COMPOSITIONS WITH ARYLAMIN STRUCTURES

Description

[0001] The present invention describes arylamine derivatives substituted with diazanaphthalene groups, particularly for use in electronic devices. The invention further relates to a process for preparing the compounds according to the invention and to electronic devices containing these compounds.

[0002] In organic electroluminescent devices (OLEDs), organometallic complexes that exhibit phosphorescence are often used as emitting materials. For quantum mechanical reasons, using organometallic compounds as phosphorescence emitters can achieve up to four times the energy and power efficiency. In general, there is still room for improvement in OLEDs, especially in OLEDs that exhibit phosphorescence, for example, with regard to efficiency, operating voltage, and lifetime.

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

[0004] WO 2012 / 143080 describes bridged carbazole derivatives that can be substituted by (hetero)aromatic groups, where these aromatic groups can be substituted by a diarylamino group. WO 2014 / 079527 describes compounds in which an N-carbazolyl group and a diarylamino group are linked via an aromatic group. All of these compounds can be used in OLEDs.

[0005] According to the prior art, heteroaromatic compounds, such as quinazoline derivatives, are frequently used as matrix materials for phosphorescent compounds and as electron-transport materials. Triarylamine derivatives are also used as matrix materials, and compounds containing both triarylamine structures and groups derived from quinazoline are also known. However, these compounds do not necessarily have aryl or heteroaryl substitution on at least two of the aryl radicals derived from the triarylamine structure that are bonded to the nitrogen atom. Furthermore, not all of these compounds are substituted with another aryl or heteroaryl group on the ring of the diazanaphthalene structure to which the diarylamine group is bonded. Furthermore, some of the compounds form carbazole groups with an aryl radical bonded to the nitrogen atom of the diarylamine group.

[0006] In general, there is still room for improvement in these materials, for example for use as matrix materials, hole transport materials or electron transport materials, particularly with regard to lifetime, but also with regard to the efficiency and operating voltage of the device.

[0007] The object of the present invention is therefore to provide compounds which are suitable for use in an organic electronic device, in particular in an organic electroluminescent device, and which, when used in this device, lead to good device properties, as well as to provide the corresponding electronic device.

[0008] In particular, the object of the present invention is to provide compounds that result in a long lifetime, good efficiency, and low operating voltage. The properties of the matrix materials, the hole-transport materials, or the electron-transport materials in particular have a significant influence on the lifetime and efficiency of the organic electroluminescent device.

[0009] A further object of the present invention can be seen in providing compounds suitable for use in a phosphorescent or fluorescent OLED, in particular as a matrix material. In particular, it is an object of the present invention to provide matrix materials suitable for red, yellow, and green phosphorescent OLEDs.

[0010] Furthermore, the compounds should lead to devices with excellent color purity, especially when used as matrix materials, as hole transport materials or as electron transport materials in organic electroluminescent devices.

[0011] Furthermore, the compounds should be as easy to process as possible, particularly exhibiting good solubility and film formation. For example, the compounds should exhibit increased oxidation stability and an improved glass transition temperature.

[0012] Another objective is to provide electronic devices with excellent performance at the lowest possible cost and with consistent quality. Furthermore, the electronic devices should be able to be used or adapted for a variety of purposes. In particular, the performance of the electronic devices should be maintained over a wide temperature range.

[0013] Surprisingly, it has been found that certain compounds, described in more detail below, achieve these objects and eliminate the disadvantage of the prior art. The use of these compounds leads to very good properties of organic electronic devices, in particular organic electroluminescent devices, particularly with regard to lifetime, efficiency, and operating voltage. Electronic devices, in particular organic electroluminescent devices, containing such compounds, as well as the corresponding preferred embodiments, are therefore the subject of the present invention.

[0014] The present invention therefore relates to a compound comprising at least one structure according to the following formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa) or (XXIVb) where the symbols used are: L is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which may be substituted by one or more non-aromatic radicals R 1<; Z 1< , Z 2< , Z 3< , Z 4< is X; X is the same or different on each occurrence and is N or CR 1<, where a maximum of two X per ring is N, preferably CR 1< , or C, if a radical Ar a< is bonded to X; X 1< is the same or different on each occurrence and is N or CR 1<; n, o, p is 0; m is 0 or 1; i is 0, 1 or 2, preferably 0 or 1; j is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1; his is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0 or 1;Ar a< is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 1<, where the radical Ar a< does not comprise a carbazole group or form one with the aryl or heteroaryl group to which Ar a< binds, this including substituents R 1<, R 2< and R 3< which may be bound to the radical Ar a<; Ar b< is an aromatic or heteroaromatic ring system having 5 to 45 aromatic ring atoms, which may be substituted by one or more radicals R 1<;R 1< is, on each occurrence, identical or different, H, D, CN, N(Ar 1< ) 2 , a straight-chain alkyl group having 1, 2, 3 or 4 C atoms or a branched or cyclic alkyl group having 3 to 8 C atoms or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R 2<, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 2<, or a combination of these systems; two or more, preferably adjacent, substituents R 1< can also form a monocyclic, aliphatic or aromatic ring system with one another; Ar 1< is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R 2<;two radicals Ar 1< which are bonded to the same Si atom, N atom, P atom or B atom can also be bridged to one another by a single bond or a bridge selected from B(R 2< ), C(R 2< ) 2 , Si(R 2< ) 2 , C=O, C=NR 2< , C=C(R 2< ) 2 , O, S, S=O, SO 2 , N(R 2< ), P(R 2< ) and P(=O)R 2< ; R 2< is, on each occurrence, identical or different, H, D, CN, a straight-chain alkyl group having 1, 2, 3 or 4 C atoms or a branched alkyl group having 3 or 4 C atoms, each of which may be substituted by one or more radicals R 3<, where one or more H atoms may be replaced by D or CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R 3<, or a combination of these systems; two or more, preferably adjacent, substituents R 2< can also form a monocyclic, aliphatic or aromatic ring system with one another;R 3< is, at each occurrence, identical or different, selected from the group consisting of H, D, CN, an aliphatic hydrocarbon radical having 1, 2, 3 or 4 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by DI or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; two or more, preferably adjacent, substituents R 3< may form a monocyclic, aliphatic ring system with one another; ; with the proviso that at least one group X 1< in formula (IIIa) or (IIIb) is N, and with the proviso that compounds of formula (A) are excluded, where the symbols X, Ar b< and R 1< have the meaning set out above and k is 0 or 1.

[0015] From the above formulation, it can be seen that, since the indices n, o, and p = 0, the corresponding bridges Y 1< , Y 2< , Y 3< are not present, and the corresponding symbol Z 1< , Z 2< , Z 3< , Z 4< in this case stands for X. In contrast, m = 0 means that a single bond is present between the nitrogen atom and the heteroaromatic. Particularly preferred is m = 0. This means that the diazanaphthalene group or quinazoline group binds directly to the nitrogen atom of the diarylamine group.

[0016] Furthermore, it is evident from the above structures of formulas (IIIa) and (IIIb) that the group Ar b< and the group L bond to the same ring of the diazanaphthyl group, wherein the two bonding sites to the diazanaphthyl group are not adjacent but separated by a group X 1<. Preferably, the group L bonds to a site on the diazanaphthyl group that is adjacent to an N atom of the diazanaphthyl group, so that the symbol X', which is adjacent to the bonding site of the group L, represents a nitrogen atom. Preferably, the group Ar b< bonds to a site on the diazanaphthyl group that is adjacent to an N atom of the diazanaphthyl group, so that the symbol X', which is adjacent to the bonding site of the group Ar b<, represents a nitrogen atom.

[0017] For the purposes of the present invention, adjacent carbon atoms are carbon atoms that are directly linked to one another. Furthermore, "adjacent radicals" in the definition of radicals means that these radicals are bonded to the same carbon atom or to adjacent carbon atoms. These definitions apply accordingly, among other things, to the terms "adjacent groups" and "adjacent substituents."

[0018] For the purposes of this description, the phrase "two or more residues can form a ring" is understood to mean, among other things, that the two residues are linked by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme.

[0019] Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring. This is illustrated by the following scheme:

[0020] A fused aryl group, a fused aromatic ring system, or a fused heteroaromatic ring system within the meaning of the present invention is a group in which two or more aromatic groups are fused, i.e., annulated, to one another via a common edge, so that, for example, two C atoms belong to the at least two aromatic or heteroaromatic rings, as in naphthalene, for example. In contrast, fluorene, for example, is not a fused aryl group within the meaning of the present invention, since in fluorene the two aromatic groups do not have a common edge. Corresponding definitions apply to heteroaryl groups and to fused ring systems, which may, but do not necessarily, contain heteroatoms.

[0021] An aryl group within the meaning of this invention contains 6 to 40 C atoms; a heteroaryl group within the meaning of this invention contains 2 to 40 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e. benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc., or a condensed aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.

[0022] An aromatic ring system within the meaning of this invention contains 6 to 40 C atoms in the ring system. A heteroaromatic ring system within the meaning of this invention contains 1 to 40 C atoms and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O, and / or S. An aromatic or heteroaromatic ring system within the meaning of this invention is understood to mean a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be interrupted by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as a C, N, or O atom or a carbonyl group. For example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc.are understood as aromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group. Furthermore, systems in which two or more aryl or heteroaryl groups are directly bonded to one another, such as biphenyl, terphenyl, quaterphenyl, or bipyridine, are also to be understood as aromatic or heteroaromatic ring systems.

[0023] A cyclic alkyl, alkoxy or thioalkoxy group in the sense of this invention is understood to mean a monocyclic, a bicyclic or a polycyclic group.

[0024] In the context of the present invention, a C 1 - to C 20 -alkyl group, in which individual H atoms or CH 2 groups can also be substituted by the above-mentioned groups, is understood to mean, for example, the radicals methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, Cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2,2,2]octyl, 2-bicyclo[2,2,2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-Trifluoroethyl, 1,1-Dimethyl-n-hex-1-yl-, 1,1-Dimethyl-n-hept-1-yl-, 1,1-Dimethyl-n-oct-1-yl-, 1,1-Dimethyl-n-dec-1-yl-, 1,1-Dimethyl-n-dodec-1-yl-, 1,1-Dimethyl-n-tetradec-1-yl-, 1,1-Dimethyl-n-hexadec-1-yl-, 1,1-Dimethyl-n-octadec-1-yl-, 1,1-Diethyl-n-hex-1-yl-, 1,1-Diethyl-n-hept-1-yl-, 1,1-Diethyl-n-oct-1-yl-, 1,1-Diethyl-n-dec-1-yl-, 1,1-Diethyl-n-dodec-1-yl-, 1,1-Diethyl-n-tetradec-1-yl-, 1,1-Diethyln-n-hexadec-1-yl-, 1,1-Diethyl-n-octadec-1-yl-, 1-(n-propyl)-cyclohex-1-yl-, 1-(n-butyl)-cyclohex-1-yl-, 1-(n-hexyl)-cyclohex-1-yl-, 1-(n-Octyl)-cyclohex-1-yl- and 1-(n-Decyl)-cyclohex-1-yl- An alkenyl group is understood to mean, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, or cyclooctadienyl. An alkynyl group is understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, or octynyl. A C 1 - to C 40 -alkoxy group is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, or 2-methylbutoxy.

[0025] An aromatic or heteroaromatic ring system with 5 - 40 aromatic ring atoms, which can also be substituted with the above-mentioned radicals and which can be linked to the aromatic or heteroaromatic ring via any position, is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, Isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine,Benzo-5,6-chinolin, Benzo-6,7-chinolin, Benzo-7,8-chinolin, Phenothiazin, Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1,2-Thiazol, 1,3-Thiazol, Benzothiazol, Pyridazin, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1,5-Diazaanthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1,6-Diazapyren, 1,8-Diazapyren, 4,5-Diazapyren, 4,5,9,10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1,2,3-Triazol, 1,2,4-Triazol, Benzotriazol, 1,2,3-Oxadiazol, 1,2,4-Oxadiazol, 1,2,5-Oxadiazol, 1,3,4-Oxadiazol, 1,2,3-Thiadiazol, 1,2,4-Thiadiazol, 1,2,5-Thiadiazol, 1,3,4-Thiadiazol, 1,3,5-Triazin, 1,2,4-Triazin, 1,2,3-Triazin, Tetrazol, 1,2,4,5-Tetrazin, 1,2,3,4-Tetrazin, 1,2,3,5-Tetrazin, Purin, Pteridin, Indolizin und Benzothiadiazol.,

[0026] Furthermore, compounds having structures according to formula (IIIa) or (IIIb) are preferred, in which at least two, preferably at least three of the symbols X stand for CR 1<, particularly preferably at least three of the symbols X are selected from CH and CD.

[0027] Preferably, the compounds according to the invention may comprise at least one structure of formula (IVa) and / or (IVb), where the symbols m, n, o, p, L, R 1< , Ar a< , Ar b< , Y 1< , Y 2< , Y 3< , Z 1< , Z 2< , Z 3< , Z 4< and X 1< have the meaning set out above, at least one group X 1< stands for N and i stands for 0, 1 or 2, preferably for 0 or 1.

[0028] Preferably, the compounds according to the invention may comprise at least one structure of formula (Va) and / or (Vb), where the symbols used m, n, o, p, L, R 1< , Ar a< , Ar b< , Y 1< , Y 2< , Y 3< , Z 1< , Z 2< , Z 3< , Z 4< and X have the meaning set out above and i stands for 0, 1 or 2, preferably for 0 or 1.

[0029] In a further preferred embodiment, the compounds according to the invention may have at least one structure of the formula (VIa) and / or (VIb), where the symbols used m, n, o, L, R 1< , Ar a< , Ar b< , Y 1< , Y 2< , Y 3< , Z 3< , Z 4< and X have the meaning given above, i stands for 0, 1 or 2, preferably for 0 or 1 and j stands for 0, 1, 2 or 3, preferably for 0, 1 or 2, particularly preferably for 0 or 1.

[0030] Furthermore, it can be provided that compounds according to the invention comprise at least one structure of formula (VIIa) and / or (VIIb), where the symbols m, L, Ar a< , Ar b< , R 1< and X used have the meaning set out above, i stands for 0, 1 or 2, preferably for 0 or 1 and h stands for 0, 1, 2, 3 or 4, preferably for 0, 1 or 2, particularly preferably for 0 or 1.

[0031] Furthermore, compounds comprising at least one structure of formula (VIIIa) and / or (VIIIb) are preferred, where the symbols m, L, Ar a< , Ar b< and R 1< have the meaning set out above and h stands for 0, 1, 2, 3 or 4, preferably for 0, 1 or 2, particularly preferably for 0 or 1.

[0032] Preferably, the radical Ar a<, in particular in the formulas (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (VIIa), (VIIb), (VIIIa), (VIIIb) may comprise a spirobifluorene, fluorene, dibenzofuran or dibenzothiophene group or form it with the aryl or heteroaryl radical to which the radical Ar a< is bound.

[0033] In a further preferred embodiment, the compounds according to the invention may comprise at least one structure of formula (IXa) or (IXb), where the symbols m, L, Ar a< , Ar b< , R 1< and X used have the meaning set out above, j stands for 0, 1, 2 or 3, preferably for 0, 1 or 2, particularly preferably for 0 or 1 and h stands for 0, 1, 2, 3 or 4, preferably for 0, 1 or 2, particularly preferably for 0 or 1 and i stands for 0, 1 or 2, preferably for 0 or 1.

[0034] Furthermore, the compounds according to the invention may comprise at least one structure of formula (Xa) or (Xb), where the symbols m, L, Ar a< , Ar b< and R 1< have the meaning set out above, j stands for 0, 1, 2 or 3, preferably for 0, 1 or 2, particularly preferably for 0 or 1 and h stands for 0, 1, 2, 3 or 4, preferably for 0, 1 or 2, particularly preferably for 0 or 1.

[0035] In a further preferred embodiment, the compounds according to the invention may have at least one structure of the formula (XIa), (XIb), (XIc), (XId), (XIe) or (XIf), where the symbols m, L, Ar a< , Ar b< , R 1< and X used have the meaning set out above, i stands for 0, 1 or 2, preferably for 0 or 1, j stands for 0, 1, 2 or 3, preferably for 0, 1 or 2, particularly preferably for 0 or 1 and h stands for 0, 1, 2, 3 or 4, preferably for 0, 1 or 2, particularly preferably for 0 or 1.

[0036] Furthermore, it can be provided that compounds according to the invention comprise at least one structure of formula (XIIa) or (XIIb), where the symbols m, L, Ar a< , Ar b< , R 1< and X used have the meaning set out above, i stands for 0, 1 or 2, preferably for 0 or 1, j stands for 0, 1, 2 or 3, preferably for 0, 1 or 2, particularly preferably for 0 or 1 and h stands for 0, 1, 2, 3 or 4, preferably for 0, 1 or 2, particularly preferably for 0 or 1.

[0037] Preferably, the group L can form a continuous conjugation with the diazanaphthalene radical to which the group L is bonded according to formulas (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (Vlla), (Vllb), (Vllla), (Vllb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (Xlla), (Xllb), and with the diarylamine group of these formulas. In a further preferred embodiment of the invention, L represents an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic or heteroaromatic ring system having 6 to 13 carbon atoms, which may be substituted by one or more radicals R 1<, but is preferably unsubstituted, where R 1< may have the meaning given above.L particularly preferably represents an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which may be substituted by one or more radicals R 1<, but is preferably unsubstituted, where R 1< may have the meaning given above.

[0038] Furthermore, the symbol L shown, inter alia, in the structures according to formulas (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (VIIa), (VIIb), (VIIIa), (VIIIb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIIa) and / or (XIIb) is, identically or differently on each occurrence, a bond, which corresponds to m = 0, or an aryl or heteroaryl radical having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, particularly preferably 6 to 10 ring atoms, so that an aromatic or heteroaromatic group of an aromatic or heteroaromatic ring system is bonded directly, ie via an atom of the aromatic or heteroaromatic group, to the respective atom of the further group.

[0039] Furthermore, it can be provided that the group L shown, inter alia, in the structures according to formulas (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (VIIa), (VIIb), (VIIIa), (VIIIb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIIa) and / or (XIIb) comprises an aromatic ring system with at most two fused aromatic and / or heteroaromatic six-membered rings, preferably no fused aromatic or heteroaromatic ring system. Accordingly, naphthyl structures are preferred over anthracene structures. Furthermore, fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structures are preferred over naphthyl structures.

[0040] Particularly preferred are structures that do not exhibit condensation, such as, for example, phenyl, biphenyl, terphenyl and / or quaterphenyl structures. Especially preferred for the group L shown in formulas (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (VIIa), (VIIb), (VIIIa), (VIIIb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIlla) and / or (XIIb) are phenyl, biphenyl, dibenzofuranyl and / or dibenzothienyl structures, which may be substituted by one or more radicals R 1< as defined above.Examples of suitable aromatic or heteroaromatic ring systems L are selected from the group consisting of ortho-, meta- or para-phenylene, ortho-, meta- or para-biphenylene, terphenylene, in particular branched terphenylene, quaterphenylene, in particular branched quaterphenylene, fluorenylene, spirobifluorenylene, dibenzofuranylene, dibenzothienylene and carbazolylene, which may each be substituted by one or more radicals R 2<, but are preferably unsubstituted.

[0041] Furthermore, it can be provided that the group L set out, inter alia, in the structures according to formulas (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (VIIa), (VIIb), (VIIIa), (VIIIb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIIa) and / or (XIIb) has at most 1 nitrogen atom, preferably at most 2 heteroatoms, particularly preferably at most one heteroatom and particularly preferably no heteroatom.

[0042] Preferred are compounds comprising structures of the formulas (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (VIIa), (VIIb), (VIIIa), (VIIIb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIIa) and / or (XIIb), in which the group L represents a group selected from the formulas (L-1) to (L-15), where the dashed bonds each mark the attachment positions, the index I is 0, 1 or 2, the index j is independently 0, 1, 2 or 3 at each occurrence, the index h is independently 0, 1, 2, 3 or 4 at each occurrence, the index g is 0, 1, 2, 3, 4 or 5, the symbol is YO, S or NR 2<, preferably O or S, and the symbol R 1< has the meaning given above, in particular for formula (I).

[0043] Particularly preferred are the formulas (L-1) to (L-4) and (L-10) to (L-15), where Y in the preferred formulas (L-10) to (L-15) is O or S. Preferably, it can be provided that the sum of the indices k, l, g, h and j in the structures of the formulas (L-1) to (L-15) is in each case at most 3, preferably at most 2 and particularly preferably at most 1.

[0044] In a preferred embodiment, the compounds according to the invention may contain a structure of formula (XIII), where Z 5< and Z 6< are the same or different and stand for X or C, the symbols m, n, o, p, Ar a< , Ar b< , Y 1< , Y 2< , Y 3< , Z 1< , Z 2< , Z 3< , Z 4< , X and X 1< have the meaning given above and at least two groups X 1< stand for N. Preferably, a maximum of two groups X or X 1< per ring stand for N.

[0045] Preferably, the compounds according to the invention may comprise at least one structure of formula (XIVa) and / or (XIVb), where the symbols m, n, o, p, Ar a< , Ar b< , Y 1< , Y 2< , Y 3< , Z 1< , Z 2< , Z 3< , Z 4< , Z 5< , Z 6< , X and X 1< have the meaning given above or in formula (XIII) and at least one group X 1< stands for N. Preferably, a maximum of two groups X or X 1< per ring stand for N.

[0046] Preferably, the compounds according to the invention may comprise structures according to formula (XVa) and / or (XVb), where the symbols m, n, o, p, Ar a< , Ar b< , Y 1< , Y 2< , Y 3< , Z 1< , Z 2< , Z 3< , Z 4< , Z 5< , Z 6< , X and X 1< have the meaning given above or in formula (XIII), at least one group X 1< stands for N and i stands for 0, 1 or 2, preferably for 0 or 1. Preferably, a maximum of two groups X per ring stand for N.

[0047] Furthermore, compounds having structures according to formula (XIVa), (XIVb), (XVa) or (XVb) are preferred, in which at least six, preferably at least eight of the symbols X stand for CR 1<, particularly preferably at least six of the symbols X are selected from CH and CD.

[0048] Preferably, the compounds according to the invention may comprise at least one structure of formula (XVIa) and / or (XVIb), where the symbols m, n, o, p, Ar a< , Ar b< , Y 1< , Y 2< , Y 3< , Z 1< , Z 2< , Z 3< , Z 4< , Z 5< , Z 6< and X 1< have the meaning given above or in formula (XIII), at least one group X 1< stands for N and i stands for 0, 1 or 2, preferably for 0 or 1.

[0049] Preferably, the compounds according to the invention may comprise at least one structure of formula (XVIIa) and / or (XVIIb), where the symbols used m, n, o, p, Ar a< , Ar b< , Y 1< , Y 2< , Y 3< , Z 1< , Z 2< , Z 3< , Z 4< , Z 5< , Z 6< and X have the meaning given above, in particular for formula (XIII) and i stands for 0, 1 or 2, preferably for 0 or 1.

[0050] In a further preferred embodiment, the compounds according to the invention may have at least one structure of the formula (XVIIIa) and / or (XVIIIb), where the symbols used m, n, o, Ar a< , Ar b< , Y 1< , Y 2< , Y 3< , Z 3< , Z 4< , Z 5< , Z 6< and X have the meaning given above, in particular for formula (XIII), i stands for 0, 1 or 2, preferably for 0 or 1 and j stands for 0, 1, 2 or 3, preferably for 0, 1 or 2, particularly preferably for 0 or 1.

[0051] Furthermore, it can be provided that the compounds according to the invention comprise at least one structure of the formula (XIXa) and / or (XIXb), where the symbols m, Ar a< , Ar b< , R 1< and X used have the meaning set out above, i stands for 0, 1 or 2, preferably for 0 or 1 and h stands for 0, 1, 2, 3 or 4, preferably for 0, 1 or 2, particularly preferably for 0 or 1.

[0052] Furthermore, compounds comprising at least one structure of formula (XXa) and / or (XXb) are preferred, where the symbols m, Ar a< , Ar b< and R 1< have the meaning set out above and h stands for 0, 1, 2, 3 or 4, preferably for 0, 1 or 2, particularly preferably for 0 or 1.

[0053] Preferably, the radical Ar a< can, identically or differently on each occurrence, in particular in the formulas (XIII), (XIVa), (XIVb), (XVa), (XVb), (XVIa), (XVIb), (XVIIa), (XVIIb), (XVIIIa), (XVIIIb), (XIXa), (XIXb), (XXa) and / or (XXb), comprise a spirobifluorene, fluorene, dibenzofuran or dibenzothiophene group or form it with the aryl or heteroaryl radical to which the radical Ar a< is bound.

[0054] Furthermore, the compounds according to the invention may comprise at least one structure of formula (XXIIa) or (XXIIb), where the symbols m, Ar a< , Ar b< and R 1< have the meaning set out above, j stands for 0, 1, 2 or 3, preferably for 0, 1 or 2, particularly preferably for 0 or 1 and h stands for 0, 1, 2, 3 or 4, preferably for 0, 1 or 2, particularly preferably for 0 or 1.

[0055] In a further preferred embodiment, the compounds according to the invention may have at least one structure of the formula (XXIIIa), (XXIIIb), (XXIIIc), (XXIIId), (XXIIIe) or (XXIIIf), where the symbols m, Ar a< , Ar b< , R 1< and X used have the meaning set out above, i stands for 0, 1 or 2, preferably for 0 or 1, j stands for 0, 1, 2 or 3, preferably for 0, 1 or 2, particularly preferably for 0 or 1 and h stands for 0, 1, 2, 3 or 4, preferably for 0, 1 or 2, particularly preferably for 0 or 1.

[0056] Furthermore, compounds comprising at least one structure of the formula (XXVa), (XXVb), (XXVc), (XXVd), (XXVe), (XXVf), (XXVg) or (XXVh) are preferred, where the symbols Ar a< , Ar b< , R 1< and X used have the meaning set out above, i stands for 0, 1 or 2, preferably for 0 or 1 and h stands for 0, 1, 2, 3 or 4, preferably for 0, 1 or 2, particularly preferably for 0 or 1.

[0057] In a preferred embodiment, the index m can be 0, so that the nitrogen atom of the diarylamine group is directly bonded to the diazanaphthyl group. Therefore, compounds with structures of the formulas (XXVa) and / or (XXVb) are particularly preferred.

[0058] In a preferred embodiment of the invention, a maximum of four symbols X 1< stand for N per structure of the formulas presented above. Particularly preferably, a maximum of three symbols X 1< stand for N. Very particularly preferably, exactly two symbols X 1< stand for N in structures of the formulas (IIIa), (IIIb) or (XIII) presented above, and exactly one symbol X 1< stands for N in structures of the formulas (IIIa), (IIIb), (IVa), (IVb), (XIVa), (XIVb), (XVa), (XVb), (XVIa) or (XVIb) presented above.

[0059] In a further preferred embodiment of the invention, a maximum of four X symbols represent N per structure of the formulas presented above. Particularly preferably, a maximum of two X symbols represent N. Most preferably, none of the X symbols represents N in structures of the formulas presented above.

[0060] The radical Ar a< represents an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 1<. For the sake of completeness, it should be noted that the radical Ar a< together with the aryl or heteroaryl group to which the radical Ar a< binds can form an aromatic or heteroaromatic ring system, whereby the number of ring atoms of the ring system formed can increase accordingly.

[0061] Preferably, the radical Ar a< , in particular in the formulas (XXVa), (XXVb), (XXVc), (XXVd), (XXVe), (XXVf), (XXVg) or (XXVh), may comprise a spirobifluorene, fluorene, dibenzofuran or dibenzothiophene group or form it with the aryl or heteroaryl radical to which the radical Ar a< is bound.

[0062] It can preferably be provided that the radical Ar a<, in particular in the formulas (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (Vlla), (Vllb), (Vllla), (Vlllb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIIa), (XIIb), (XIII), (XIVa), (XIVb), (XVa), (XVb), (XVIa), (XVIb), (XVIIa), (XVIIb), (XVIIIa), (XVIIIb), (XIXa), (XIXb), (XXa), (XXb), (XXIa), (XXIb), (XXIIa), (XXIIb), (XXIIIa), (XXIIIb), (XXIIIc), (XXIIId), (XXIIIe), (XXIIIf), (XXIVa), (XXIVb), (XXVa), (XXVb), (XXVc), (XXVd), (XXVe), (XXVf), (XXVg) or (XXVh) represents an aryl or heteroaryl radical having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 1<, where the radical Ar a< does not comprise or form a carbazole group with the aryl or heteroaryl group to which Ar a< binds, this including substituents R 1<, R 2< and R 3< which may be bound to the radical Ar a<.Particularly preferably, the radical Ar a< has at most 3, especially preferably at most 2 radicals R 1< and can be unsubstituted in a very particularly preferred embodiment.

[0063] Preferably, the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system represented by the symbol Ar a< is bonded directly, ie via an atom of the aromatic or heteroaromatic group, to the respective atom of the further group, wherein the symbol Ar a< particularly preferably represents an aryl or heteroaryl radical.

[0064] In a further preferred embodiment of the invention, Ar a< is identical or different on each occurrence and represents an aromatic or heteroaromatic ring system, preferably an aryl or heteroaryl radical having 5 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, particularly preferably an aromatic ring system, preferably an aryl radical having 6 to 12 aromatic ring atoms or a heteroaromatic ring system, preferably a heteroaryl group having 5 to 13 aromatic ring atoms, which may in each case be substituted by one or more radicals R 1<, but is preferably unsubstituted, where R 1< may have the meaning shown above.

[0065] The radical Ar a< does not comprise a carbazole group or does not form a carbazole group with the aryl or heteroaryl group to which Ar a< is bonded, this including substituents R 1< , R 2< and R 3< which may be bonded to the radical Ar a<. Preferably, it can be provided that substituents R 1< with which the aryl or heteroaryl group to which the radical Ar a< is bonded and which is bonded to the nitrogen atom of the diarylamine group may be substituted do not comprise a carbazole group or form a carbazole group with the aryl or heteroaryl group to which Ar a< is bonded, this including substituents R 2< and R 3< which may be bonded to the radical R 1<.

[0066] Preferably, it can be provided that the radical Ar b < in particular in the formulas (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (Vlla), (Vllb), (Vllla), (Vlllb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIIa), (XIIb), (XIII), (XIVa), (XIVb), (XVa), (XVb), (XVIa), (XVIb), (XVIIa), (XVIIb), (XVIIIa), (XVIIIb), (XIXa), (XIXb), (XXa), (XXb), (XXIa), (XXIb), (XXIIa), (XXIIb), (XXIIIa), (XXIIIb), (XXIIIc), (XXIIId), (XXIIIe), (XXIIIf), (XXIVa), (XXIVb), (XXVa), (XXVb), (XXVc), (XXVd), (XXVe), (XXVf), (XXVg) or (XXVh) represents an aryl or heteroaryl radical having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 1<. The radical Ar b< particularly preferably has at most 3, especially preferably at most 2, radicals R 1< and may be unsubstituted in a very particularly preferred embodiment.

[0067] Preferably, the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system represented by the symbol Ar b< is bonded directly, ie via an atom of the aromatic or heteroaromatic group, to the respective atom of the further group, wherein the symbol Ar b< particularly preferably represents an aryl or heteroaryl radical.

[0068] In a further preferred embodiment of the invention, Ar b< is identical or different on each occurrence and represents an aromatic or heteroaromatic ring system, preferably an aryl or heteroaryl radical having 5 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, particularly preferably an aromatic ring system, preferably an aryl radical having 6 to 12 aromatic ring atoms or a heteroaromatic ring system, preferably a heteroaryl group having 5 to 13 aromatic ring atoms, which may in each case be substituted by one or more radicals R 1<, but is preferably unsubstituted, where R 1< may have the meaning shown above.

[0069] Furthermore, it can be provided that in the structures according to formulas (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (Vlla), (Vllb), (Vllla), (Vlllb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (Xlla), (XIIb), (XIII), (XIVa), (XIVb), (XVa), (XVb), (XVIa), (XVIb), (XVIIa), (XVIIb), (XVIIIa), (XVIIIb), (XIXa), (XIXb), (XXa), (XXb), (XXIa), (XXIb), (XXIIa), (XXIIb), (XXIIIa), (XXIIIb), (XXIIIc), (XXIIId), (XXIIIe), (XXIIIf), (XXIVa), (XXIVb), (XXVa), (XXVb), (XXVc), (XXVd), (XXVe), (XXVf), (XXVg) and / or (XXVh) the group Ar b< represents a group of the formula (Ar b< -1), wherein L' is a bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 1<, the symbol R 1< has the meaning set out above, h is 0, 1, 2, 3 or 4, preferably 0, 1 or 2 and the dashed line represents the bond.

[0070] According to a preferred embodiment, compounds according to the invention are characterized by structures according to formula (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (VIIa), (VIIb), (VIIIa), (VIIIb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIIa), (XIIb), (XIII), (XIVa), (XIVb), (XVa), (XVb), (XVIa), (XVIb), (XVIIa), (XVIIb), (XVIIa), (XVIIb), (XVIIa), (XVIIIb), (XIXa), (XIXb), (XXa), (XXb), (XXIa), (XXIb), (XXIIa), (XXIIb), (XXIIa), (XXIIb), (XXIIIa), (XXIIIb), (XXIIIc), (XXIIId), (XXIIIe), (XXIIIf), (XXIVa), (XXIVb), (XXVa), (XXVb), (XXVc), (XXVd), (XXVe), (XXVf), (XXVg) and / or (XXVh) can be displayed.Preferably, compounds according to the invention, in particular comprising structures according to formula (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (VIIa), (VIIb), (VIIIa), (VIIIb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIIa), (XIIb), (XIII), (XIVa), (XIVb), (XVa), (XVb), (XVIa), (XVIb), (XVIIa), (XVIIb), (XVIIa), (XVIIb), (XVIIIa), (XVIIIb), (XIXa), (XIXb), (XXa), (XXb), (XXIa), (XXIb), (XXIIa), (XXIIb), (XXIIa), (XXIIb), (XXIIIa), (XXIIIb), (XXIIIc), (XXIIId), (XXIIIe), (XXIIIf), (XXIVa), (XXIVb), (XXVa), (XXVb), (XXVc), (XXVd), (XXVe), (XXVf), (XXVg) and / or (XXVh), have a molecular weight of less than or equal to 5000 g / mol, preferably less than or equal to 4000 g / mol, particularly preferably less than or equal to 3000 g / mol, especially preferably less than or equal to 2000 g / mol and very particularly preferably less than or equal to 1200 g / mol.

[0071] Furthermore, preferred compounds according to the invention are characterized by their sublimability. These compounds generally have a molecular weight of less than approximately 1200 g / mol.

[0072] If X stands for CR 1< or if the aromatic and / or heteroaromatic groups are substituted by substituents R 1<, then these substituents R 1< are preferably selected from the group consisting of H, D, CN, N(Ar 1<) 2 , a straight-chain alkyl group having 1, 2, 3 or 4 C atoms or a branched or cyclic alkyl group having 3 to 8 C atoms, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2<, but is preferably unsubstituted; optionally two substituents R 1< bonded to the same carbon atom or to adjacent carbon atoms may form a monocyclic, aliphatic or aromatic ring system.Preferably, Ar 1<, identically or differently on each occurrence, represents an aryl or heteroaryl group having 5 to 24, preferably 5 to 12 aromatic ring atoms, each of which may be substituted by one or more radicals R 2<, but is preferably unsubstituted.

[0073] Most preferably, the substituents R 1< are selected from the group consisting of H or an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably having 6 to 13 aromatic ring atoms, which may each be substituted by one or more non-aromatic radicals R 2<, but is preferably unsubstituted. Examples of suitable substituents R 1< are selected from the group consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl, in particular branched terphenyl, quaterphenyl, in particular branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl and 1-, 2-, 3- or 4-carbazolyl, which may each be substituted by one or more radicals R 2<, but are preferably unsubstituted.

[0074] Preferably, the R 1< radicals do not form a fused aromatic or heteroaromatic ring system with the ring atoms of the aryl group or heteroaryl group to which the R 1< radicals are bonded, and preferably not a fused ring system. This includes the formation of a fused ring system with possible R 2< substituents that may be bonded to the R 1< radicals.

[0075] Furthermore, it can be provided that the R 1< radicals do not form a fused aromatic or heteroaromatic ring system with further groups, preferably not a fused ring system. This includes the formation of a fused ring system with possible substituents R 2<, which may be bonded to the R 1< radicals. These further groups can be spatially adjacent or distant, and these groups include the ring systems and radicals shown in formulas (IIIa) or (IIIb) and their preferred embodiments.

[0076] Preferably, the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system represented by the symbol Ar 1< is bonded directly, ie via an atom of the aromatic or heteroaromatic group, to the respective atom of the further group, wherein the symbol Ar 1< particularly preferably represents an aryl or heteroaryl radical.

[0077] In a further preferred embodiment of the invention, Ar 1< is identical or different on each occurrence and represents an aromatic or heteroaromatic ring system, preferably an aryl or heteroaryl radical having 5 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, particularly preferably an aromatic ring system, preferably an aryl radical having 6 to 12 aromatic ring atoms or a heteroaromatic ring system, preferably a heteroaryl group having 5 to 13 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2<, but is preferably unsubstituted, where R 2< may have the meaning shown above.

[0078] Examples of suitable groups Ar 1< are selected from the group consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl, in particular branched terphenyl, quaterphenyl, in particular branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl and 1-, 2-, 3- or 4-carbazolyl, which may each be substituted by one or more radicals R 2<, but are preferably unsubstituted.

[0079] In a further embodiment, it can be provided that the radicals Ar a< or the radical Ar b< are each substituted by radicals R 2< instead of by radicals R 1<.

[0080] Furthermore, it can be provided that in a structure according to formula (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (Vlla), (Vllb), (Vllla), (Vllb), (Vllla), (Vlllb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (Xlla), (XIIb), (XIII), (XIVa), (XIVb), (XVa), (XVb), (XVIa), (XVIb), (XVIIa), (XVIIa), (XVIIb), (XVIIIa), (XVIIIb), (XIXa), (XIXb), (XXa), (XXb), (XXIa), (XXIb), (XXIIa), (XXIIa), (XXIIb), (XXIIIa), (XXIIIb), (XXIIIc), (XXIIId), (XXIIIe), (XXIIIf), (XXIVa), (XXIVb), (XXVa), (XXVb), (XXVc), (XXVd), (XXVe), (XXVf), (XXVg) and / or (XXVh) at least one radical R 1< , Ar a< or Ar b< represents a group selected from the formulas (R 1< -1) to (R 1< - 80) where the following applies to the symbols used: Y is O, S or NR 2< , preferably O or S; i is independently 0, 1 or 2 at each occurrence; j is independently 0, 1, 2 or 3 at each occurrence; his is independently 0, 1, 2, 3 or 4 at each occurrence; g is independently 0, 1, 2, 3, 4 or 5 at each occurrence; R 2< can have the meaning given above, in particular for formula (I), and the dashed bond marks the attachment position.

[0081] The groups of the formulas R 1< -1 to R 1< -51 are preferred, with the groups R 1< -1, R 1< -3, R 1< -5, R 1< -6, R 1< -15, R 1< -29, R 1< -30, R 1< -31, R 1< -32, R 1< -33, R 1< -38, R 1< -39, R 1< -40, R 1< -41, R 1< -42, R 1< -43, R 1< -44 and / or R 1< -45 being particularly preferred.

[0082] Preferably, it can be provided that the sum of the indices i, j, h and g in the structures of the formulas (R 1< -1) to (R 1< -80) is in each case at most 3, preferably at most 2 and particularly preferably at most 1.

[0083] Preferably, the R 2< radicals in the formulas (R 1< -1) to (R 1< -80) do not form a fused aromatic or heteroaromatic ring system with the ring atoms of the aryl group or heteroaryl group to which the R 2< radicals are bonded, preferably not a fused ring system. This includes the formation of a fused ring system with possible R 3< substituents that may be bonded to the R 2< radicals.

[0084] In the formulas R 1< -1 to R 1< -80, preferred groups Ar a< and Ar b< are represented by radicals R 2<. Of course, radicals which essentially correspond to the formulas R 1< -1 to R 1< -80, but have radicals R 1< instead of R 2< as substituents, represent preferred groups Ar a< and Ar b<. The previously mentioned preferences for these formulas R 1< -1 to R 1< -80, which, however, have radicals R 1< instead of R 2< as substituents, also apply.

[0085] Preferably, the group L' can form a continuous conjugation with the diazanaphthalene radical to which the group L' is bonded according to formula (Ar b< -1), and with the carbazole group of formula (Ar b< -1). Further preferences for the group L' in formula (Ar b< -1) have been described previously in connection with the group L' set out, inter alia, in formulas (I), (IIa), (IIb), (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (Vlla), (Vllb), (Vllla), (Vlllb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (Xlla), (Xllb), which also apply to the formula (Ar b< -1).

[0086] Furthermore, it can be provided that the group L is substituted by radicals R 2< instead of by radicals R 1<.

[0087] Preferred are compounds comprising structures of the formulas (I), (IIa), (IIb), (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (VIIa), (VIIb), (VIIIa), (VIIIb), (IXa), (IXb), (Xa), (Xb), (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIIa), (XIIb) and (Ar b< -1), in which the group L or L' stands for a bond or for a group selected from the formulas (L 1< -1) to (L 1< -108), where the dashed bonds each mark the attachment positions, the index k is 0 or 1, the index I is 0, 1 or 2, the index j is independently 0, 1, 2 or 3 at each occurrence; the index h is independently 0, 1, 2, 3 or 4 at each occurrence, the index g is 0, 1, 2, 3, 4 or 5; the symbol is YO, S or NR 2< , preferably O or S; and the symbol R 2< has the meaning given above.

[0088] Preferably, it can be provided that the sum of the indices k, l, g, h and j in the structures of the formula (L 1< -1) to (L 1< -108) is in each case at most 3, preferably at most 2 and particularly preferably at most 1.

[0089] Preferred compounds according to the invention comprise a group L which represents a bond, in which m = 0, or which is selected from one of the formulas (L 1< -1) to (L 1< -78) and / or (L 1< -92) to (L 1< -108), preferably the formulas (L 1< -1) to (L 1< -54) and / or (L 1< -92) to (L 1< -108), especially preferably the formulas (L 1< -1) to (L 1< -29) and / or (L 1< -92) to (L 1< -103). Advantageously, the sum of the indices k, l, g, h and j in the structures of the formulas (L 1< -1) to (L 1< -78) and / or (L 1< -92) to (L 1< -108), preferably of the formulas (L 1< -1) to (L 1< -54) and / or (L 1< -92) to (L 1< -108), especially preferably of the formulas (L 1< -1) to (L 1< -29) and / or (L 1< -92) to (L 1< -103) can each be at most 3, preferably at most 2 and particularly preferably at most 1.

[0090] Preferably, the R 2< radicals in the formulas (L 1< -1) to (L 1< -108) do not form a fused aromatic or heteroaromatic ring system with the ring atoms of the aryl group or heteroaryl group to which the R 2< radicals are bonded, preferably not a fused ring system. This includes the formation of a fused ring system with possible R 3< substituents that may be bonded to the R 2< radicals.

[0091] In the formulas L 1< -1 to L 1< -108, preferred L groups are represented by radicals R 2<. Of course, radicals that essentially correspond to the formulas L 1< -1 to L 1< -108, but have radicals R 1< instead of R 2< as substituents, represent preferred L groups. The previously mentioned preferences for these formulas L 1< -1 to L 1< -108, which, however, have radicals R 1< instead of R 2< as substituents, also apply.

[0092] If the compound according to the invention is substituted with aromatic or heteroaromatic groups R 1 or R 2 , it is preferred if these do not contain any aryl or heteroaryl groups with more than two directly fused aromatic six-membered rings. Particularly preferably, the substituents do not contain any aryl or heteroaryl groups with directly fused aromatic six-membered rings. This preference is due to the low triplet energy of such structures. Condensed aryl groups with more than two directly fused aromatic six-membered rings that are nevertheless also suitable according to the invention are phenanthrene and triphenylene, since these also have a high triplet level.

[0093] In a further preferred embodiment of the invention, R 2<, for example in a structure according to formula (IIIa) or (IIIb) and preferred embodiments of this structure or the structures in which reference is made to these formulas, is selected on each occurrence, identically or differently, from the group consisting of H, D, an aliphatic hydrocarbon radical having 1, 2, 3 or 4 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, preferably having 5 to 24 aromatic ring atoms, particularly preferably having 5 to 13 aromatic ring atoms, which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0094] Preferably, the R 2< radicals do not form a fused aromatic or heteroaromatic ring system with the ring atoms of the aryl group or heteroaryl group to which the R 2< radicals are bonded, preferably not a fused ring system. This includes the formation of a fused ring system with possible R 3< substituents that may be bonded to the R 2< radicals.

[0095] In a further preferred embodiment of the invention, R 3< , for example in a structure according to formula (IIIa) or (IIIb) and preferred embodiments of this structure or the structures in which reference is made to these formulas, is selected on each occurrence, identically or differently, from the group consisting of H, D, CN, an aliphatic hydrocarbon radical having 1, 2, 3 or 4 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, preferably having 5 to 24 aromatic ring atoms, particularly preferably having 5 to 13 aromatic ring atoms, which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0096] According to the invention, compounds of formula (A) excepted, the symbols used having the meanings set out above, in particular for formula (I).

[0097] Preferably, compounds of formula (A-1) excepted, the symbols used having the meanings set out above, in particular for formula (I) or formulas (XXIa) and (XXIb).

[0098] Particularly preferred are compounds of formula (A-2) excepted, whereby the symbols used have the meanings set out above.

[0099] In a particular embodiment of the present invention, a compound according to formula (IIIa) or (IIIb), or a preferred embodiment of this formula, has at most one group Ar a< which comprises a 4-spirobifluorene, 4-fluorene, 1-dibenzofuran or 1-dibenzothiophene group or forms it with the aryl or heteroaryl radical to which the radical Ar a< binds. Particularly preferably, a compound according to formula (IIIa) or (IIIb), or a preferred embodiment of this formula, has at most one group Ar a< which comprises a spirobifluorene, fluorene, dibenzofuran or dibenzothiophene group or forms it with the aryl or heteroaryl radical to which the radical Ar a< binds.

[0100] Furthermore, it can preferably be provided that at least one of the radicals Ar a< according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa) or (XXIVb) or a preferred embodiment of this formula is unbridged, so that there is exactly one bond to the aryl radical which is connected to the nitrogen atom of the diaryl group.

[0101] Examples of suitable compounds according to the invention are the structures shown below according to the following formulas 1 to 131: formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Formula 6 Formula 7 Formula 8 Formula 9 Formula 10 Formula 11 Formula 12 Formula 13 Formula 14 Formula 15 Formula 16 Formula 17 Formula 18 Formula 19 Formula 20 Formula 21 Formula 22 Formula 23 Formula 24 Formula 26 Formula 27 Formula 28 Formula 29 Formula 30 Formula 31 Formula 32 Formula 33 Formula 34 Formula 35 Formula 36 Formula 37 Formula 38 Formula 39 Formula 40 Formula 41 Formula 42 Formula 43 Formula 44 Formula 45 Formula 46 Formula 47 Formula 48 Formula 49 Formula 50 Formula 51 Formula 52 Formula 53 Formula 54 Formula 55 Formula 56 Formula 57 Formula 58 Formula 59 Formula 60 Formula 61 Formula 62 Formula 63 Formula 64 Formula 65 Formula 66 Formula 67 Formula 68 Formula 69 Formula 70 Formula 71 Formula 72 Formula 73 Formula 74 Formula 75 Formula 76 Formula 77 Formula 78 Formula 79 Formula 80 Formula 81 Formula 82 Formula 83 Formula 84 Formula 85 Formula 86 Formula 87 Formula 88 Formula 89 Formula 90 Formula 91 Formula 92 Formula 93 Formula 94 Formula 95 Formula 96 Formula 97 Formula 98 Formula 99 Formula 100 Formula 101 Formula 102 Formula 103 Formula 104 Formula 105 Formula 106 Formula 107 Formula 108 Formula 109 Formula 110 Formula 111 Formula 112 Formula 113 Formula 114 Formula 115 Formula 116 Formula 117 Formula 118 Formula 119 Formula 120 Formula 121 Formula 122 Formula 123 Formula 124 Formula 125 Formula 126 Formula 127 Formula 128 Formula 129 Formula 130 Formula 131 Formula 132 Formula 133 Formula 134 Formula 135 Formula 136 Formula 137 Formula 138

[0102] Preferred embodiments of compounds according to the invention are explained in more detail in the examples, whereby these compounds can be used alone or in combination with others for all purposes according to the invention.

[0103] Provided that the conditions stated in claim 1 are met, the above-mentioned preferred embodiments can be combined with one another in any way. In a particularly preferred embodiment of the invention, the above-mentioned preferred embodiments apply simultaneously.

[0104] The compounds of the invention can, in principle, be prepared by various methods. However, the methods described below have proven particularly suitable.

[0105] Therefore, a further subject of the present invention is a process for preparing the compounds according to the invention in which a diarylamine compound is combined with a compound comprising at least one diazanaphthyl group in a coupling reaction.

[0106] Suitable compounds containing a diazanaphthyl group or diarylamine compounds can often be obtained commercially, the starting compounds presented in the examples being obtainable by known processes, so that reference is made thereto.

[0107] These compounds can be reacted with other aryl compounds by known coupling reactions. The necessary conditions are known to the person skilled in the art, and detailed information in the examples assists the person skilled in the art in carrying out these reactions. Particularly suitable and preferred coupling reactions, all of which lead to CC and / or CN bond formations, are those according to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA, and HIYAMA. These reactions are widely known, and the examples provide further guidance to the person skilled in the art.

[0108] In all of the following synthesis schemes, the compounds are shown with a small number of substituents to simplify the structures. This does not exclude the presence of any additional substituents in the processes.

[0109] An example implementation is shown in the following diagrams, without any restrictions. The sub-steps of the individual diagrams can be combined in any way.

[0110] Journal of Materials Chemistry, 22(14), 6878-6884; 2012.

[0111] The meaning of the symbols used in Schemes 1 to 3 essentially corresponds to that defined for formula (I), whereby numbering has been omitted in many cases for reasons of clarity, but the diaryl or triarylamine structure has been presented with the symbols Ar 1 , Ar 2 and partly L' for better readability in order to make it clear that the aryl groups can be different.

[0112] The processes shown for synthesizing the compounds of the invention are to be understood as examples. Those skilled in the art can develop alternative synthesis routes within the scope of their general technical knowledge. The principles of the preparation processes presented above are, in principle, known from the literature for similar compounds and can be easily adapted by those skilled in the art for preparing the compounds of the invention. Further information can be found in the examples.

[0113] By these processes, optionally followed by purification, such as recrystallization or sublimation, the compounds according to the invention, comprising structures according to formula (I), can be obtained in high purity, preferably more than 99% (determined by 1< H-NMR and / or HPLC).

[0114] The compounds according to the invention can also have suitable substituents, for example longer alkyl groups (approx. 4 to 20 C atoms), in particular branched alkyl groups, or optionally substituted aryl groups, for example xylyl, mesityl, or branched terphenyl or quaterphenyl groups, which impart solubility in common organic solvents, such as toluene or xylene, which are soluble at room temperature in sufficient concentration to enable processing of the compounds from solution. These soluble compounds are particularly suitable for processing from solution, for example by printing processes. Furthermore, it should be noted that the compounds according to the invention, comprising at least one structure of the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb), already possess increased solubility in these solvents.

[0115] The compounds according to the invention can also be mixed with a polymer. It is also possible to covalently incorporate these compounds into a polymer. This is particularly possible with compounds substituted by reactive leaving groups, such as bromine, iodine, chlorine, boronic acid, or boronic acid esters, or by reactive, polymerizable groups, such as olefins or oxetanes. These can be used as monomers to produce corresponding oligomers, dendrimers, or polymers. The oligomerization or polymerization preferably takes place via the halogen functionality or the boronic acid functionality, or via the polymerizable group, respectively. It is also possible to crosslink the polymers via such groups. The compounds and polymers according to the invention can be used as crosslinked or uncrosslinked layers.

[0116] The invention therefore further provides oligomers, polymers or dendrimers comprising one or more of the above-listed structures of the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or compounds according to the invention, wherein one or more bonds of the compounds according to the invention or of the structures of the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) to the polymer, oligomer or dendrimer are present. Depending on the linkage of the structures of the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or of the compounds, these therefore form a side chain of the oligomer or polymer or are linked in the main chain. The polymers, oligomers or dendrimers can be conjugated, partially conjugated or non-conjugated. The oligomers or polymers can be linear, branched or dendritic. The same preferences as described above apply to the repeating units of the compounds according to the invention in oligomers, dendrimers and polymers.

[0117] To prepare the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. Copolymers are preferred, wherein the units according to formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments described above and below are present in amounts of 0.01 to 99.9 mol%, preferably 5 to 90 mol%, particularly preferably 20 to 80 mol%. Suitable and preferred comonomers which form the polymer backbone are selected from fluorenes (e.g. according to EP 842208 or WO 2000 / 022026), spirobifluorenes (e.g. according to EP 707020, EP 894107 or WO 2006 / 061181), para-phenylenes (e.g. according to WO 92 / 18552), carbazoles (e.g. according to WO 2004 / 070772 or WO 2004 / 113468), thiophenes (e.g. according to EP 1028136), dihydrophenanthrenes (e.g. according to WO 2005 / 014689), cis- and trans-indenofluorenes (e.g. according to WO 2004 / 041901 or WO 2004 / 113412), ketones (e.g. according to WO 2005 / 040302), phenanthrenes (e.g.according to WO 2005 / 104264 or WO 2007 / 017066) or several of these units. The polymers, oligomers, and dendrimers may contain further units, for example hole-transport units, in particular those based on triarylamines, and / or electron-transport units.

[0118] Of particular interest are also compounds according to the invention that are characterized by a high glass transition temperature. In this context, particular preference is given to compounds according to the invention comprising structures of the general formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments described above and below, which have a glass transition temperature of at least 70 °C, more preferably of at least 110 °C, most preferably of at least 125 °C, and especially preferably of at least 150 °C, determined according to DIN 51005 (version 2005-08).

[0119] For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and 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, butylbenzoate, 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, hexamethylindane or mixtures of these solvents.

[0120] The present invention therefore further provides a formulation comprising a compound according to the invention and at least one further compound. The further compound can, for example, be a solvent, in particular one of the above-mentioned solvents or a mixture of these solvents. However, the further compound can also be at least one further organic or inorganic compound that is also used in the electronic device, for example an emitting compound, in particular a phosphorescent dopant, and / or a further matrix material. This further compound can also be polymeric.

[0121] The present invention therefore further provides a composition comprising a compound according to the invention and at least one further organic functional material. Functional materials are generally the organic or inorganic materials that are introduced between the anode and cathode. The organic functional material is preferably selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF (thermally activated delayed fluorescence), host materials, electron-transport materials, electron-injection materials, hole-conductor materials, hole-injection materials, electron-blocking materials, hole-blocking materials, wide-band-gap materials, and n-dopants.

[0122] The present invention therefore also relates to a composition comprising at least one compound comprising structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments described above and below, as well as at least one further matrix material. According to a particular aspect of the present invention, the further matrix material has hole-transporting properties.

[0123] The present invention further provides a composition comprising at least one compound comprising at least one structure according to formula (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments described above and below, as well as at least one wide-band gap material, wherein wide-band gap material is understood to mean a material within the meaning of the disclosure of US Pat. No. 7,294,849. These systems exhibit particularly advantageous performance data in electroluminescent devices.

[0124] Preferably, the additional compound can have a band gap of 2.5 eV or more, preferably 3.0 eV or more, most preferably 3.5 eV or more. The band gap can be calculated, among other things, from the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

[0125] Molecular orbitals, in particular the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), their energy levels, and the energy of the lowest triplet state T1 and the lowest excited singlet state S1 of the materials are determined using quantum chemical calculations. For the calculation of organic substances without metals, a geometry optimization is first performed using the "Ground State / Semi-empirical / Default Spin / AM1 / Charge 0 / Spin Singlet" method. Subsequently, an energy calculation is performed based on the optimized geometry. The method "TD-SCF / DFT / Default Spin / B3PW91" with the "6-31 G(d)" basis set is used (Charge 0, Spin Singlet). For metal-containing compounds, the geometry is optimized using the "Ground State / Hartree-Fock / Default Spin / LanL2MB / Charge 0 / Spin Singlet" method.The energy calculation is carried out analogously to the method described above for organic substances, with the difference that the basis set "LanL2DZ" is used for the metal atom and the basis set "6-31 G(d)" for the ligands. The energy calculation yields the HOMO energy level HEh and the LUMO energy level LEh in Hartree units. From this, the HOMO and LUMO energy levels, calibrated using cyclic voltammetry measurements, are determined in electronvolts as follows: . HOMO(eV) = ((HEh*27.212)-0.9899) / 1.1206 LUMO(eV) = ((LEh*27.212)-2.0041) / 1.385

[0126] For the purposes of this application, these values ​​are to be regarded as HOMO or LUMO energy levels of the materials.

[0127] The lowest triplet state T 1 is defined as the energy of the triplet state with the lowest energy resulting from the quantum chemical calculation described.

[0128] The lowest excited singlet state S 1 is defined as the energy of the excited singlet state with the lowest energy resulting from the described quantum chemical calculation.

[0129] The method described here is independent of the software package used and always produces the same results. Examples of commonly used programs for this purpose are "Gaussian09W" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.).

[0130] The present invention also relates to a composition comprising at least one compound comprising structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments set out above and below, and at least one phosphorescent emitter, wherein the term phosphorescent emitters is also understood to include phosphorescent dopants.

[0131] In a system containing a matrix material and a dopant, a dopant is understood to be the component whose proportion in the mixture is the smaller. Similarly, in a system containing a matrix material and a dopant, a matrix material is understood to be the component whose proportion in the mixture is the larger.

[0132] Preferred phosphorescent dopants for use in matrix systems, preferably mixed matrix systems, are the preferred phosphorescent dopants listed below.

[0133] The term phosphorescent dopants typically includes compounds in which light emission occurs through a spin-forbidden transition, for example a transition from an excited triplet state or a state with a higher spin quantum number, for example a quintet state.

[0134] Particularly suitable phosphorescent compounds (= triplet emitters) are compounds that emit light upon suitable excitation, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are used as phosphorescent emitters, in particular compounds containing iridium or platinum. For the purposes of the present invention, all luminescent compounds containing the above-mentioned metals are considered phosphorescent compounds.

[0135] Examples of the emitters described above can be found in the applications WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626, WO 2011 / 066898, WO 2011 / 157339, WO 2012 / 007086, WO 2014 / 008982, WO 2014 / 023377, WO 2014 / 094961, WO 2014 / 094960, WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO 2016 / 015815, WO 2016 / 124304, WO 2017 / 032439 and the not yet published applications EP16179378.1 and EP16186313.9. In general, all phosphorescent complexes as used according to the prior art for phosphorescent OLEDs and as known to the person skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art can use further phosphorescent complexes without inventive step.

[0136] Examples of phosphorescent dopants are listed below.

[0137] The compounds described above, comprising structures of the formula (IIIa), (IIIb), (XXIa), (XXIb), XXIVa), (XXIVb) or the preferred embodiments listed above, can preferably be used as an active component in an electronic device. An electronic device is understood to be a device which contains an anode, a cathode, and at least one layer located between the anode and the cathode, said layer containing at least one organic or organometallic compound. The electronic device according to the invention therefore contains an anode, a cathode, and at least one layer located therebetween, which contains at least one compound comprising structures of the formula (I).Preferred electronic devices are selected from the group consisting of organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), organic electrical sensors, light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and organic plasmon-emitting devices, preferably organic electroluminescent devices (OLEDs, PLEDs), in particular phosphorescent OLEDs, containing at least one compound comprising structures of formula (I) in at least one layer. Particular preference is given to organic electroluminescent devices.Active components are generally the organic or inorganic materials that are introduced between the anode and cathode, for example charge injection, charge transport or charge blocking materials, but in particular emission materials and matrix materials.

[0138] A preferred embodiment of the invention is organic electroluminescent devices. The organic electroluminescent device comprises a cathode, an anode, and at least one emitting layer. In addition to these layers, it may contain further layers, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers, and / or organic or inorganic p / n junctions. It is possible for one or more hole transport layers to be p-doped, for example with metal oxides such as MoO or WO, or with (per)fluorinated electron-deficient aromatics, and / or for one or more electron transport layers to be n-doped.Interlayers can also be inserted between two emitting layers, for example, to have an exciton-blocking function and / or to control the charge balance in the electroluminescent device. However, it should be noted that not all of these layers are necessarily present.

[0139] The organic electroluminescent device can contain one emitting layer or it can contain several emitting layers. If several emitting layers are present, these preferably have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, i.e. different emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. Particular preference is given to three-layer systems, wherein the three layers exhibit blue, green and orange or red emission (for the basic structure see, for example, WO 2005 / 011013) or systems which have more than three emitting layers. Tandem OLEDs are also preferred. It can also be a hybrid system, wherein one or more layers fluoresce and one or more other layers phosphoresce.

[0140] In a preferred embodiment of the invention, the organic electroluminescent device contains the compound according to the invention comprising structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments listed above as matrix material, preferably as electron-conducting matrix material in one or more emitting layers, preferably in combination with a further matrix material, preferably a hole-conducting matrix material. In a further preferred embodiment of the invention, the further matrix material is an electron-transporting compound. In yet another preferred embodiment, the further matrix material is a compound with a wide band gap that is not involved, or not involved to a significant extent, in hole and electron transport in the layer. An emitting layer comprises at least one emitting compound.

[0141] Suitable matrix materials which can be used in combination with the compounds according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or according to the preferred embodiments are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g. according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triarylamines, in particular monoamines, e.g. according to WO 2014 / 015935, carbazole derivatives, e.g. B. CBP (N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851, indolocarbazole derivatives, e.g. according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, e.g. according to WO 2010 / 136109 and WO 2011 / 000455, azacarbazole derivatives, e.g. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, e.g. B. according to WO 2007 / 137725, silanes, e.g. according to WO 005 / 111172, azaboroles or boronate esters, e.g.according to WO 2006 / 117052, triazine derivatives, e.g. according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, diazasilole or tetraazasilole derivatives, e.g. according to WO 2010 / 054729, diazaphosphole derivatives, e.g. according to WO 2010 / 054730, bridged carbazole derivatives, e.g. B. according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107, WO 2011 / 088877 or WO 2012 / 143080, triphenylene derivatives, e.g. B. according to WO 2012 / 048781, lactams, e.g. B. according to WO 2011 / 116865, WO 2011 / 137951 or WO 2013 / 064206, 4-spirocarbazole derivatives, e.g. B. according to WO 2014 / 094963 or WO 2015 / 192939, or dibenzofuran derivatives, e.g. B. according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565. Likewise, another phosphorescent emitter, which emits at a shorter wavelength than the actual emitter, can be present in the mixture as a co-host.

[0142] Preferred co-host materials are triarylamine derivatives, especially monoamines, indenocarbazole derivatives, 4-spirocarbazole derivatives, lactams and carbazole derivatives.

[0143] Preferred triarylamine derivatives used as co-host materials together with the compounds of the invention are selected from the compounds of the following formula (TA-1), where Ar 3<, identical or different on each occurrence, represents an aromatic or heteroaromatic ring system having 6 to 40 C atoms, which may each be substituted by one or more radicals R 2<, where optionally two or more adjacent substituents R 2< can form a mono- or polycyclic, aliphatic ring system which may be substituted by one or more radicals R 3<, where the symbol R 2< has the meaning given above. Preferably, Ar 3<, identical or different on each occurrence, represents an aryl or heteroaryl group having 5 to 24, preferably 5 to 12 aromatic ring atoms, which may each be substituted by one or more radicals R 2<, but is preferably unsubstituted.

[0144] Examples of suitable groups Ar 3< are selected from the group consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl, in particular branched terphenyl, quaterphenyl, in particular branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl and 1-, 2-, 3- or 4-carbazolyl, which may each be substituted by one or more radicals R 2<, but are preferably unsubstituted.

[0145] Preferably, the groups Ar 3< are identical or different at each occurrence and are selected from the abovementioned groups R 1< -1 to R 1< -80, particularly preferably R 1< -1 to R 1< -51.

[0146] In a preferred embodiment of the compounds of formula (TA-1), at least one Ar 1< group is selected from a biphenyl group, which may be an ortho-, meta-, or para-biphenyl group. In a further preferred embodiment of the compounds of formula (TA-1), at least one Ar 1< group is selected from a fluorene group or spirobifluorene group, which may each be bonded to the nitrogen atom in the 1-, 2-, 3-, or 4-position. In yet another preferred embodiment of the compounds of formula (TA-1), at least one group Ar 3< is selected from a phenylene or biphenyl group, which is an ortho-, meta- or para-linked group which is substituted by a dibenzofuran group, a dibenzothiophene group or a carbazole group, in particular a dibenzofuran group, wherein the dibenzofuran or dibenzothiophene group is linked via the 1-, 2-, 3- or 4-position to the phenylene or biphenyl group.biphenyl group and wherein the carbazole group is linked to the phenylene or biphenyl group via the 1-, 2-, 3- or 4-position or via the nitrogen atom.

[0147] In a particularly preferred embodiment of the compounds of formula (TA-1), one group Ar 3< is selected from a fluorene or spirobifluorene group, in particular a 4-fluorene or 4-spirobifluorene group, and one group Ar 3< is selected from a biphenyl group, in particular a para-biphenyl group, or a fluorene group, in particular a 2-fluorene group, and the third group Ar 3< is selected from a para-phenylene group or a para-biphenyl group substituted by a dibenzofuran group, in particular a 4-dibenzofuran group, or a carbazole group, in particular an N-carbazole group or a 3-carbazole group.

[0148] Preferred indenocarbazole derivatives used as co-host materials together with the compounds of the invention are selected from the compounds of the following formula (TA-2), where Ar 3< and R 1< have the meanings listed above, in particular for formulas (I) and / or (TA-3). Preferred embodiments of the group Ar 3< are the structures R 1< -1 to R 1< -80 listed above, particularly preferably R 1< -1 to R 1< -51.

[0149] A preferred embodiment of the compounds of formula (TA-2) are the compounds of the following formula (TA-2a), where Ar 3< and R 1< have the meanings listed above, in particular for formulas (I) and / or (TA-1). The two groups R 1< which are bonded to the indenocarbon atom are preferably identical or different and are an alkyl group having 1 to 4 C atoms, in particular methyl groups, or an aromatic ring system having 6 to 12 C atoms, in particular phenyl groups. The two groups R 1< which are bonded to the indenocarbon atom are particularly preferably methyl groups. Furthermore, the substituent R 1< which is bonded to the indenocarbazole parent structure in formula (TA-2a) is preferably H or a carbazole group which can be bonded to the indenocarbazole parent structure via the 1-, 2-, 3- or 4-position or via the N atom, in particular via the 3-position.

[0150] Preferred 4-spirocarbazole derivatives used as co-host materials together with the compounds of the invention are selected from the compounds of the following formula (TA-3), where Ar 3< and R 1< have the meanings listed above, in particular for formulas (TA-1), (I), (II) and / or (Q-1). Preferred embodiments of the group Ar 3< are the structures R 1< -1 to R 1< -80 listed above, particularly preferably R 1< -1 to R 1< -51.

[0151] A preferred embodiment of the compounds of formula (TA-3) are the compounds of the following formula (TA-3a), where Ar 3< and R 1< have the meanings listed above, in particular for formulas (TA-1), (I), (II) and / or (Q-1). Preferred embodiments of the group Ar 3< are the structures R 1< -1 to R 1< -80 listed above, particularly preferably R 1< -1 to R 1< -51.

[0152] Preferred lactams used as co-host materials together with the compounds of the invention are selected from the compounds of the following formula (LAC-1), where R 1< has the meaning given above, in particular for formula (I).

[0153] A preferred embodiment of the compounds of formula (LAC-1) are the compounds of the following formula (LAC-1a), where R 1< has the meaning given above. R 1< is preferably the same or different on each occurrence and is H or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 2<, where R 2< may have the meaning given above. The substituents R 1< are very particularly preferably selected from the group consisting of H or an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably having 6 to 13 aromatic ring atoms, each of which may be substituted by one or more non-aromatic radicals R 2<, but is preferably unsubstituted.Examples of suitable substituents R 1< are selected from the group consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl, in particular branched terphenyl, quaterphenyl, in particular branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl and 1-, 2-, 3- or 4-carbazolyl, which may each be substituted by one or more radicals R 2<, but are preferably unsubstituted. Suitable structures R 1< are the same structures as previously shown for R-1 to R-79, particularly preferably R 1< -1 to R 1< -51.

[0154] It may also be preferable to use several different matrix materials as a mixture, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material. Likewise preferred is the use of a mixture of a charge-transporting matrix material and an electrically inert matrix material that is not involved, or not significantly involved, in charge transport, as described, for example, in WO 2010 / 108579.

[0155] It is further preferred to use a mixture of two or more triplet emitters together with a matrix. The triplet emitter with the shorter-wavelength emission spectrum serves as a co-matrix for the triplet emitter with the longer-wavelength emission spectrum.

[0156] Particularly preferably, a compound according to the invention comprising structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) can be used in a preferred embodiment as a matrix material in an emission layer of an organic electronic device, in particular in an organic electroluminescent device, for example in an OLED or OLEC. The matrix material comprising the compound comprising structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments described above and below is present in the electronic device in combination with one or more dopants, preferably phosphorescent dopants.

[0157] In this case, the proportion of the matrix material in the emitting layer is between 50.0 and 99.9 vol.%, preferably between 80.0 and 99.5 vol.% and particularly preferably for fluorescent emitting layers between 92.0 and 99.5 vol.% and for phosphorescent emitting layers between 85.0 and 97.0 vol.%.

[0158] Accordingly, the proportion of the dopant is between 0.1 and 50.0 vol.%, preferably between 0.5 and 20.0 vol.% and particularly preferably for fluorescent emitting layers between 0.5 and 8.0 vol.% and for phosphorescent emitting layers between 3.0 and 15.0 vol.%.

[0159] An emitting layer of an organic electroluminescent device can also contain systems comprising multiple matrix materials (mixed-matrix systems) and / or multiple dopants. In this case, too, the dopants are generally the materials whose proportion is the smaller in the system, and the matrix materials are the materials whose proportion is the larger in the system. In individual cases, however, the proportion of a single matrix material in the system may be smaller than the proportion of a single dopant.

[0160] In a further preferred embodiment of the invention, the compounds comprising structures according to formula (I) or the preferred embodiments described above and below are used as a component of mixed-matrix systems. The mixed-matrix systems preferably comprise two or three different matrix materials, particularly preferably two different matrix materials. Preferably, one of the two materials is a material with hole-transporting properties and the other material is a material with electron-transporting properties. However, the desired electron-transporting and hole-transporting properties of the mixed-matrix components can also be combined mainly or completely in a single mixed-matrix component, with the further mixed-matrix component(s) fulfilling other functions.The two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1, and most preferably 1:4 to 1:1. Mixed-matrix systems are preferably used in phosphorescent organic electroluminescent devices. More detailed information on mixed-matrix systems can be found, among other things, in the application WO 2010 / 108579.

[0161] Furthermore, an electronic device, preferably an organic electroluminescent device, is the subject of the present invention, which comprises one or more compounds according to the invention and / or at least one oligomer, polymer or dendrimer according to the invention in one or more electron-conducting layers as an electron-conducting compound.

[0162] Metals with a low work function, metal alloys, or multilayer structures made of different metals are preferred as the cathode, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys made of an alkali or alkaline earth metal and silver, for example, an alloy of magnesium and silver, are also suitable. In multilayer structures, in addition to the metals mentioned, other metals with a relatively high work function can be used, such as Ag, in which case combinations of the metals, such as Mg / Ag, Ca / Ag, or Ba / Ag, are generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor.Suitable materials for this purpose include 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 , etc.). Organic alkali metal complexes, such as Liq (lithium quinolinate), are also suitable. The thickness of this layer is preferably between 0.5 and 5 nm.

[0163] Materials with a high work function are preferred as the anode. The anode preferably has a work function greater than 4.5 eV vs. vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Metal / metal oxide electrodes (e.g., Al / Ni / NiO x , Al / PtO x ) may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to enable either the irradiation of the organic material (O-SC) or the coupling out of light (OLED / PLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive, doped organic materials, in particular conductive doped polymers, e.g., PEDOT, PANI, or derivatives of these polymers.It is also preferred if a p-doped hole-transport material is applied to the anode as a hole-injection layer. Suitable p-dopants are metal oxides, for example, MoO 3 or WO 3 , or (per)fluorinated electron-deficient aromatics. Other suitable p-dopants are HAT-CN (hexacyanohexaazatriphenylene) or the compound NPD9 from Novaled. Such a layer simplifies hole injection in materials with a deep HOMO, i.e., a large HOMO.

[0164] In the further layers, generally all materials can be used as used for the layers according to the prior art, and the person skilled in the art can combine any of these materials with the materials according to the invention in an electronic device without inventive step.

[0165] The device is structured accordingly (depending on the application), contacted and finally hermetically sealed, since the lifetime of such devices is drastically reduced in the presence of water and / or air.

[0166] Also preferred is an electronic device, in particular an organic electroluminescent device, characterized in that one or more layers are applied using a sublimation process. The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of typically less than 10 -5 mbar, preferably less than 10 -6 mbar. It is also possible for the initial pressure to be even lower or higher, for example, less than 10 -7 mbar.

[0167] Also preferred is an electronic device, in particular an organic electroluminescent device, characterized in that one or more layers are applied using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are applied at a pressure between 10 -5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured.

[0168] Also preferred is an electronic device, in particular an organic electroluminescent device, characterized in that one or more layers are produced from solution, such as by spin coating, or by any printing process, such as screen printing, flexographic printing, offset printing, or nozzle printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or inkjet printing. Soluble compounds are required for this, which are obtained, for example, by suitable substitution.

[0169] The electronic device, in particular the organic electroluminescent device, can also be manufactured as a hybrid system by applying one or more layers from solution and vapor-depositing one or more other layers. For example, it is possible to apply an emitting layer containing a compound according to the invention comprising structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) and a matrix material from solution, and to vacuum-deposit a hole-blocking layer and / or an electron-transport layer thereon.

[0170] These processes are generally known to the person skilled in the art and can be applied by him without problems to electronic devices, in particular organic electroluminescent devices containing compounds according to the invention comprising structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments listed above.

[0171] The electronic devices according to the invention, in particular organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art: 1. Electronic devices, in particular organic electroluminescent devices containing compounds, oligomers, polymers or dendrimers with structures according to the formula (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments set out above and below, in particular as electron-conducting materials and / or hole-conducting materials and / or as matrix materials, have a very good lifetime. 2. Electronic devices, in particular organic electroluminescent devices containing compounds, oligomers, polymers or dendrimers with structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments set out above and below, in particular as electron-transport materials, hole-conducting materials and / or as host materials, have excellent efficiency.In particular, the efficiency is significantly higher compared to analogous compounds which do not contain a structural unit according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb). Compounds, oligomers, polymers or dendrimers according to the invention with structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments set out above and below bring about a low operating voltage when used in electronic devices. In particular, these compounds bring about a low roll-off, i.e. a low drop in the power efficiency of the device at high luminances. 3. Electronic devices, in particular organic electroluminescent devices containing compounds, oligomers, polymers or dendrimers with structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) orThe preferred embodiments described above and below as electron-transport materials, hole-conductor materials, and / or as host materials exhibit excellent color purity. 4. The compounds, oligomers, polymers, or dendrimers according to the invention with structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments described above and below exhibit very high thermal and photochemical stability and lead to compounds with a very long lifetime. 5. The use of compounds, oligomers, polymers, or dendrimers with structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments described above and below in layers of electronic devices, in particular organic electroluminescent devices, leads to high mobility of the electron-conductor structures. 6.Compounds, oligomers, polymers or dendrimers with structures according to the formula (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments outlined above and below are characterized by excellent thermal stability, with compounds with a molecular mass of less than approximately 1200 g / mol being readily sublimable. 7. Compounds, oligomers, polymers or dendrimers with structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments outlined above and below exhibit excellent glass film formation. 8. Compounds, oligomers, polymers or dendrimers with structures according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or the preferred embodiments outlined above and below form very good films from solutions.

[0172] These advantages mentioned above are not accompanied by a deterioration of the other electronic properties.

[0173] The compounds and mixtures according to the invention are suitable for use in an electronic device. An electronic device is understood to be a device that contains at least one layer containing at least one organic compound. However, the component can also contain inorganic materials or layers composed entirely of inorganic materials.

[0174] A further object of the present invention is therefore the use of the compounds or mixtures according to the invention in an electronic device, in particular in an organic electroluminescent device.

[0175] A further object of the present invention is the use of a compound according to the invention and / or an oligomer, polymer or dendrimer according to the invention in an electronic device as a host material, hole-conducting material, electron injection material and / or electron transport material, preferably as a host material and / or electron transport material.

[0176] The present invention further provides an electronic device comprising at least one of the compounds or mixtures according to the invention described above. The preferences described above for the compound also apply to the electronic devices.Particularly preferably, the electronic device is selected from the group consisting of organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), organic electrical sensors, light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic plasmon-emitting devices, preferably organic electroluminescent devices (OLEDs, PLEDs), in particular phosphorescent OLEDs.

[0177] In a further embodiment of the invention, the organic electroluminescent device according to the invention does not contain a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, i.e. the emitting layer directly adjoins the hole injection layer or the anode, and / or the emitting layer directly adjoins the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051. Furthermore, it is possible to use a metal complex that is the same as or similar to the metal complex in the emitting layer directly adjacent to the emitting layer as a hole transport or hole injection material, as described, for example, in WO 2009 / 030981.

[0178] In the further layers of the organic electroluminescent device according to the invention, all materials commonly used in the prior art can be used. Therefore, without inventive effort, the skilled person can use all materials known for organic electroluminescent devices in combination with the compounds according to the invention according to the formulas (IIIa), (IIIb), (XXIa), (XXIb), (XXIVa), (XXIVb) or according to the preferred embodiments.

[0179] The compounds of the invention generally exhibit very good properties when used in organic electroluminescent devices. In particular, when the compounds of the invention are used in organic electroluminescent devices, their lifetime is significantly improved compared to similar compounds according to the prior art. The other properties of the organic electroluminescent device, in particular the efficiency and voltage, are also improved or at least comparable.

[0180] It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Any feature disclosed in the present invention may, unless explicitly excluded, be replaced by alternative features serving the same, equivalent, or similar purpose. Thus, unless otherwise stated, any feature disclosed in the present invention is to be considered an example of a generic series or an equivalent or similar feature.

[0181] All features of the present invention may be combined with each other in any way, unless certain features and / or steps are mutually exclusive. This applies in particular to preferred features of the present invention. Likewise, features of non-essential combinations may be used separately (and not in combination).

[0182] It should further be noted that many of the features, and particularly those of the preferred embodiments of the present invention, are inventive in their own right and should not be considered merely part of the embodiments of the present invention. Independent protection may be sought for these features in addition to or alternatively to any presently claimed invention.

[0183] The teaching of technical action disclosed in the present invention can be abstracted and combined with other examples.

[0184] The invention is further illustrated by the following examples, without intending to limit it. Those skilled in the art can use the descriptions to produce further electronic devices according to the invention without inventive step and thus implement the invention within the entire scope of the claims. Examples Synthesis examples

[0185] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The compounds of the invention can be prepared using synthesis methods known to those skilled in the art. a) Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-1-yl)amine

[0186]

[0187] 36 g (212 mmol, 1.0 eq) of 4-aminobiphenyl, 57.8 g (177 mmol, 1.0 eq) of 1-bromodimethylfluorene, and 2.4 g (212 mmol, 1.20 eq) of sodium t-pentoxide [14593-46-5] were placed in 600 ml of absolute toluene and degassed for 30 minutes. Subsequently, 398 mg (1.77 mmol, 0.01 eq) of palladium(II) acetate [3375-31-3] and 1.46 g (3.56 mmol, 0.02 eq) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos) [657408-07-6] were added, and the mixture was heated under reflux overnight. After the reaction is complete, the mixture is cooled to room temperature and extracted with 500 ml of water. The aqueous phase is then washed three times with toluene, the combined organic phases are dried over sodium sulfate, and the solvent is removed using a rotary evaporator. The brown residue is dissolved in approximately 200 ml of toluene and filtered through silica gel. For further purification, recrystallization from toluene / heptane is performed. Yield: 59 g (164 mmol), 79% of theory.

[0188] The following connections can be represented analogously: Educt 1 Educt 2 product Yield [%] 1a [92-67-1] [942615-32-9] 65 2a [90-41-5] [942615-32-9] 63 3a [18998-24-8] [942615-32-9] 60 4a [92-67-1] [1161009-88-6 62 5a [90-41-5] [171408-76-7] 64 6a [90-41-5] [1361305-36-3] 68 7a [18998-24-8] [942615-32-9] 71 8a [18998-24-8] [320-31-2] 72 9a [18998-24-8] [574750-94-0] 83 10a [18998-24-8] [1225053-54-2] 64 11a [578027-21-1] [942615-32-9] 67 12a [50548-43-1] [942615-32-9] 56 13a [50548-43-1] 75 14a [108714-73-4] [1161009-88-6] 85 15a [90-41-5] [942615-32-9] 69 16a [578027-21-1] [942615-32-9] 67 17a [1579281-06-3] [86-76-0] 88 18a [1579281-06-3] [942615-32-9] 81 19a [92-67-1] [1225053-54-2] 77 20a [92-67-1] [1450933-18-2] 70 21a [1579281-06-3] [86-76-0] 84 22a [1579281-06-3] [955959-84-9] 91 23a [1579281-06-3] [1297532-85-4] 74 24a [108714-73-4] [1161009-88-6] 85 25a [90-41-5] [942615-32-9] 69 26a [108714-73-4] [1407005-83-8] 67 27a [108714-73-4] [942615-28-3] 71 28a [92-67-1] [713125-22-5] 70 b) Biphenyl-4-yl-(4-bromophenyl)-(9,9-dimethyl-9H-fluoren-4-yl)amine

[0189]

[0190] In a 1L four-necked flask, 51.3 g (142 mmol, 1.00 eq) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-4-yl)-amine, 75.6 g (426 mmol, 3.00 eq) of 1-bromo-4-fluorobenzene [460-00-4], and 92.5 g (284 mmol, 2.00 eq) of cesium carbonate [534-17-8] are placed. 500 ml of dimethylacetamide are added. The reaction mixture is stirred at 150 °C for three days. After the reaction, the mixture is cooled to room temperature, and the solid is filtered through Celite. The mother liquor is concentrated, and the precipitated solid is filtered and extracted with hot methanol. Yield: 43 g (135 mmol), 95% of theory.

[0191] The following connections can be represented analogously: reactant product Yield [%] 1b 78 2b 26 3b 84 4b 68 5b 67 6b 44 7b 59 8b 65 9b 67 10b 71 11b ]1852534-95-2] 70 c) Biphenyl-4-yl-(3'-bromo-biphenyl-3-yl)-(9,9-dimethyl-9H-fluoren-2-yl)amine

[0192]

[0193] 29 g (80 mmol, 1.0 eq) of the intermediate from reaction a) together with 25 g (80 mmol, 1.0 eq) of 3,3'-dibromo-1,1'-biphenyl (CAS 16400-51-4) are dissolved in 600 ml of toluene and degassed for 30 minutes. Subsequently, 45 g (240 mmol, 3.0 eq) of sodium tert-butoxide, 890 mg (0.40 mmol, 0.050 eq) of palladium(II) acetate, and 8 ml (8.0 mmol, 0.10 eq) of a 1M tri-tert-butylphosphine solution are added. The mixture is heated under reflux overnight and, after the reaction, filtered twice over aluminum oxide with toluene. After removing the solvent on a rotary evaporator, the oil is dissolved in a small amount of THF and added to heptane. The resulting solid is filtered off with suction and purified by hot extraction in heptane / toluene 1:1. This yields 16.6 g (28 mmol, 35%) of the desired product.

[0194] The following connections can be represented analogously: Educt 3 Educt 4 product yield 1c 28320-32-3 49% 2c [1206544-88-8] 65% 3c 16400-51-4 72% 4c 105946-82-5 82% 5c 16400-51-4 41% 6c 201138-91-2 27% 7c 49602-91-7 56% 8c 31458-17-0 47% 9c 16400-51-4 57% 10c [1822311-12-5] 64 11c [1807910-82-2] 67 12c [1643716-58-8] 72 13c [1627589-28-9] 59 d) Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-1-yl)-[4-(4-phenylquinazolin-2-yl)phenyl]amine

[0195]

[0196] 27.5 g (110.0 mmol) of 4-phenylquinazoline-2-boronic acid, 56 g (110.0 mmol) of biphenyl-4-yl-(4-bromophenyl)-(9,9-dimethyl-9H-fluoren-1-yl)-amine, and 26 g (210.0 mmol) of sodium carbonate were suspended in 500 mL of ethylene glycol dimethyl ether and 500 mL of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate were added to this suspension, and the reaction mixture was heated under reflux for 16 h. After cooling, the organic phase was separated, filtered through silica gel, washed three times with 200 mL of water, and then evaporated to dryness. The product is purified by column chromatography on silica gel with toluene / heptane (1:2) and finally sublimed under high vacuum (p = 5 x 10 -7 < mbar) (purity 99.9%). The yield is 53 g (83 mmol), corresponding to 73% of theory.

[0197] The following connections can be represented analogously: reactant 1 Educt 2 product Yield [%] 1d [1874309-53-1] 71 2d [1616841-71-4] 70 3d [1616841-71-4] 67 4d [1616841-71-4] 65 5d [1616841-71-4] 68 6d [1616841-71-4] 69 7d [1874309-53-1] 66 8d [1616841-71-4] 62 9d [1874309-53-1] 68 10d [1018833-74-3] 68 11d [1018833-74-3] 71 12d [1616841-71-4] 70 13d [1874309-53-1] 69 14d [1616841-71-4] 67 15d [1616841-71-4] 63 16d [1616841-71-4] 64 17d [1018833-74-3] 67 18d [1616841-71-4] 60 19d [1616841-71-4] 68 20d [1616841-71-4] 67 21d [1616841-71-4] 62 22d [1616841-71-4] 64 23d [1616841-71-4] 61 24d [1616841-71-4] 63 25d [1018833-74-3] 67 26d [1018833-74-3] 65 27d [1018833-74-3] 63 30d [1616841-71-4] 61 31d [1616841-71-4] 55 e) Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-4-yl)-(4-phenylquinazolin-2-yl)amine

[0198]

[0199] A mixture of 14.4 g (60 mmol) of 2-chloro-4-phenylquinazoline, 18.7 g (60 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-4-yl)amine, 7.7 g (80 mmol) of sodium tert-butoxide, 1.4 g (5 mmol) of tricyclohexylamine, 561 mg (2.5 mmol) of palladium(II) acetate, and 300 ml of mesitylene was heated under reflux for 24 h. After cooling, 200 ml of water was added, and the mixture was stirred for 30 min. The organic phase was separated, filtered through a short bed of Celite, and the solvent was removed in vacuo. The residue was recrystallized five times from DMF and then fractionally sublimed twice (p ca. 10 -6 < mbar, T = 350 - 380 °C). Yield: 23 g (40 mmol), 69% of theory: 99.9% by HPLC.

[0200] The following connections can be represented analogously: e.g. Educt 1 Educt 2 product Yield [%] 1e [6484-25-9] 65 2e [1292317-90-8] 71 3e [29874-83-7] 70 4e [6484-25-9] 64 5e [29874-83-7] 64 6e [29874-83-7] 71 7e [6484-25-9] 62 8e [14003252-55-0] 71 9e [29874-83-7] 64 10e [1413376-86-9] 65 11e [14003252-55-0] 54 12e [1373265-66-7] 63 13e [540466-42-0] 62 14e [6484-25-9] 57 15e [6484-25-9] 61 16e [1632307-99-3] 62 17e [1632307-97-1] 57 18e [1632294-77-9] 66 19e [29874-83-7] 58 20e [29874-83-7] 67 21e [29874-83-7] 76 22e [29874-83-7] 70 23e [29874-83-7] 68 24e [1262866-84-1] 71 25e 64 26e [1469860-57-8] 58 27e [1561960-15-3] 63 28e 67 f) 9-(2-chloroquinazolin-4-yl)-3-phenyl-9H-carbazole (not according to the invention)

[0201]

[0202] 14.4 g (60 mmol) of 3-phenyl-9H-carbazole are dissolved in 300 mL of dimethylformamide under a protective gas atmosphere, and 3 g of 60% NaH in mineral oil (75 mmol) are added. After 1 h at room temperature, a solution of 12.3 g (62 mmol) of 2,4-dichloroquinazoline in 150 mL of dimethylformamide is added dropwise. The reaction mixture is then stirred at room temperature for 12 h, poured onto ice, and extracted three times with dichloromethane. The combined organic phases are dried over Na 2 SO 4 and concentrated. The residue is recrystallized from toluene. The yield is 21 g (51 mmol), corresponding to 75% of theory.

[0203] The following connections can be represented analogously: e.g. Educt 1 Educt 2 product Yield [%] 1f [607-68-1] 55 2f [607-68-1] 57 3f [607-68-1] [1257220-47-5] 57 4f [607-68-1] [1313395-18-4] 55

[0204] The following connections can be represented analogously: e.g. Educt 1 Educt 2 product Yield [%] 5f [1262866-84-1] 66 6f [1257220-47-5] 65 7f [1313395-18-4] 57 8f [1313395-18-4] 53 9f 54 10f 50 11f [1313395-18-4] 51 12f [1257220-47-5] 55 13f [1333324-90-5] 51 14f [1333324-90-5] [1262866-84-1] 56

[0205] The compounds 5f to 14f are sublimed after recrystallization (p ca. 10 -6< mbar, T = 350 - 390 °C). Production of OLEDs

[0206] The following examples E1 to E20 (see Table 1) present the use of the materials according to the invention in OLEDs.

[0207] Pretreatment for examples E1-E20:Glass plates coated with 50 nm thick, patterned ITO (indium tin oxide) are treated with an oxygen plasma followed by an argon plasma prior to coating. These plasma-treated glass plates form the substrates onto which the OLEDs are applied.

[0208] OLEDs generally have the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emission layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL), and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of the OLEDs can be found in Table 1. The materials required for OLED production are shown in Table 2.

[0209] All materials are thermally evaporated in a vacuum chamber. The emission layer always consists of at least one matrix material (host material) and an emissive dopant (emitter), which is mixed with the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as EG1:TER (95%:5%) means that the EG1 material is present in the layer at a volume fraction of 95% and the TER at a volume fraction of 5%. Similarly, the electron-transport layer can also consist of a mixture of two materials.

[0210] The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd / A), and the external quantum efficiency (EQE, measured in percent) are determined as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming a Lambertian radiation pattern. The electroluminescence spectra are determined at a luminance of <1000 cd / m², and the CIE 1931 x and y color coordinates are calculated from them. Use of mixtures according to the invention in OLEDs

[0211] The compound EG1 according to the invention shows in the structure of an OLED according to Example E1 at a luminance of 1000 cd / m 2< a voltage of 3.9 V and an efficiency of 24 cd / A with a color coordinate of CIEx=0.67 and CIEy= 0.33.

[0212] The compounds EG2 to EG17 according to the invention are used as matrix material in the emission layer in Examples E2 to E17. The color coordinates of the electroluminescence spectra of the OLEDs from these experiments are CIEx=0.67 and CIEy=0.33. Thus, the materials are suitable for use in the emission layer of red OLEDs.

[0213] Furthermore, the materials of the invention can be successfully used in the electron transport layer (ETL) or the hole blocking layer (HBL). This is demonstrated in experiments E18 - E20. Here, too, the color coordinates of the OLED spectrum are CIEx = 0.67 and CIEy = 0.33. Table 1: Structure of the OLEDs Example HIL thickness HTL thickness EBL thickness EML thickness HBL thickness ETL thickness EIL thickness E1 HATCN 5nm SpMA1 125nm SpMA2 10nm EG1:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E2 HATCN 5nm SpMA1 125nm SpMA2 10nm EG2:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E3 HATCN 5nm SpMA1 125nm SpMA2 10nm EG3:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E4 HATCN 5nm SpMA1 125nm SpMA2 10nm EG4:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E5 HATCN 5nm SpMA1 125nm SpMA2 10nm EG5:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E6 HATCN 5nm SpMA1 125nm SpMA2 10nm EG6:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E7 HATCN 5nm SpMA1 125nm SpMA2 10nm EG7:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E8 HATCN 5nm SpMA1 125nm SpMA2 10nm EG8:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E9 HATCN 5nm SpMA1 125nm SpMA2 10nm EG9:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E10 HATCN 5nm SpMA1 125nm SpMA2 10nm EG10:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E11 HATCN 5nm SpMA1 125nm SpMA2 10nm EG11:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E12 HATCN 5nm SpMA1 125nm SpMA2 10nm EG12:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E13 HATCN 5nm SpMA1 125nm SpMA2 10nm EG13:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E14 HATCN 5nm SpMA1 125nm SpMA2 10nm EG14:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E15 HATCN 5nm SpMA1 125nm SpMA2 10nm EG15:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E16 HATCN 5nm SpMA1 125nm SpMA2 10nm EG16:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E17 HATCN 5nm SpMA1 125nm SpMA2 10nm EG17:TER (95%:5%) 40nm --- ST:LiQ (50%:50%) 35nm --- E18 HATCN 5nm SpMA1 125nm SpMA2 10nm EG1:TER (95%:5%) 40nm --- EG18:LiQ (50%:50%) 35nm --- E19 HATCN 5nm SpMA1 125nm SpMA2 10nm EG1:TER (95%:5%) 40nm EG19 5nm ST:LiQ (50%:50%) 35nm --- E20 HATCN 5nm SpMA1 125nm SpMA2 10nm EG1:TER (95%:5%) 40nm EG20 5nm ST:LiQ (50%:50%) 35nm --- Table 2: Structural formulas of the materials for the OLEDs HATCN SpMA1 SpMA2 ST TER LiQ EG1 EG2 EG3 EG4 EG5 EG6 EG7 EG8 EG9 EG10 EG11 EG12 EG13 EG14 EG15 EG16 EG17 EG18 EG19 EG20

Claims

1. Compound comprising at least one structure of the formula (IIIa), (IIIb), (XXIa), XXIb), (XXIVa) or (XXIVb), where the following applies to the symbols used: L is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R1; Z1, Z2, Z3, Z4 are X; X is on each occurrence, identically or differently, N or CR1, where a maximum of two X per ring stand for N, preferably CR1, or C if a radical Ara is bonded to X; X1 is on each occurrence, identically or differently, N or CR1; n, o, p are 0; m is 0 or 1; i is 0, 1 or 2; j is 0, 1, 2 or 3; h is 0, 1, 2, 3 or 4; Ara is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R1, where the radical Ara does not comprise a carbazole group or form a carbazole group with the aryl or heteroaryl group to which Ara is bonded, where this includes substituents R1, R2 and R3 which may be bonded to the radical Ara; Arb is an aromatic or heteroaromatic ring system having 5 to 45 aromatic ring atoms, which may be substituted by one or more radicals R1; R1 is on each occurrence, identically or differently, H, D, CN, N(Ar')2, a straight-chain alkyl group having 1, 2, 3 or 4 C atoms or a branched or cyclic alkyl group having 3 to 8 C atoms, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R2, or a combination of these systems; two or more substituents R1 may also form a monocyclic aliphatic ring system or an aromatic ring system with one another; Ar1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R2; two radicals Ar1 that are bonded to the same Si atom, N atom, P atom or B atom may also be bridged to one another by a single bond or a bridge selected from B(R2), C(R2)2, Si(R2)2, C=O, C=NR2, C=C(R2)2, O, S, S=O, SO2, N(R2), P(R2) and P(=O)R2; R2 is on each occurrence, identically or differently, H, D, CN, a straight-chain alkyl group having 1, 2, 3 or 4 C atoms or a branched alkyl group having 3 or 4 C atoms, which may in each case be substituted by one or more radicals R3, where one or more H atoms may be replaced by D or CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R3, or a combination of these systems; two or more substituents R2 may also form a monocyclic aliphatic ring system or an aromatic ring system with one another; R3 is selected on each occurrence, identically or differently, from the group consisting of H, D, CN, an aliphatic hydrocarbon radical having 1, 2, 3 or 4 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D or CN and which may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms; two or more substituents R3 may form a monocyclic aliphatic ring system with one another; with the proviso that at least one group X1 in formula (IIIa) or (IIIb) stands for N, and with the proviso that compounds of the formula (A) are excluded, where the symbols X, Arb and R1 used have the meaning described above and k is 0 or 1.

2. Compound according to Claim 1, comprising at least one structure of the formula (Va) or (Vb), where the symbols m, n, o, p, L, R1, Ara, Arb, Z1, Z2, Z3, Z4 and X used have the meaning given in Claim 1, and i stands for 0, 1 or 2.

3. Compound according to Claim 2, comprising at least one structure of the formula (XVIIIa) or (XVIIIb), where the symbols m, n, o, Ara, Arb, Z3, Z4 and X used have the meaning given in Claim 1, Z5 and Z6 stand, identically or differently, for X or C, i stands for 0, 1 or 2 and j stands for 0, 1, 2 or 3.

4. Compound according to Claim 3, comprising at least one structure of the formula (XIXa) or (XIXb), where the symbols m, Ara, Arb, R1 and X used have the meaning given in Claim 1, i stands for 0, 1 or 2 and h stands for 0, 1, 2, 3 or 4.

5. Compound according to Claim 1, comprising at least one structure of the formula (XXIIa) or (XXIIb), where the symbols m, Ara, Arb and R1 used have the meaning given in Claim 1, j stands for 0, 1, 2 or 3 and h stands for 0, 1, 2, 3 or 4.

6. Compound according to Claim 1, comprising at least one structure of the formula (XXIIIa), (XXIIIb), (XXIIIc), (XXIIId), (XXIIIe) or (XXIIIf), where the symbols m, Ara, Arb, R1 and X used have the meaning given in Claim 1, i stands for 0, 1 or 2, j stands for 0, 1, 2 or 3 and h stands for 0, 1, 2, 3 or 4.

7. Compound according to one of Claims 1 to 6, comprising at least one structure of the formula (XXVa), (XXVb), (XXVc), (XXVd), (XXVe), (XXVf), (XXVg) or (XXVh), where the symbols Ara, Arb, R1 and X used have the meaning given in Claim 1, i stands for 0, 1 or 2 and h stands for 0, 1, 2, 3 or 4.

8. Compound according to at least one of the preceding claims, characterised in that the group Arb represents a group of the formula (Arb-1), in which L1 is a bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R1, the symbol R1 has the meaning given in Claim 1, h is 0, 1, 2, 3 or 4 and the dashed line represents the bond.

9. Oligomer, polymer or dendrimer comprising one or more compounds according to one or more of Claims 1 to 8, where, instead of a hydrogen atom or a substituent, one or more bonds are present from the compounds to the polymer, oligomer or dendrimer.

10. Composition comprising at least one compound according to one or more of Claims 1 to 8 or an oligomer, polymer or dendrimer according to Claim 9 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters which exhibit TADF, host materials, electron-transport materials, electron-injection materials, hole-conductor materials, hole-injection materials, electron-blocking materials and hole-blocking materials.

11. Formulation comprising at least one compound according to one or more of Claims 1 to 8 and / or an oligomer, polymer or dendrimer according to Claim 9 and / or a composition according to Claim 10 and at least one solvent.

12. Use of a compound according to one or more of Claims 1 to 8, an oligomer, polymer or dendrimer according to Claim 9 or a composition according to Claim 10 in an electronic device, in particular as host material or electron-transport material.

13. Process for the preparation of a compound according to one or more of Claims 1 to 8 or an oligomer, polymer and / or dendrimer according to Claim 9, characterised in that a diarylamine compound is connected to a compound comprising at least one diazanaphthyl group in a coupling reaction.

14. Electronic device containing at least one compound according to one or more of Claims 1 to 8, an oligomer, polymer or dendrimer according to Claim 9 or a composition according to Claim 10, where the electronic device is preferably selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells or organic laser diodes.