene compound having two reactive groups X and two carboxylic acid ester groups, a benzene group having a reactive group X is bonded to one side of the central benzene group and a benzene group having an aromatic substituent Ar is bonded to the other side by two consecutive Suzuki couplings to prepare an intermediate. The aromatic substituent is in the ortho or meta position with respect to the bond between the two benzene groups.

[0146] Subsequently, the carboxylic acid ester group of this compound is 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 under the action of an acid to form a ring. Finally, an amino group is introduced by Buchwald coupling or a diarylaminoaryl or diarylaminoheteroaryl group is introduced by a Suzuki reaction so that the compound of formula (I) is obtained.

[0147]

Chemical formula

[0148] In an alternative preferred method (Scheme 3), starting from a benzene compound having two reactive groups X and two carboxylic acid ester groups, an intermediate is prepared by two successive Suzuki couplings in which a benzene group having a reactive group X is bonded on one side to the central benzene group and a benzene group having an amino group A is bonded on the other side. The reactive group X is in the ortho or meta position with respect to the bond between the two benzene groups.

[0149] Subsequently, the carboxylic acid ester groups of this compound are converted to tertiary alkoxy groups by reaction with a metal alkyl compound, preferably a lithium alkyl compound or a Grignard alkyl compound. These tertiary alkoxy groups cyclize under the action of an acid to form a ring. Finally, an aromatic substituent Ar is introduced by a Suzuki reaction, and as a result, a compound of formula (I) is obtained.

[0150]

Chemical formula

[0151] A preferred method for preparing the compound of formula (II) is shown in Scheme 4 below. In this case, first, starting from a benzene compound having two reactive groups X and two carboxylic acid ester groups, an intermediate is prepared by two successive Suzuki couplings in which a benzene group is bonded on one side to the central benzene group and a benzene group having two reactive X groups is bonded 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. Subsequently, the carboxylic acid ester groups of this compound are converted to tertiary alkoxy groups by reaction with a metal alkyl compound, preferably a lithium alkyl compound or a Grignard alkyl compound. These tertiary alkoxy groups cyclize under the action of an acid to form a ring. Then, an amino group is introduced by a Buchwald coupling or a diarylaminoaryl or diarylaminoheteroaryl group is introduced by a Suzuki reaction. Finally, an aromatic substituent Ar is introduced by a Suzuki reaction, and as a result, a compound of formula (II) is obtained.

[0152] [Chemical formula]

[0153] Accordingly, the present application further provides a method for preparing a compound of formula (I) or (II), the method comprising reacting a benzene compound having two carboxylic acid ester groups and at least one reactive group 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. In this case, at least one group selected from the boronic acid group and the X and Ar groups is in the ortho or meta position 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 reacting a benzene compound having two carboxylic acid 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 by reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic acid ester, can find use as monomers for producing corresponding oligomers, dendrimers or polymers. Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boronic acid, boronic acid ester, amine, alkenyl or alkynyl groups having a terminal C-C double bond or C-C triple bond, oxirane, oxetane, groups involved in cycloaddition, for example 1,3-dipolar cycloaddition, such as diene or azide, carboxylic acid derivatives, alcohols and silanes.

[0156] Accordingly, 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 R in formula (I) or (II) 1 、R 2, R 3 , R 4 or R 5 may be localized at any desired position substituted thereby. Depending on the bond of the compound, the compound becomes part of the side chain or the main chain of the oligomer or polymer. The oligomer according to the present invention is understood to mean a compound formed from at least three monomer units. The polymer according to the present invention is understood to mean a compound formed from at least ten monomer units. The polymer, oligomer or dendrimer of the present invention may be conjugated, partially conjugated, or non-conjugated. The oligomer or polymer of the present invention may be linear, branched or dendritic. In a structure having a linear bond, the units of formula (I) or (II) may be directly 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 valent group, for example via a trivalent or higher valent aromatic or heteroaromatic group, to form a branched or dendritic oligomer or polymer.

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

[0158] For the preparation of oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with additional 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 further contain additional 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 the polymerization of one or more monomers, at least one of which provides repeating units of formula (I) or (II) in the polymer. Suitable polymerization reactions are known to those skilled in the art and are described in the literature. Particularly suitable preferred polymerization reactions that result in the formation of C-C or C-N bonds are Suzuki polymerization, Yamamoto polymerization, Still polymerization and Hartwig-Buchwald polymerization.

[0160] To process the compounds of the invention from the liquid phase, for example by spin coating or printing methods, formulations of the compounds of the invention are required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. 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, especially 3-phenoxytoluene, (-)-fencon, 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, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or mixtures of these solvents.

[0161] Accordingly, 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. Methods for preparing such solutions are known to those skilled in the art.

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

[0163] Accordingly, the present invention further provides for the use of a compound of formula (I) or (II) in an electronic device. This electronic device is preferably selected from the group consisting of an organic integrated circuit (OIC), an organic field effect transistor (OFET), an organic thin film transistor (OTFT), an organic light emitting transistor (OLET), an organic solar cell (OSC), an organic optical detector, an organic photoreceptor, an organic field quenching device (OFQD), an organic light emitting electrochemical cell (OLEC), an organic laser diode (O-laser), and more preferably an organic electroluminescent device (OLED).

[0164] As already mentioned above, the present invention further provides an electronic device comprising at least one compound of formula (I) or (II). This electronic device is 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, wherein at least one organic layer, which may be the light emitting layer, a hole transport layer or another layer, comprises at least one compound of formula (I) or (II).

[0166] In addition to the cathode, anode, and light emitting layer, the organic electroluminescent device may further comprise additional layers. These are in each case 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 sequence of the organic electroluminescent device containing the compound of formula (I) or (II) is preferably as follows: anode - hole injection layer - hole transport layer - any further hole transport layer(s) - any electron blocking layer - light emitting layer - any hole blocking layer - electron transport layer - electron injection layer - cathode. In addition, it is also possible for further layers to be present in the OLED.

[0168] The organic electroluminescent device of the present invention may contain two or more light emitting layers. More preferably, these light emitting layers, in this case, have several emission maxima as a whole in the range of 380 nm to 750 nm and produce white light emission as a whole; in other words, they can emit fluorescence or phosphorescence, and various light emitting compounds that emit blue, green, yellow, orange or red light are used in the light emitting layer. Particularly preferred is a three-layer system, i.e., a system having three light emitting layers, where the three layers exhibit blue, green and orange or red light emission. The compound of the present invention is preferably present in the hole transport layer, hole injection layer, electron blocking layer, and / or light emitting layer here, more preferably as a matrix material in the light 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 containing one or more phosphorescent compounds. In this case, the compound may be present in different layers, preferably in the hole transport layer, electron blocking layer, hole injection layer, and / or light emitting layer. More preferably, the compound is present in the electron blocking layer or in the light emitting layer in combination with the phosphorescent compound. 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" typically includes compounds in which light emission occurs by spin-forbidden transitions 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, in particular, compounds that preferably emit light in the visible region when appropriately excited and further contain at least one atom having an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. As the phosphorescent compound, it is preferable to use a compound containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular, a compound containing iridium, platinum or copper. Regarding the present invention, all luminescent iridium, platinum or copper complexes are regarded as phosphorescent compounds.

[0172] Generally, all phosphorescent complexes that are used in phosphorescent OLEDs according to the prior art and are known to those skilled in the art in the field of organic electroluminescent devices are suitable. Those skilled in the art can also use additional phosphorescent complexes in combination with the compounds of formula (I) or (II) in organic electroluminescent devices without exercising any inventive creativity. Further examples are given in the following table:

[0173]

Chemical formula

[0174]

Chemical formula

[0175]

Chemical formula

[0176]

Chemical formula

[0177]

Chemical formula

[0178] [Chemical]

[0179] [Chemical]

[0180] [Chemical]

[0181] [Chemical]

[0182] [Chemical]

[0183] [Chemical]

[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 the hole transport layer. 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 the hole transport layer, the latter is preferably an electron blocking layer. This is preferably directly adjacent to the light emitting layer on the anode side.

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

[0186] For the present application, the hole injection layer and the electron blocking layer are understood to be specific embodiments of the hole transport layer. When there are multiple hole transport layers between the anode and the light-emitting layer, the hole injection layer is a hole transport layer that is directly adjacent to the anode or is separated from the anode by a single coating of the anode. 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 includes 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), and more preferably only one or two contain a compound of formula (I) or (II).

[0187] When a compound of formula (I) or (II) is used as a hole transport material in a hole transport layer, a hole injection layer, or an electron blocking layer, the compound can be used as a pure material, i.e., used in the hole transport layer at a rate of 100%, or can also be used in combination with one or more additional compounds. In that case, in a preferred embodiment, the organic layer containing the compound of formula (I) or (II) additionally contains one or more p-dopants. The p-dopant used according to the present invention is preferably an organic electron acceptor compound 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 a metal of Group 3, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd, and Pt having a ligand containing at least one oxygen atom as a binding site. Transition metal oxides are more preferred as dopants, preferably oxides of rhenium, molybdenum, and tungsten, more preferably Re 2 O 7 , MoO 3 , WO 3 and ReO 3It is as follows.

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

[0190] Preferred p-dopants are, inter alia, the following compounds:

[0191] [Chemical formula]

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

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

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

[0195] Correspondingly, the proportion of the light-emitting compound is 0.1% to 50.0% by volume, preferably 0.5% to 20.0% by volume, more preferably 3.0% to 15.0% by volume.

[0196] The light-emitting layer of an organic electroluminescent device may include a system containing a plurality of matrix materials (mixed matrix system) and / or a plurality of light-emitting compounds. Also in this case, the light-emitting compound is generally the compound with the lower proportion in the system, and the matrix material is the compound with the higher proportion in 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 compound of formula (I) or (II) is preferably used as a component of a mixed matrix system for a phosphorescent emitter. The mixed matrix system preferably contains 2 or 3 different matrix materials, more preferably 2 different matrix materials. Preferably, in this case, one of the two materials is a material having hole-transporting properties, and the other material is a material having electron-transporting properties. The compound of formula (I) or (II) is preferably a matrix material having hole-transporting properties. Correspondingly, the compound of formula (I) or (II) is used as a matrix material for a phosphorescent emitter in the light-emitting layer of an OLED, and a second matrix compound having electron-transporting properties is present in the light-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, and most preferably 1:4 to 1:1.

[0198] However, the desired electron-transporting and hole-transporting properties of the mixed matrix component may be mainly or completely possessed by a single mixed matrix component, and in this case, a further mixed matrix component(s) serves other functions.

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

[0200] Particularly suitable matrix materials that can be used as matrix components of a mixed matrix system in combination with the compounds of the present invention are selected from the preferred matrix materials defined below for phosphorescent compounds, especially those having electron transport 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. The arylamine or aromatic amine according to the present invention is understood to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, more preferably having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthraceneamine, aromatic anthracenediamine, aromatic pyreneamine, aromatic pyrenediamine, aromatic chryseneamine or aromatic chrysenediamine. Aromatic anthraceneamine is understood to mean a compound in which a diarylamino group is directly bonded to an anthracene group, preferably at the 9-position. Aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably at the 9,10-positions. Aromatic pyreneamine, pyrenediamine, chryseneamine and chrysenediamine are similarly defined, where the diarylamino group is bonded to pyrene, preferably at the 1-position or 1,6-positions. Further preferred luminescent compounds are indenofluoreneamine or diamine, benzoindenofluoreneamine or diamine, and dibenzoindenofluoreneamine or diamine, and indenofluorene derivatives having a condensed aryl group. Similarly preferred are pyrenearyl amine, benzoindenofluoreneamine, benzofluoreneamine, extended benzoindenofluorene, phenoxazine, and fluorene derivatives substituted by furan units or thiophene units.

[0203] Preferably, useful matrix materials for fluorescent emitting compounds include materials of various classes of substances. Preferred matrix materials are selected from oligophenylene (e.g., 2,2’,7,7’-tetraphenylspirobifluorene or dinaphthylanthracene), especially oligophenylene containing condensed aromatic groups, oligophenylene vinylene (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 benzoanthracene classes. Particularly preferred matrix materials are selected from oligophenylene containing naphthalene, anthracene, benzoanthracene and / or pyrene or atropisomers of these compounds, oligophenylene vinylene, ketones, phosphine oxides, and sulfoxides. Particularly very preferred matrix materials are selected from the class of oligophenylene containing anthracene, benzoanthracene, benzophenanthrene and / or pyrene or atropisomers of these compounds. The oligophenylene according to the present invention is of course understood to mean a compound in which at least three aryl or arylene groups are bonded to each other.

[0204] Preferred matrix materials for phosphorescent emitting compounds include, 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, diazasilole or tetraazasilole derivatives, diazaphosphole derivatives, crosslinked carbazole derivatives, triphenylene derivatives and lactams.

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

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

[0207]

Chemical formula

[0208]

Chemical formula

[0209]

Chemical formula

[0210] Preferably, the OLED of the present invention includes two or more different hole transport layers. The compound of formula (I) or (II) may be used herein 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 compound of formula (I) or (II), additional compounds preferably used in the hole transport layer of the OLED of the present invention include, inter alia, indenofluoreneamine derivatives, amine derivatives, hexaazatriphenylene derivatives, amine derivatives containing a condensed aromatic system, monobenzoindenofluoreneamine, dibenzoindenofluoreneamine, spirobifluoreneamine, fluoreneamine, spirodibenzopyranamine, dihydroacridine derivatives, spirodibenzofuran and spirodibenzothiophene, phenanthrenediarylamine, spirotribenzotropolone, spirobifluorene having a metaphenyldiamine group, spirobisacridine, xantenediarylamine, and 9,10-dihydroanthracene spiro compounds having a diarylamino group.

[0211] The material used in the electron transport layer may be any material that can be used as an electron transport material in the electron transport layer 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 following table are particularly preferred:

[0212]

Chemical formula

[0213]

Chemical formula

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

[0215] Preferred anodes are materials having a high work function. Preferably, the anode has a work function exceeding 4.5 eV with respect to vacuum. First, metals having a high redox potential are suitable for this purpose, such as Ag, Pt or Au. Second, metal / metal oxide electrodes (e.g., Al / Ni / NiO x 2, Al / PtO x) may also be preferred. Depending on the application, at least one of the electrodes must be transparent or partially transparent in order to enable either irradiation of the organic material (organic solar cell) or light emission (OLED, O-LASER). 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 appropriately structured (depending on the application), the contacts are connected, and finally sealed in order 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 this case, the material is deposited by evaporation in a vacuum sublimation system at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6 mbar. However, in this case, it is also possible to make the initial pressure even lower, for example less than 10 -7 mbar.

[0218] Similarly, an electronic device characterized in that one or more layers are coated by the OVPD (organic vapor deposition) method or with the assistance of carrier gas sublimation is preferred. In this case, the material is deposited at a pressure of 10 -5 mbar to 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, in which the material is deposited directly by a nozzle and thus structured (for example M.S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0219] In addition, it is preferable that one or more layers are formed from a solution, for example, by spin coating, or by any printing method such as screen printing, flexographic printing, nozzle printing or offset printing, 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 appropriate substitution of the compounds.

[0220] It is more preferable that the electronic device of the present invention is manufactured by applying one or more layers from a solution and applying one or more layers by a sublimation process.

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

[0222] [Example] A) Synthesis example Example 1-1: Synthesis of Compound 1-1 and isomers of the present invention

[0223] [Chemical formula]

[0224] Intermediate I-1 22 g of boronic acid ester derivative 0-1 (34.8 mmol) and 11.7 g of 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 saturated with N 2 and then 0.6 g (0.51 mmol) of Pd(Ph 3 P) 4 is added. The reaction mixture is heated to boiling under a protective atmosphere for 16 hours. Subsequently, the mixture is fractionated between toluene and water, the organic phase is washed three times with water, and Na 2 SO4 Dry it above and concentrate it by rotary evaporation. Extract the remaining residue by stirring it in heptane. The yield is 23 g (87% of the theoretical value). Intermediate II-1 Suspend 6.3 g of (2-phenylphenyl)boronic acid (31.6 mmol) and 23 g of chlorine derivative I-1 (30 mmol) in 260 ml of toluene and 100 ml of water. Add 8.3 g of potassium carbonate thereto. Degas the solution and saturate it with N 2 . Then, add 276 mg (0.3 mmol) of Pd 2 (dba) 3 and 250 mg of SPhos (0.3 mmol). Heat and boil the reaction mixture under a protective atmosphere for 12 hours. Subsequently, fractionate the mixture between toluene and water, wash the organic phase three times with water, and dry it over Na 2 SO 4 . Concentrate it by rotary evaporation. Filter the crude product through silica gel with toluene, and then recrystallize the remaining residue from EtOH. The yield is 20.7 g (80% of the theoretical value).

[0225] Prepare the following compounds in a similar manner:

[0226]

Chemical formula

[0227]

Chemical formula

[0228]

Chemical formula

[0229]

Chemical formula

[0230]

Chemical formula

[0231] Compound 1-1 Dissolve 15.0 g (17.4 mmol) of Intermediate II-1 in 150 ml of dry THF in a fired flask. Saturate the solution with N 2 . Cool the clear solution to -5 °C and then add 35 ml (105 mmol) of 3 M methylmagnesium chloride solution. Gradually warm the reaction mixture to room temperature and then quench with ammonium chloride. Subsequently, fractionate the mixture between ethyl acetate and water, wash the organic phase three times with water, dry over Na 2 SO 4 and concentrate by rotary evaporation. Dissolve the solution concentrated by rotary evaporation in toluene and add 8 g of Amberlyst 15. Heat the mixture to 110 °C and hold at this temperature for 4 hours. A white solid precipitates during this time. Then cool the mixture to room temperature, filter the precipitated solid by suction and wash with heptane. Dry the residue at 40 °C under reduced pressure. After filtering the crude product through silica gel with 1:1 heptane:ethyl acetate, 13 g (90% of theory) of the product is obtained. Finally, sublime this material under high vacuum. The purity is 99.9%.

[0232] Prepare the following compounds in a similar manner:

[0233]

Chemical formula

[0234]

Chemical formula

[0235]

Chemical formula

[0236]

Chemical formula

[0237] Compound 2-1

[0238]

Chem.

[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 saturate it with N 2 . Then, add 0.28 g (0.302 mmol) of Pd 2 (dba) 3 and 0.6 ml of a 1 M solution of (tBu) 3 P to it, and then add 4.3 g of sodium tert-butoxide (45.3 mmol). Heat the reaction mixture to boiling under a protective atmosphere for 6 hours. Subsequently, fractionate the mixture between toluene and water, wash the organic phase three times with water, dry it over Na 2 SO 4 , and concentrate it by rotary evaporation. After filtering the crude product through silica gel with toluene, recrystallize the remaining residue from heptane / toluene. The yield is 14.3 g (72% of theory). Finally, sublime this material under high vacuum. The purity is 99.9%.

[0240] Prepare the following compounds in a similar manner:

[0241]

Chem.

[0242]

Chem.

[0243]

Chem.

[0244] Compound 3-1

[0245]

Chem.

[0246] 17.1 g (28.51 mmol) of the pinacol boronic acid ester derivative IV-1 and 12 g (28.51 mmol) of the 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 taken out, filtered through silica gel, washed three times with 80 ml of water, and then concentrated until dry. 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, this material is sublimated under high vacuum. The purity is 99.9%.

[0247] The following compounds are prepared in a similar manner:

[0248]

Chem.

[0249]

Chem.

[0250]

Chem.

[0251] B) Device Example 1) General manufacturing method of OLED and characterization of OLED A glass plaque coated with structured ITO (indium tin oxide) with a thickness of 50 nm is the substrate to 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) / emission layer (EML) / electron transport layer (ETL) / electron injection layer (EIL), and finally the 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 the following table. The materials required for the manufacture of the OLED are shown in the following table.

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

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

[0255] The OLED is 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 characteristics assuming Lambertian emission characteristics, and the lifetime are determined. The parameter EQE@10 mA / cm 2 refers to the external quantum efficiency achieved at 10 mA / cm 2 The parameter U@10 mA / cm 2 refers to the operating voltage at 10 mA / cm 2 The lifetime LT80@60 mA / cm 2 is defined as the time until it drops to 80% of the initial value without using an acceleration factor when operated at a current density of 60 mA / cm 2 2) Use of the compounds of the present invention in the HIL and HTL of blue fluorescent light-emitting devices Manufacture an OLED having the following structure:

[0256]

Table 1

[0257] As a result, very good results are obtained regarding the performance data of the OLED: EQE@10mA / cm 2 is about 7.5%, and the operating voltage U@10mA / cm 2 is about 4V, and the lifetime LT80@60mA / cm 2 exceeds 300 hours. 3) Use of the compound of the present invention in the EBL of a green phosphorescent light-emitting device Manufacture an OLED having the following structure:

[0258]

Table 2

[0259] As a result, very good results are obtained regarding the performance data of the OLED 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 exceeds 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 Manufacture the OLED I6 of the present invention having the same structure as the OLED I1 described in 2), and the only difference is that the compound HTM-1 is present in the HIL and HTL of the OLED instead of the compound HTM-2.

[0260] For comparison, manufacture an OLED C1 having the same structure as the OLED I6 of the present invention, and the only difference is 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 distinct improvement in the EQE value and a slight decrease in the operating voltage were observed as compared with the comparative OLED C1. The lifetime LT80@60mA / cm 2 exceeds 300 hours in both cases. The obtained values are shown in the following table:

[0262]

Table 3

[0263]

Table 4-1

[0264]

Table 4-2

Claims

1. The compound represented by the following formula (I) or (II): 【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 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 a heteroaryl group optionally substituted by a radical; 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 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 a heteroaryl group optionally substituted by a radical; X １ are the same or different in each occurrence, -C(R ４ ) ２ -, -C(R ４ ) ２ -C(R ４ ) ２ -, -CR ４ =CR ４ -, -Si(R ４ ) ２ -, N.R. ４ is a divalent group selected from O and S; 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 ０ has H, D, 6 to 40 aromatic ring atoms, and one or more R 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 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; ０ 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; 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), CR １ At least one Z １ group is present) Compound.

2. In one of the formulas (I) and (II), 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. X １ C(R ４ ) ２ The compound according to any one of claims 1 to 3, characterized in that

4. A compound according to any one of claims 1 to 3, characterized in that k is 0.

5. k is not 0, -(Ar Ｌ ) ｋ - is of the formula: 【Chemistry 2-1】 【Chemistry 2-2】 【Chemistry 2-3】 【Chemistry 2-4】 Compounds according to any one of claims 1 to 3, characterized in that they comply with one of the following formulae: in which the dotted line in each case represents a bond to the remainder of said formula (I) or (II).

6. Ar ２ 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, wherein said mentioned groups each may be selected from one or more R ５ The compound according to any one of claims 1 to 5, which may be substituted by a radical.

7. In formulas (I) and (II), 【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 radicals, preferably unsubstituted at said unoccupied positions, and the bond shown with a dashed line represents the bond to the remainder of formula (I) or (II) as defined above.

7. The compound according to claim 1, characterized in that it is selected from:

8. R ０ The compound according to any one of claims 1 to 7, characterized in that is H.

9. R １ 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 ６ The compound according to any one of claims 1 to 8, which may be substituted by a radical.

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

11. Formula (I) is of the following formula: 【Chemistry 5】 A compound according to any one of claims 1 to 10, characterized in that it meets the following:

12. A process for preparing a compound of formula (I) or (II) according to any one of claims 1 to 11, characterized in that a benzene compound having two carboxylic acid 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.

13. 12. An oligomer, polymer or dendrimer containing one or more compounds of formula (I) or (II) according to any one of claims 1 to 11, wherein the bond(s) to the polymer, oligomer or dendrimer are selected from the group consisting of R １ , R ２ , R ３ , R ４ Or R ５ The substituted aryl groups may be located at any desired position in the oligomer, polymer or dendrimer.

14. A formulation comprising at least one compound according to any one of claims 1 to 11 or at least one polymer, oligomer or dendrimer according to claim 13 and at least one solvent.

15. An electronic device comprising at least one compound according to any one of claims 1 to 11 or at least one polymer, oligomer or dendrimer according to claim 13.

16. 16. The electronic device of claim 15, comprising an organic electroluminescent device comprising an anode, a cathode and at least one light-emitting layer, and wherein said compound is present in a hole-transporting layer of said device.

17. 17. The organic electroluminescent device of claim 16, wherein the compound is present in an electron blocking layer of the device.

18. Use of a compound according to any one of claims 1 to 11 in an electronic device.

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