BENZOFURO[3,2-D]PYRIMIDINE-2,4-DICARBONITRILE DERIVATIVES AND SIMILAR COMPOUNDS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Description

Technisches Gebiet

[0001] The present invention relates to dicyano-substituted monoaza or diazadibenzofuran derivatives and dicyano-substituted monoaza or diazadibenzothiophene derivatives, as well as electronic devices containing these compounds, in particular organic electroluminescent devices containing these compounds as triplet matrix materials, optionally in combination with a further triplet matrix material and suitable phosphorescent emitters, suitable mixtures and formulations. Stand der Technik

[0002] Phosphorescent metal-organic complexes are frequently used in organic electroluminescent devices (OLEDs). In general, there is still room for improvement in OLEDs, for example, regarding efficiency, operating voltage, and lifetime. The properties of phosphorescent OLEDs are not solely determined by the triplet emitters used. Other materials employed, such as matrix materials, are also of particular importance. Improvements to these materials can therefore lead to significant enhancements in the OLED properties.

[0003] According to the state of the art, carbazole derivatives, dibenzofuran derivatives, indenocarbazole derivatives, indolocarbazole derivatives, azadibenzofuran derivatives and azadibenzothiophene derivatives are among the materials used as matrix materials for phosphorescent emitters.

[0004] WO2014097866 describes a cyanosubstituted host material H1-12 containing a monoazadibenzothiophene unit and a monoazadibenzofuran unit.

[0005] EP2826781 describes specifically substituted diazadibenzofuran, diazadibenzothiophene and diazadibenzoselenophene derivatives and their use in organic electroluminescent compounds.

[0006] KR20170068927 describes monocyano-substituted diazadibenzofurans or -thiophenes, and their use as host material in combination with compounds of formula 2, as described.

[0007] In CN109912610, WO15105313, WO15108301, WO18060307, ​​special azadibenzofuran derivatives or azadibenzothiophene derivatives are described and their use in organic electroluminescent compounds.

[0008] WO2018060218 describes special diazadibenzofuran or diazadibenzothiophene derivatives substituted with two cyano groups and their use in organic electroluminescent compounds.

[0009] WO2017115608, WO2019160315 and KR20190141598 describe special dibenzofuran or dibenzothiophene derivatives which may be substituted with one or two cyano groups and whose use in organic electroluminescent compounds.

[0010] US2017186969 describes an organic light-emitting device wherein the organic layer contains special monoarylamines which may be unsubstituted or partially deuterated, in particular contained in an emitting auxiliary layer.

[0011] Special monoarylamines, which may be unsubstituted or partially deuterated, are described in patent applications WO2015022051, WO2017148564, WO2018083053 CN112375053, WO2019192954, WO2021156323 and WO21107728.

[0012] In general, there is still room for improvement in the suitability of these materials for use as matrix materials. The object of the present invention is to provide compounds that are particularly suitable for use as matrix materials in a phosphorescent OLED. In particular, the object of the present invention is to provide matrix materials that lead to an improved lifetime. This applies especially to the use of low to medium emitter concentrations, i.e., emitter concentrations in the range of 3 to 20%, and particularly 3 to 15%, since the device lifetime is especially limited in these cases.

[0013] It has now been found that electroluminescent devices containing compounds according to the following formula (1) exhibit improvements over the prior art, particularly when the compounds are used as matrix material for phosphorescent dopants.

[0014] It was further found that the combination of at least one compound of formula (1) as the first host material and at least one hole-transporting compound of formula (2) as the second host material in a light-emitting layer of an organic electroluminescent device solves this problem and eliminates the disadvantages of the prior art. Zusammenfassung der Erfindung

[0015] A first object of the present invention is a compound according to formula (1), where the following applies to the symbols and indices used: Ring A 1 in formula (1) corresponds to formula (1A) Y is N, C, or CR+ independently at each occurrence, where at least one Y represents N and at least two Y represent C to which the CN group is attached; if two Y represent N, they are separated from each other by at least one C-CN group; Vist is O or S; List is a single bond or an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, which may be unsubstituted or partially or completely substituted with D, provided that the heteroaromatic ring system excludes a carbazole group bonded via the N atom; Rx is an aromatic ring system with 6 to 30 ring atoms, which may be substituted with one or more R 2< residues, or a heteroaromatic ring system with 5 to 30 ring atoms, which may be substituted with one or more R 2< residues, provided that the ring system and any substituents attached to it do not contain an N-bonded carbazole group;R+ is an aromatic ring system with 6 to 30 ring atoms, which may be substituted with one or more R 2< residues, or a heteroaromatic ring system with 5 to 30 ring atoms, which may be substituted with one or more R 2< residues; R#, in each occurrence, is either an aromatic ring system with 6 to 30 ring atoms, which may be substituted with one or more R 2< residues, or a heteroaromatic ring system with 5 to 30 ring atoms, which may be substituted with one or more R 2< residues, provided that the ring system and any substituents attached to it do not contain an N-bonded carbazole group;R 2< is selected in each occurrence, either the same or differently, from the group consisting of D, F, CN, a straight-chain alkyl group with 1 to 20 C atoms, or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein one or more non-adjacent CH 2 groups may be replaced by O or S and wherein one or more H atoms may be replaced by D, F, or CN, or an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups with 1 to 4 carbon atoms each; in which case two or more adjacent substituents R 2< may together form a mono- or polycyclic, aliphatic ring system; bis 0 or 1; nist 0, 1, 2 or 3.

[0016] Another object of the invention is a mixture comprising at least one compound according to formula (1) as previously described or more preferably described later, and at least one further compound selected from the group consisting of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0017] Another object of the invention is a formulation comprising at least one compound according to formula (1), as previously described or subsequently preferably described, or a mixture as previously described, and at least one solvent.

[0018] Another object of the invention is an organic electroluminescent device comprising an anode, a cathode and at least one organic layer, containing at least one compound according to formula (1), as previously described or more preferably described later.

[0019] Another object of the invention is a method for producing an organic electroluminescent device, as previously described or preferably described below, characterized in that the organic layer is applied by vapor deposition or from solution. Beschreibung der Erfindung

[0020] In the present patent application, "D" or "D-atom" denotes deuterium.

[0021] An aryl group according to this invention contains 6 to 40 ring atoms, preferably carbon atoms. A heteroaryl group according to this invention contains 5 to 40 ring atoms, wherein the ring atoms comprise carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from nitrogen, oxygen, and / or sulfur. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e., phenyl, derived from benzene, or a simple heteroaromatic cycle, for example, derived from pyridine, pyrimidine, or thiophene, or a fused aryl or heteroaryl group, for example, derived from naphthalene, anthracene, phenanthrene, quinoline, or isoquinoline. An aryl group with 6 to 18 carbon atoms is therefore preferably phenyl, naphthyl, phenanthryl or triphenylenyl, whereby the attachment of the aryl group as a substituent is not restricted.The aryl or heteroaryl group according to this invention can bear one or more substituents, the suitable substituent being described below. If no such substituent is described, the aryl or heteroaryl group is unsubstituted.

[0022] An aromatic ring system according to this invention contains 6 to 40 carbon atoms in the ring system. The aromatic ring system also includes aryl groups, as previously described.

[0023] An aromatic ring system with 6 to 18 C atoms is preferably selected from phenyl, fully deuterated phenyl, biphenyl, naphthyl, phenanthryl and triphenylenyl.

[0024] A heteroaromatic ring system according to this invention contains 5 to 40 ring atoms and at least one heteroatom. A preferred heteroaromatic ring system has 9 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system also includes heteroaryl groups, as previously described. The heteroatoms in the heteroaromatic ring system are preferably selected from N, O and / or S.

[0025] For the purposes of this invention, an aromatic or heteroaromatic ring system is understood to be a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups may also be interrupted by a non-aromatic unit (preferably less than 10% of the atoms other than hydrogen), such as a carbon or oxygen atom or a carbonyl group. For example, systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diaryl ethers, stilbene, etc., are to be understood as aromatic or heteroaromatic 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, also included in the definition of the aromatic or heteroaromatic ring system.

[0026] Aromatic or heteroaromatic ring systems with 5–40 ring atoms, which can be linked via any position on the aromatic or heteroaromatic compound, include, 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, and isobenzothiophene. Dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine,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.,

[0027] The abbreviation Ar, in any instance, signifies an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be substituted with one or more R 7< substituents, where the R 7< substituent(s) has / have a meaning as described above or below. A preferred meaning of Ar is described below.

[0028] The abbreviation Ar 1, in any occurrence, signifies an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, which may be substituted with one or more non-aromatic residues R 5<. Two residues Ar 1 bonding to the same nitrogen, phosphorus, or phosphorus atom may also be bridged by a single bond or a bridge selected from C(R 5< ) 2, O, or S, where the residue R 5< or the substituents R 5< have a meaning as described above or below. A preferred meaning of Ar 1 is described below.

[0029] The abbreviation Ar 5, whether used interchangeably or differently, represents an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be substituted with one or more R 7< groups, where the R 7< group or substituents have a meaning as described above or below. A preferred meaning of Ar 5 is described below.

[0030] For the purposes of this invention, a cyclic alkyl, alkoxy or thioalkyl group is understood to be a monocyclic, a bicyclic or a polycyclic group.

[0031] Im Rahmen der vorliegenden Erfindung werden unter einer geradkettigen, verzweigten oder cyclischen C 1 - bis C 20 -Alkylgruppe beispielsweise die Reste 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, Trifluormethyl, Pentafluorethyl, 2,2,2-Trifluorethyl, 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- are understood.,

[0032] Examples of straight-chain or branched C1 to C20 alkoxy groups include methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2-methylbutoxy.

[0033] Straight-chain C1 to C20 thioalkyl groups include, for example, S-alkyl groups such as thiomethyl, 1-thioethyl, 1-thio-i-propyl, 1-thio-n-propoyl, 1-thio-i-butyl, 1-thio-n-butyl or 1-thio-t-butyl.

[0034] An aryloxy or heteroaryloxy group with 5 to 40 aromatic ring atoms means O-aryl or O-heteroaryl and means that the aryl or heteroaryl group is bonded via an oxygen atom, the aryl or heteroaryl group having a meaning as described above.

[0035] The phrase "two or more residues can form a ring system" refers to the formation of an aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system. Within the context of this description, it is understood, among other things, that the two residues are linked to each other by a chemical bond, formally involving the elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0036] 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 diagram:

[0037] The compounds of formula (1) and their preferred embodiments are described below. The preferred embodiments also apply to the mixture, formulation, and organic electroluminescent device according to the invention.

[0038] In compounds of formula (1), Y is N, C or CR+ at each occurrence independently of one another, where at least one Y represents N and at least two Y represent C to which the CN group is bonded; if two Y represent N, they are separated from each other by at least one C-CN group.

[0039] Preferred embodiments of the compounds of formula (1) are compounds of formulas (1a), (1b), (1c), (1d), (1e) or (1f), wherein the symbols used V, L, R+, b, Rx, R# and n have a previously stated or subsequently preferred meaning,

[0040] Another object of the invention is therefore compounds of formulas (1a), (1b), (1c), (1d), (1e) or (1f), as previously described or preferably described below.

[0041] Preferred compounds of formula (1) correspond to formulas (1a), (1b), (1d) and (1e).

[0042] Particularly preferred compounds of formula (1) correspond to formulas (1a) or (1b). Very particularly preferred compounds of formula (1) correspond to formula (1a).

[0043] In combinations of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), V preferably represents O.

[0044] Another object of the invention is therefore compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) or (1f), as previously described or preferably described below, in which VO means.

[0045] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably named compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), n is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1 and most particularly preferably 0.

[0046] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), R+ is preferably an aromatic ring system with 6 to 30 ring atoms, which may be substituted with one or more R 2< groups, or a heteroaromatic ring system with 5 to 30 ring atoms, which may be substituted with one or more R 2< groups, provided that the ring system and the substituents attached thereto do not contain an N-bonded carbazole group and wherein the substituent R 2< has a previously or subsequently preferably named meaning.

[0047] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), R+ is preferably phenyl, dibenzofuranyl, carbazol-N-yl or N-arylcarbazolyl, which may be substituted with one or more R2< groups, wherein the abbreviation "aryl" denotes an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, which may be substituted with one or more R2< groups, wherein the substituent R2< has a meaning previously or subsequently preferably mentioned. Phenyl, 1,3-biphenyl, 1,4-biphenyl, dibenzofuranyl or dibenzothiophenyl is preferred. Phenyl is particularly preferred.

[0048] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), R+ is particularly preferably phenyl, dibenzofuranyl or N-arylcarbazolyl, which may be substituted with one or more R 2< groups, wherein the abbreviation "aryl" means an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, which may be substituted with one or more R 2< groups, wherein the substituent R 2< has a previously or subsequently preferably mentioned meaning, with the condition that substituents R 2< bonded to "aryl" do not represent an N-bonded carbazole group. Preferred compounds are "aryl" phenyl, 1,3-biphenyl, 1,4-biphenyl, dibenzofuranyl, or dibenzothiophenyl. "Aryl" phenyl is particularly preferred.

[0049] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), R+ is most preferably phenyl, dibenzofuran-1-yl, dibenzofuran-3-yl or N-phenylcarbazol-3-yl when it occurs.

[0050] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), R# is preferably an aromatic ring system with 6 to 18 ring atoms, which may be substituted with one or more R 2< groups, or a heteroaromatic ring system with 9 to 13 ring atoms, which may be substituted with one or more R 2< groups, provided that the ring system and the substituents attached thereto do not contain an N-bonded carbazole group, wherein the substituent R 2< has a previously mentioned or subsequently preferably mentioned meaning.In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), R# is particularly preferably phenyl, 1,3-biphenyl, 1,4-biphenyl, dibenzothiophenyl or dibenzofuranyl, which may be substituted with one or more R 2< groups. In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), R# is most preferably 1,3-biphenyl or dibenzofuran-1-yl.

[0051] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably named compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), (1g) b is preferably 0.

[0052] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), the substituent Rx preferably represents an aromatic ring system with 6 to 20 ring atoms or a heteroaromatic ring system with 6 to 21 ring atoms, each of which may be substituted with one or more residues R 2<, wherein the residue R 2< has a previously mentioned or subsequently preferably mentioned meaning, with the condition that the ring system and the substituents bound to it do not contain an N-bonded carbazole group.

[0053] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), the substituent Rx particularly preferably represents an aromatic ring system with 6 to 20 ring atoms, each of which may be substituted with one or more R 2< groups, or di-arylpyridine, di-arylpyrimidine, di-aryltriazine, quinazoline, dibenzofuran, dibenzothiophene or N-arylcarbazole, each of which may be substituted with one or more R 2< groups, wherein the R 2< group has a previously or subsequently preferably mentioned meaning and wherein the abbreviation "aryl" means an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, which may be substituted with one or more residues R 2< can be substituted, wherein the substituent R 2< has a previously mentioned or subsequently preferably mentioned meaning, with the condition thatthat substituents bonded to "aryl" R 2< do not represent an N-bonded carbazole group. Preferably, "aryl" in Rx is phenyl, 1,3-biphenyl, 1,4-biphenyl, dibenzofuranyl, dibenzothiopenyl, 9,9-dimethylfluorenyl, or triphenylenyl, wherein the bonding of "aryl" to the corresponding N atom of the N-arylcarbazole is not restricted, unless otherwise specified.

[0054] If the substituent Rx is substituted with one or more R 2< groups as described above, R 2< is preferably selected independently from the group consisting of D, CN, a straight-chain or branched alkyl group with 1 to 20 carbon atoms, phenyl, 1,4-biphenyl, 1,3-biphenyl, N-arylcarbazolyl and dibenzofuranyl, wherein "aryl" in N-arylcarbazolyl has any previously mentioned meaning or any previously mentioned preferred meaning.

[0055] If the substituent Rx, as described above, is substituted with one or more R2< groups, then R2< is preferably, independently of each other, D, phenyl, or tert-butyl. In one embodiment of the substituent Rx, as described above or preferably, this substituent is deuterated. In a preferred embodiment of the substituent Rx, as described above or preferably, the substituent Rx has one R2< group, two R2< groups, or it is unsubstituted, wherein the R2< group has one of the aforementioned or preferably mentioned meanings. A preferred aromatic ring system as Rx is, for example, phenyl, 1,3-biphenyl, 1,4-biphenyl, terphenyl, spirobifluorenyl, 9,9-dimethylfluorenyl, 9-phenyl-9-methylfluorenyl, triphenylenyl or fluoranthenyl, which may be substituted with one or more substituents R 2<, where R 2< has a previously mentioned or preferably mentioned meaning.

[0056] Rx is particularly preferably phenyl, 1,3-biphenyl, terphenyl, spirobifluorenyl, 9,9-dimethylfluorenyl, triphenylenyl, fluoranthenyl, triphenyleno[1,12-bcd]furanyl, di-aryl-triazinyl, dibenzofuranyl, dibenzothiophenyl or N-aryl-carbazolyl, which may be substituted with one or more substituents R 2<, wherein "aryl" and R 2< have a previously mentioned or preferably mentioned meaning.

[0057] Rx is most preferably Spirobifluorenyl, Triphenylenyl, Di-Aryl-Triazinyl, Dibenzofuranyl or Dibenzothiophenyl, which may be substituted with one or more substituents R 2<, wherein R 2< has a previously mentioned or preferably mentioned meaning.

[0058] Rx is most preferably triphenylenyl, di-aryl-triazinyl or dibenzofuranyl, which may be substituted with one or more substituents R 2<, wherein R 2< has a previously mentioned or preferably mentioned meaning.

[0059] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), the symbol L represents a linker for a single bond or an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, which may be unsubstituted or partially or completely substituted with D, provided that the heteroaromatic ring system excludes a monovalent carbazole group bonded via the N atom.

[0060] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably named compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), the symbol L preferably represents a single bond or a linker selected from the group L-1 to L-33, where V1 independently represents O, S, C(R1<)2 or N-aryl, R1< is independently selected from methyl or phenyl, and "aryl" has a previously specified or preferably specified meaning, and the dashed lines denote the linkage to Rx and the remainder of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f). The linkers L-1 to L-33 may be partially or completely deuterated. Preferably, V1 is O or N-aryl. Particularly preferably, V1 is O.

[0061] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably named compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), the symbol L preferably represents a single bond or a linker selected from the group L-2, L-3, L-22 and L-23, as previously or preferably described, particularly preferably a single bond or L-2, most preferably a single bond.

[0062] The compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) or preferably the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) as previously described, are in a preferred embodiment partially or completely deuterated.

[0063] Examples of suitable host materials for formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) are the structures listed below in Table 1.

[0064] Particularly suitable compounds of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f) are compounds E1 to E27 of Table 2. Table 2: E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11 E12 E13 E14 E15 E16 E17 E18 E19 E20 E21 E22 E23 E24 E25 E26 E27.

[0065] The compounds according to the invention can be prepared according to synthesis steps known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc.

[0066] Suitable compounds with an azadibenzofuran or azadibenzothiophene group can often be obtained commercially, with the starting compounds presented in the examples being obtainable by known methods, which are therefore referenced here.

[0067] In the following synthesis schemes, the compounds are shown with a small number of substituents to simplify the structures. This does not preclude the presence of any further substituents in the processes. The methods shown for the synthesis of the compounds according to the invention are to be understood as examples. A person skilled in the art can develop alternative synthetic routes within the scope of their general technical knowledge.

[0068] An implementation can be achieved by following the diagrams below, without this being intended to be a limitation. The individual steps of the diagrams can be combined as desired.

[0069] The preparation of precursors for compounds of formula (1) can be carried out, for example, according to the following scheme 1, where V and L-Rx have one of the previously given or preferably given meanings.

[0070] By these methods, possibly followed by purification, such as recrystallization or sublimation, the compounds of formula (1) can be obtained in high purity, preferably more than 99% (determined by < 1 H-NMR and / or HPLC).

[0071] For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes, formulations of the compounds according to the invention or of mixtures of compounds according to the invention with further functional materials, such as matrix materials, fluorescent emitters, phosphorescent emitters and / or emitters exhibiting TADF, 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 include, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, 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-Dimethylanisol, 3,5-Dimethylanisol, Acetophenon, α-Terpineol, Benzothiazol, Butylbenzoat, Cumol, Cyclohexanol, Cyclohexanon, Cyclohexylbenzol, Decalin, Dodecylbenzol, Ethylbenzoat, Indan, NMP, p-Cymol, Phenetol, 1,4-Diisopropylbenzol, Dibenzylether, Diethylenglycolbutylmethylether, Triethylenglycolbutylmethylether, Diethylenglycoldibutylether, Triethylenglycoldimethylether, Diethylenglycolmonobutylether, Tripropyleneglycoldimethylether, Tetraethylenglycoldimethylether, 2-Isopropylnaphthalin, Pentylbenzol, Hexylbenzol, Heptylbenzol, Octylbenzol, 1,1-Bis(3,4-dimethylphenyl)ethan, 2-Methylbiphenyl, 3-Methylbiphenyl, 1-Methylnaphthalin, 1-Ethylnaphthalin, Ethyloctanoat, Sebacinsäure-diethylester, Octyloctanoat, Heptylbenzol, Menthyl-isovalerat, Cyclohexylhexanoat oder Mischungen dieser Lösemittel.,

[0072] The compounds of formula (1) according to the invention, as previously described or preferably described, are suitable for use in an organic electroluminescent device, in particular as a matrix material.

[0073] When the compound according to the invention is used as a matrix material or synonymously host material in an emitting layer, it is preferably used in combination with another compound.

[0074] Another object of the invention is therefore a mixture containing at least one compound of formula (1) or at least one preferred compound of one of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), or a compound of Table 1 or one of the compounds E1 until E27and at least one further compound selected from the group consisting of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence). Suitable matrix materials and emitters that can be used in this mixture according to the invention are described below.

[0075] Another object of the present invention is a formulation comprising at least one compound or mixture according to the invention, as described above, and at least one solvent. The solvent may be one of the solvents mentioned above or a mixture of these solvents.

[0076] Another object of the present invention is an organic electroluminescent device comprising an anode, a cathode and at least one organic layer, containing at least one compound of formula (1) or at least one preferred compound of one of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), or a compound of Table 1 or one of the compounds E1 to E27.

[0077] The organic electroluminescent device according to the invention (synonymously organic electroluminescence device) is, for example, an organic light-emitting transistor (OLET), an organic field-quench device (OFQD), an organic light-emitting electrochemical cell (OLEC, LEC, LEEC), an organic laser diode (O-Laser), or an organic light-emitting diode (OLED). The organic electroluminescent device according to the invention is, in particular, an organic light-emitting diode or an organic light-emitting electrochemical cell. An OLED is especially preferred.

[0078] The organic layer of the device according to the invention preferably comprises, in addition to a light-emitting layer (EML), a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), an exciton blocking layer, an electron blocking layer, and / or charge-generation layers. The device according to the invention may also contain several layers of this group, preferably selected from EML, HIL, HTL, ETL, EIL, and HBL. Likewise, interlayers, which, for example, have an exciton-blocking function, may be introduced between two emitting layers.

[0079] If multiple emission layers are present, these preferably exhibit multiple emission maxima between 380 nm and 750 nm, resulting in overall white emission, i.e., different emitting compounds that can fluoresce or phosphoresce are used in the emitting layers.

[0080] Systems with three emitting layers are particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission. The organic electroluminescent device according to the invention can also be a tandem electroluminescent device, especially for white-emitting OLEDs. The device can also contain inorganic materials or layers composed entirely of inorganic materials.

[0081] It presents no difficulty for a person skilled in the art to draw upon a multitude of materials known in the prior art to select suitable materials for use in the previously described layers of the organic electroluminescent device. In doing so, the person skilled in the art makes standard considerations regarding the chemical and physical properties of the materials, since it is known that the materials in an organic electroluminescent device are interrelated with one another. This relates, for example, to the energy positions of the orbitals (HOMO, LUMO) or the positions of triplet and singlet energies, as well as other material properties. The compound of formula (1) according to the invention, as previously described or preferably described, can be used in different layers, depending on the precise structure. An organic electroluminescent device containing a compound according to formula (1) is preferred.The preferred embodiments described above are used in an emitting layer as a matrix material for fluorescent emitters, phosphorescent emitters, or emitters exhibiting TADF (thermally activated delayed fluorescence), particularly for phosphorescent emitters. Furthermore, the compound according to the invention can also be used in an electron transport layer and / or in a hole transport layer and / or in an exciton blocking layer and / or in a hole blocking layer. The compound according to the invention is particularly preferably used as a matrix material in an emitting layer or as an electron transport or hole blocking material in an electron transport or hole blocking layer.

[0082] Another object of the present invention is an organic electroluminescent device as previously described, wherein the organic layer contains at least one light-emitting layer comprising the at least one compound of formula (1) or the at least one preferred compound of one of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), or a compound of Table 1 or one of the compounds E1 until E27 contains.

[0083] In one embodiment of the invention, a further matrix material is selected for the light-emitting layer of the device according to the invention, which is composed of compounds of formula (1) as previously described or preferably described, or of the compounds of Table 1 or the compounds E1 until E27 is used.

[0084] Another object of the present invention is therefore an organic electroluminescent device as previously described, wherein the organic layer contains at least one light-emitting layer comprising the at least one compound of formula (1) or the at least one preferred compound of one of formulas (1), (1a), (1b), (1c), (1d), (1e) and (1f), or a compound of Table 1 or one of the compounds E1 until E27 and contains another matrix material.

[0085] Suitable matrix materials that can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, biscarbazoles, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, azaborols or boron esters, triazine derivatives, zinc complexes, diazasilol or tetraazasilol derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or dibenzofuran derivatives. Likewise, another phosphorescent emitter, which emits at a shorter wavelength than the actual emitter, can be present in the mixture as a co-host, or a compound that does not participate, or does not participate to a significant extent, in charge transport, such as, for example, a wide band gap Connection.

[0086] Under wide - band - gap-Material is understood herein to mean a material in the sense of the revelation of US 7,294,849, which is characterized by a band gap of at least 3.5 eV, where band gap is understood to be the distance between HOMO and LUMO energy of a material.

[0087] Particularly suitable matrix materials, which are advantageously combined with compounds of formula (1), as previously or preferably described, in a mixed matrix system, can be selected from the compounds of formulas (6), (7), (8), (9), (10) or (11), as described below.

[0088] A further object of the invention is therefore an organic electroluminescent device comprising an anode, a cathode and at least one organic layer, containing at least one light-emitting layer, wherein the at least one light-emitting layer comprises at least one compound of formula (1) as matrix material 1, as previously described or preferably described, and at least one compound of formulas (6), (7), (8), (9) or (10) as matrix material 2. the following applies to the symbols and indices used: A 1< is C(R 7< ) 2 , NR 7< , O or S; A is, at each occurrence independently of each other, a group of formula (3) or (4), X 2 is the same or different CH, CR 6< or N in each occurrence, where a maximum of 2 symbols X 2 N can mean; * indicates the binding site to formula (9); R 6< is, in each occurrence, the same or different D, CN, a straight-chain alkyl group with 1 to 20 C atoms, or an alkenyl or alkynyl group with 2 to 20 C atoms, or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the alkyl, alkenyl, or alkynyl group may each be substituted with one or more R 7< residues, and wherein one or more non-adjacent CH 2 groups may be replaced by Si(R 7< ) 2 , C=O, NR 7< , O, S, or CONR 7<, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which may be substituted by one or more R 7< residues; two R 6< residues may also form an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system together;Arist, whether the same or different, represents an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be substituted with one or more R 7< residues; Ar 5<, whether the same or different, represents an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be substituted with one or more R 7< residues;R 7< is the same or different in each occurrence D, F, Cl, Br, I, N(R 8< ) 2 , CN, NO 2 , OR 8< , SR 8< , Si(R 8< ) 3 , B(OR 8< ) 2 , C(=O)R 8< , P(=O)(R 8< ) 2 , S(=O)R 8< , S(=O) 2 R 8< , OSO 2 R 8< , a straight-chain alkyl group with 1 to 20 C atoms or an alkenyl or alkynyl group with 2 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group may each be substituted with one or more R 8< residues, wherein one or more are not neighboring CH2 groups may be replaced by Si(R8<)2, C=O, NR8<, O, S or CONR8<, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which may be substituted by one or more R8< residues; two or more R7< residues may together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the R7< residues do not form such a ring system;R 8< is, in each occurrence, the same or different H, D, F or an aliphatic, aromatic or heteroaromatic organic residue, in particular a hydrocarbon residue, with 1 to 20 C atoms, in which one or more H atoms may also be replaced by F; c, c1, c2 each independently mean 0 or 1 in each occurrence, wherein the sum of the indices in each occurrence c+c1+c2 means 1; d, d1, d2 each independently mean 0 or 1 in each occurrence, wherein the sum of the indices in each occurrence d+d1+d2 means 1; q, q1, q2 each independently mean 0 or 1 in each occurrence; sist is the same or different 0, 1, 2, 3 or 4 in each occurrence; tist is the same or different 0, 1, 2, or 3 in each occurrence; uist is the same or different 0, 1 or 2 in each occurrence; and vist is 0 or 1. ;

[0089] In compounds of formulas (6), (7), (8) or (10) s is preferably 0 or 1, particularly preferably 0.

[0090] In compounds of formulas (6), (7) or (8) t is preferably 0 or 1, particularly preferably 0.

[0091] In compounds of formulas (6), (7), (8) or (10) u is preferably 0 or 1, particularly preferably 0.

[0092] The sum of the indices s, t and u in compounds of formulas (6), (7), (8) or (10) is preferably at most 6, more preferably at most 4 and more preferably at most 2.

[0093] In compounds of formula (9), c, c1, c2 each independently mean 0 or 1 at each occurrence, where the sum of the indices c+c1+c2 means 1 at each occurrence. Preferably, c2 has the meaning 1.

[0094] In a preferred embodiment of the compounds of formulas (6), (7), (8), (9) or (10), which can be combined according to the invention with compounds of formula (1) as previously described, R 6< is the same or different at each occurrence selected from the group consisting of D, F, CN, NO 2 , Si(R 7< ) 3 , B(OR 7< ) 2 , a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the alkyl group may in each case be substituted with one or more R 7< groups, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more R 7< groups.

[0095] In a preferred embodiment of the compounds of formulas (6), (7), (8), (9) or (10), which can be combined according to the invention with compounds of formula (1) as described above, R 6< is selected, either the same or different in each occurrence, from the group consisting of D, an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, which may be substituted with one or more residues R 7<. A preferred residue R 7< is the group N(Ar) 2 .

[0096] Ar 5 is preferably selected in compounds of formulas (6), (7), (8) or (10) from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorenyl, which may be linked via the 1-, 2-, 3- or 4-position, spirobifluorenyl, which may be linked via the 1-, 2-, 3- or 4-position, naphthyl, in particular 1- or 2-linked naphthyl, or residues derived from indole, benzofuran, benzothiophene, carbazole, which may be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which may be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, which may be linked via the may be linked to position 1, 2, 3 or 4, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene,which can each be substituted with one or more residues R 7<. Preferably, Ar 5 is not substituted.

[0097] When A1< in formula (7) or (8) represents NR7<, the substituent R7< bonded to the nitrogen atom preferably represents an aromatic or heteroaromatic ring system with 5 to 24 aromatic ring atoms, which may also be substituted by one or more R8< groups. In a particularly preferred embodiment, this substituent R7< represents, in each instance, an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, particularly with 6 to 18 aromatic ring atoms. Preferred embodiments for R7< are phenyl, biphenyl, terphenyl, and quaterphenyl, which are preferably unsubstituted, as well as groups derived from triazine, pyrimidine, and quinazoline, which may be substituted by one or more R8< groups.

[0098] If A1< in formula (7) or (8) represents C(R7<)2, the substituents R7< bonded to this carbon atom preferably represent, either identically or differently in each instance, a linear alkyl group with 1 to 10 carbon atoms, or a branched or cyclic alkyl group with 3 to 10 carbon atoms, or an aromatic or heteroaromatic ring system with 5 to 24 aromatic ring atoms, which may also be substituted by one or more R8< groups. R7< most preferably represents a methyl group or a phenyl group. The R7< groups may also form a ring system with each other, leading to a spiro system.

[0099] In a preferred embodiment of the compounds of formulas (6), (7), (8), (9) and (10), these compounds are partially or completely deuterated, particularly preferably completely deuterated.

[0100] The preparation of the compounds of formulas (6), (7), (8), (9) and (10) is generally known and some of the compounds are commercially available.

[0101] Compounds of formula (9) are disclosed, for example, in WO2021180614, pages 110 to 119, in particular as examples on pages 120 to 127. Their preparation is disclosed in WO2021180614 on page 128 and in the synthesis examples on pages 214 to 218.

[0102] Another object of the invention is an organic electroluminescent device comprising an anode, a cathode and at least one organic layer, containing at least one light-emitting layer, wherein the at least one light-emitting layer comprises at least one compound of formula (1) as matrix material 1, as previously described or preferably described, and at least one compound of formula (11). the following applies to the symbols and indices used: Wist O, S, C(R) 2 , N-Ar 1 ; Rist is, independently of each other, a straight-chain or branched alkyl group with 1 to 4 C atoms, which may be partially or completely deuterated, or an unsubstituted or partially or completely deuterated aromatic ring system with 6 to 18 C atoms, wherein two substituents R may, with the C atom to which they are bonded, form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic unsubstituted, partially deuterated or completely deuterated ring system, which may be substituted by one or more substituents R 5< ; Ar 1 is, in each occurrence, the same or different, an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, which may be substituted by one or more substituents R 5< ; Two Ar 1 residues, which bind to the same N atom, P atom or B atom, can also be connected by a single bond or a bridge, selected from C(R 5< ) 2 , O or S,be bridged with each other; R1< is selected in each instance, either the same or different, from the group consisting of F, Cl, Br, I, CN, NO2, C(=O)R', P(=O)(Ar1)2, P(Ar1)2, B(Ar1)2, Si(Ar1)3, Si(R')3, a straight-chain alkyl, alkoxy, or thioalkyl group with 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group with 3 to 20 carbon atoms, or an alkenyl group with 2 to 20 carbon atoms, each of which may be substituted with one or more R' groups, wherein one or more non-adjacent CH2 groups are replaced by R'C=CR', Si(R')2, C=O, C=S, C=NR', P(=O)(R'), SO, SO 2 , NR', O, S or CONR' may be replaced and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO 2; R' is, in each occurrence, the same or different aliphatic, aromatic or heteroaromatic organic residue, in particular a hydrocarbon residue,with 1 to 20 carbon atoms; R4< is selected, in each occurrence, from the group consisting of F, Cl, Br, I, CN, NO2, N(Ar1)2, NH2, N(R5<)2, C(=O)Ar1, C(=O)H, C(=O)R5<, P(=O)(Ar1)2, a straight-chain alkyl, alkoxy, or thioalkyl group with 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group with 3 to 40 carbon atoms, or an alkenyl or alkynyl group with 2 to 40 carbon atoms, each of which may be substituted with one or more R5< residues, wherein one or more non-adjacent CH2 groups are replaced by HC=CH, R5< C=CR5< , C=C, Si(R 5< ) 2 , Ge(R 5< ) 2 , Sn(R 5< ) 2 , C=O, C=S, C=Se, C=NR 5< , P(=O)(R 5< ), SO, SO 2 , NH, NR 5< , O, S, CONH or CONR 5< may be replaced and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , an aromatic or heteroaromatic ring system with 5 to 60 ring atoms,which may be substituted with one or more R 5< residues, an aryloxy or heteroaryloxy group with 5 to 60 ring atoms which may be substituted with one or more R 5< residues, or a combination of these systems, wherein optionally two or more adjacent substituents R 4< may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more R 5< residues; R 5< is selected in each occurrence, either the same or different, from the group consisting of D, F, CN, a straight-chain alkyl group with 1 to 20 C atoms, or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein one or more non-adjacent CH 2 groups may be replaced by O or S, and wherein one or more H atoms may be replaced by D, F, or CN, or an aromatic or heteroaromatic ring system with 5 to 30 ring atoms.in which one or more H atoms can be replaced by D, F, Cl, Br, I or CN and which can be substituted by one or more alkyl groups with 1 to 4 carbon atoms each; two or more adjacent substituents R 5< can together form a mono- or polycyclic, aliphatic ring system; x, x1 are independently 0, 1, 2, 3 or 4 at each occurrence; y, z are each independently 0, 1 or 2; a1, a2 are each independently 0, 1, 2, 3, 4 or 5; a3 is 0, 1, 2 or 3; a4 is 0, 1, 2, 3 or 4.

[0103] The preparation of the triarylamines of formula (11) is known to those skilled in the art and some of the compounds are commercially available.

[0104] The compounds of formulas (6), (7), (8), (9), (10) or (11) are preferably partially deuterated or completely deuterated.

[0105] In compounds of formula (11), as previously described, the sum of the indices a₁ + a₂ + a₃ + a₄ is preferably selected from 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17. This additional matrix material is accordingly at least partially deuterated at each N-bonded substituent. In a preferred embodiment, two of the N-bonded substituents are partially deuterated, and the third N-bonded substituent is fully deuterated. In a further preferred embodiment, two of the N-bonded substituents are fully deuterated, and the third N-bonded substituent is partially deuterated. In a further preferred embodiment, each N-bonded substituent is fully deuterated.

[0106] In a preferred embodiment of the further matrix material, it is a mixture of deuterated compounds of formula (11), as previously described or more preferably described below, wherein the degree of deuteration of the compounds of formula (11) is at least 50% to 90%, preferably 70% to 100%. Corresponding deuteration methods are known to those skilled in the art and are described, for example, in KR2016041014, WO2017122988, KR202005282, KR101978651 and WO2018110887 or in Bulletin of the Chemical Society of Japan, 2021, 94(2), 600-605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071.

[0107] A suitable method for deuterating an arylamine or a heteroarylamine by exchanging one or more hydrogen atoms for dium atoms is to treat the arylamine or heteroarylamine to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" means any compound that contains one or more dium atoms and can release them under suitable conditions.

[0108] The platinum catalyst is preferably dry platinum on carbon, preferably 5% dry platinum on carbon. The palladium catalyst is preferably dry palladium on carbon, preferably 5% dry palladium on carbon. A suitable deuterium source is D₂O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4, or toluene-d8. A preferred deuterium source is D₂O or a combination of D₂O and a fully deuterated organic solvent. A particularly preferred deuterium source is the combination of D₂O with a fully deuterated organic solvent, the fully deuterated solvent not being restricted here. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. A particularly preferred deuterium source is a combination of D₂O and toluene-d8.The reaction is preferably carried out under heating, more preferably under heating to temperatures between 100 °C and 200 °C. Furthermore, the reaction is preferably carried out under pressure.

[0109] Preferred compounds of formula (11) are represented by formulas (11a), (11b), (11c), (11d), (11e), (11f), (11g), (11h), (11i), (11j), (11k), (11l), (11m), (11n), (11o) and (11p), Formal (11a) Formal (11b) Formal (11c) Formal (11d) Formal (11e) Formal (11f) Formal (11g) Formal (11h) Formal (11i) Formal (11j) Formal (11k) Formal (11l) Formal (11m) Formal (11n) Formal (11o) Formal (11p), where a 1 , a 2 , a 3 , a 4 , x, x1, y, z, R 1 and R 4 have a previously mentioned or previously or subsequently preferred meaning and R< c< is each independently a straight-chain or branched alkyl group with 1 to 4 carbon atoms, which may be partially or completely deuterated, or an unsubstituted or partially or completely deuterated aromatic ring system with 6 to 18 carbon atoms; x2 is 0, 1, 3 or 4; y1, z1 are each independently 0, 1 or 2; y1, z1, y2, z2 are each independently 0, 1 or 2, preferably 0; a 11 is 0, 1, 2, 3 or 4; a 33, a 44 are each independently 0, 1, 2, 3 or 4 and a 34, a 45 are each independently 0, 1, 2, 3 or 4.

[0110] R< is preferably equal to and a straight-chain or branched alkyl group with 1 to 4 C atoms, which may be partially or completely deuterated, or an unsubstituted or partially or completely deuterated phenyl.

[0111] In combinations of formulas (11), (11a), (11b), (11c), (11d), (11e), (11f), (11g), (11h), (11i), (11j), (11k), (11l), (11m), (11n), (11o) and (11p) y+z is preferably 0.

[0112] Preferably, the N atom in compounds of formulas (11), (11a), (11b), (11c), (11d), (11e), (11f), (11g), (11h), (11i), (11j), (11k), (11l), (11m), (11n), (11o) and (11p) is bound in 1-position to dibenzofuran or dibenzothiophene groups or in 4-position to fluorene or spirobifluorene groups.

[0113] Preferably, R 4< in compounds of formulas (11), (11a), (11b), (11c), (11d), (11e), (11f), (11g), (11h), (11i), (11j), (11k), (11l), (11m), (11n), (11o) and (11p) is selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorenyl, which may be linked via the 1-, 2-, 3- or 4-position, spirobifluorenyl, which may be linked via the 1-, 2-, 3- or 4-position, naphthyl, in particular 1- or 2-linked naphthyl, or residues derived from indole, Benzofuran, benzothiophene, carbazole, which may be linked via the 1, 2, 3 or 4 position, dibenzofuran, which may be linked via the 1, 2, 3 or 4 position, dibenzothiophene, which may be linked via the 1, 2, 3 or 4 position, indenocarbazole, indolocarbazole, phenanthrene or triphenylene,which can each be substituted with one or more residues R 5<. Preferably, R 4< is not substituted.

[0114] Preferably, R 1< in compounds of formulas (11), (11a), (11b), (11c), (11d), (11e), (11f), (11g), (11h), (11i), (11j), (11k), (11l), (11m), (11n), (11o) and (11p) is selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorenyl, which may be linked via the 1-, 2-, 3- or 4-position, spirobifluorenyl, which may be linked via the 1-, 2-, 3- or 4-position, naphthyl, in particular 1- or 2-linked naphthyl, or residues derived from indole, Benzofuran, benzothiophene, carbazole, which may be linked via the 1, 2, 3 or 4 position, dibenzofuran, which may be linked via the 1, 2, 3 or 4 position, dibenzothiophene, which may be linked via the 1, 2, 3 or 4 position, indenocarbazole, indolocarbazole, phenanthrene or triphenylene,which can each be substituted with one or more residues R 5<. Preferably, R 1< is not substituted.

[0115] Preferred values ​​are x, x1, y, z, x2, y1 and z1 0.

[0116] The compounds of formulas (6), (9), (10) and (11) are particularly preferred as further matrix material.

[0117] Particularly suitable compounds of formulas (6), (7), (8), (9), (10) or (11) selected according to the invention, and preferably used in combination with at least one compound of formula (1) in the electroluminescent device according to the invention, are the compounds H1 until H54 Table 3. Table 3: H1 H2 H3 H4 H5 H6 H7 H8 H9 H10 H11 H12 H13 H14 H15 H16 H17 H18 H19 H20 H21 H22 H23 H24 H25 H26 H27 H28 H29 H30 H31 H32 H33 H34 H35 H36 H37 H38 H39 H40 H41 H42 H43 H44 H45 H46 H47 H48 H49 H50 H51 H52 H53 H54

[0118] The aforementioned host materials of formula (1) and their preferably described embodiments or the compounds of Table 1 and the compounds E1 until E27 The device according to the invention can be combined arbitrarily with the aforementioned matrix materials / host materials of formulas (6), (7), (8), (9), (10) or (11) as well as their preferably described embodiments or the combinations H1 until H54 can be combined.

[0119] Particularly preferred mixtures of the compounds of formula (1) with the host materials of formulas (6), (7), (8), (9), (10) or (11) for the device according to the invention are obtained by combining the compounds E1 until E27with the connections H1 until H54 as shown in Table 4 below. Table 4: M1 E1 H1 M2 E2 H1 M3 E3 H1 M4 E4 H1 M5 E5 H1 M6 E6 H1 M7 E7 H1 M8 E8 H1 M9 E9 H1 M10 E10 H1 M11 E11 H1 M12 E12 H1 M13 E13 H1 M14 E14 H1 M15 E15 H1 M16 E16 H1 M17 E17 H1 M18 E18 H1 M19 E19 H1 M20 E20 H1 M21 E21 H1 M22 E22 H1 M23 E23 H1 M24 E24 H1 M25 E25 H1 M26 E26 H1 M27 E27 H1 M28 E1 H2 M29 E2 H2 M30 E3 H2 M31 E4 H2 M32 E5 H2 M33 E6 H2 M34 E7 H2 M35 E8 H2 M36 E9 H2 M37 E10 H2 M38 E11 H2 M39 E12 H2 M40 E13 H2 M41 E14 H2 M42 E15 H2 M43 E16 H2 M44 E17 H2 M45 E18 H2 M46 E19 H2 M47 E20 H2 M48 E21 H2 M49 E22 H2 M50 E23 H2 M51 E24 H2 M52 E25 H2 M53 E26 H2 M54 E27 H2 M55 E1 H3 M56 E2 H3 M57 E3 H3 M58 E4 H3 M59 E5 H3 M60 E6 H3 M61 E7 H3 M62 E8 H3 M63 E9 H3 M64 E10 H3 M65 E11 H3 M66 E12 H3 M67 E13 H3 M68 E14 H3 M69 E15 H3 M70 E16 H3 M71 E17 H3 M72 E18 H3 M73 E19 H3 M74 E20 H3 M75 E21 H3 M76 E22 H3 M77 E23 H3 M78 E24 H3 M79 E25 H3 M80 E26 H3 M81 E27 H3 M82 E1 H4 M83 E2 H4 M84 E3 H4 M85 E4 H4 M86 E5 H4 M87 E6 H4 M88 E7 H4 M89 E8 H4 M90 E9 H4 M91 E10 H4 M92 E11 H4 M93 E12 H4 M94 E13 H4 M95 E14 H4 M96 E15 H4 M97 E16 H4 M98 E17 H4 M99 E18 H4 M100 E19 H4 M101 E20 H4 M102 E21 H4 M103 E22 H4 M104 E23 H4 M105 E24 H4 M106 E25 H4 M107 E26 H4 M108 E27 H4 M109 E1 H5 M110 E2 H5 M111 E3 H5 M112 E4 H5 M113 E5 H5 M114 E6 H5 M115 E7 H5 M116 E8 H5 M117 E9 H5 M118 E10 H5 M119 E11 H5 M120 E12 H5 M121 E13 H5 M122 E14 H5 M123 E15 H5 M124 E16 H5 M125 E17 H5 M126 E18 H5 M127 E19 H5 M128 E20 H5 M129 E21 H5 M130 E22 H5 M131 E23 H5 M132 E24 H5 M133 E25 H5 M134 E26 H5 M135 E27 H5 M136 E1 H6 M137 E2 H6 M138 E3 H6 M139 E4 H6 M140 E5 H6 M141 E6 H6 M142 E7 H6 M143 E8 H6 M144 E9 H6 M145 E10 H6 M146 E11 H6 M147 E12 H6 M148 E13 H6 M149 E14 H6 M150 E15 H6 M151 E16 H6 M152 E17 H6 M153 E18 H6 M154 E19 H6 M155 E20 H6 M156 E21 H6 M157 E22 H6 M158 E23 H6 M159 E24 H6 M160 E25 H6 M161 E26 H6 M162 E27 H6 M163 E1 H7 M164 E2 H7 M165 E3 H7 M166 E4 H7 M167 E5 H7 M168 E6 H7 M169 E7 H7 M170 E8 H7 M171 E9 H7 M172 E10 H7 M173 E11 H7 M174 E12 H7 M175 E13 H7 M176 E14 H7 M177 E15 H7 M178 E16 H7 M179 E17 H7 M180 E18 H7 M181 E19 H7 M182 E20 H7 M183 E21 H7 M184 E22 H7 M185 E23 H7 M186 E24 H7 M187 E25 H7 M188 E26 H7 M189 E27 H7 M190 E1 H8 M191 E2 H4 M192 E3 H4 M193 E4 H8 M194 E5 H8 M195 E6 H8 M196 E7 H8 M197 E8 H8 M198 E9 H8 M199 E10 H8 M200 E11 H8 M201 E12 H8 M202 E13 H8 M203 E14 H8 M204 E15 H8 M205 E16 H8 M206 E17 H8 M207 E18 H8 M208 E19 H8 M209 E20 H8 M210 E21 H8 M211 E22 H8 M212 E23 H8 M213 E24 H8 M214 E25 H8 M215 E26 H8 M216 E27 H8 M217 E1 H9 M218 E2 H9 M219 E3 H9 M220 E4 H9 M221 E5 H9 M222 E6 H9 M223 E7 H9 M224 E8 H9 M225 E9 H9 M226 E10 H9 M227 E11 H9 M228 E12 H9 M229 E13 H9 M230 E14 H9 M231 E15 H9 M232 E16 H9 M233 E17 H9 M234 E18 H9 M235 E19 H9 M236 E20 H9 M237 E21 H9 M238 E22 H9 M239 E23 H9 M240 E24 H9 M241 E25 H9 M242 E26 H9 M243 E27 H9 M244 E1 H10 M245 E2 H10 M246 E3 H10 M247 E4 H10 M248 E5 H10 M249 E6 H10 M250 E7 H10 M251 E8 H10 M252 E9 H10 M253 E10 H10 M254 E11 H10 M255 E12 H10 M256 E13 H10 M257 E14 H10 M258 E15 H10 M259 E16 H10 M260 E17 H10 M261 E18 H10 M262 E19 H10 M263 E20 H10 M264 E21 H10 M265 E22 H10 M266 E23 H10 M267 E24 H10 M268 E25 H10 M269 E26 H10 M270 E27 H10 M271 E1 H11 M272 E2 H11 M273 E3 H11 M274 E4 H11 M275 E5 H11 M276 E6 H11 M277 E7 H11 M278 E8 H11 M279 E9 H11 M280 E10 H11 M281 E11 H11 M282 E12 H11 M283 E13 H11 M284 E14 H11 M285 E15 H11 M286 E16 H11 M287 E17 H11 M288 E18 H11 M289 E19 H11 M290 E20 H11 M291 E21 H11 M292 E22 H11 M293 E23 H11 M294 E24 H11 M295 E25 H11 M296 E26 H11 M297 E27 H11 M298 E1 H12 M299 E2 H12 M300 E3 H12 M301 E4 H12 M302 E5 H12 M303 E6 H12 M304 E7 H12 M305 E8 H12 M306 E9 H12 M307 E10 H12 M308 E11 H12 M309 E12 H12 M310 E13 H12 M311 E14 H12 M312 E15 H12 M313 E16 H12 M314 E17 H12 M315 E18 H12 M316 E19 H12 M317 E20 H12 M318 E21 H12 M319 E22 H12 M320 E23 H12 M321 E24 H12 M322 E25 H12 M323 E26 H12 M324 E27 H12 M325 E1 H13 M326 E2 H13 M327 E3 H13 M328 E4 H13 M329 E5 H13 M330 E6 H13 M331 E7 H13 M332 E8 H13 M333 E9 H13 M334 E10 H13 M335 E11 H13 M336 E12 H13 M337 E13 H13 M338 E14 H13 M339 E15 H13 M340 E16 H13 M341 E17 H13 M342 E18 H13 M343 E19 H13 M344 E20 H13 M345 E21 H13 M346 E22 H13 M347 E23 H13 M348 E24 H13 M349 E25 H13 M350 E26 H13 M351 E27 H13 M352 E1 H14 M353 E2 H14 M354 E3 H14 M355 E4 H14 M356 E5 H14 M357 E6 H14 M358 E7 H14 M359 E8 H14 M360 E9 H14 M361 E10 H14 M362 E11 H14 M363 E12 H14 M364 E13 H14 M365 E14 H14 M366 E15 H14 M367 E16 H14 M368 E17 H14 M369 E18 H14 M370 E19 H14 M371 E20 H14 M372 E21 H14 M373 E22 H14 M374 E23 H14 M375 E24 H14 M376 E25 H14 M377 E26 H14 M378 E27 H14 M379 E1 H15 M380 E2 H15 M381 E3 H15 M382 E4 H15 M383 E5 H15 M384 E6 H15 M385 E7 H15 M386 E8 H15 M387 E9 H15 M388 E10 H15 M389 E11 H15 M390 E12 H15 M391 E13 H15 M392 E14 H15 M393 E15 H15 M394 E16 H15 M395 E17 H15 M396 E18 H15 M397 E19 H15 M398 E20 H15 M399 E21 H15 M400 E22 H15 M401 E23 H15 M402 E24 H15 M403 E25 H15 M404 E26 H15 M405 E27 H15 M406 E1 H16 M407 E2 H16 M408 E3 H16 M409 E4 H16 M410 E5 H16 M411 E6 H16 M412 E7 H16 M413 E8 H16 M414 E9 H16 M415 E10 H16 M416 E11 H16 M417 E12 H16 M418 E13 H16 M419 E14 H16 M420 E15 H16 M421 E16 H16 M422 E17 H16 M423 E18 H16 M424 E19 H16 M425 E20 H16 M426 E21 H16 M427 E22 H16 M428 E23 H16 M429 E24 H16 M430 E25 H16 M431 E26 H16 M432 E27 H16 M433 E1 H17 M434 E2 H17 M435 E3 H17 M436 E4 H17 M437 E5 H17 M438 E6 H17 M439 E7 H17 M440 E8 H17 M441 E9 H17 M442 E10 H17 M443 E11 H17 M444 E12 H17 M445 E13 H17 M446 E14 H17 M447 E15 H17 M448 E16 H17 M449 E17 H17 M450 E18 H17 M451 E19 H17 M452 E20 H17 M453 E21 H17 M454 E22 H17 M455 E23 H17 M456 E24 H17 M457 E25 H17 M458 E26 H17 M459 E27 H17 M460 E1 H18 M461 E2 H18 M462 E3 H18 M463 E4 H18 M464 E5 H18 M465 E6 H18 M466 E7 H18 M467 E8 H18 M468 E9 H18 M469 E10 H18 M470 E11 H18 M471 E12 H18 M472 E13 H18 M473 E14 H18 M474 E15 H18 M475 E16 H18 M476 E17 H18 M477 E18 H18 M478 E19 H18 M479 E20 H18 M480 E21 H18 M481 E22 H18 M482 E23 H18 M483 E24 H18 M484 E25 H18 M485 E26 H18 M486 E27 H18 M487 E1 H19 M488 E2 H19 M489 E3 H19 M490 E4 H19 M491 E5 H19 M492 E6 H19 M493 E7 H19 M494 E8 H19 M495 E9 H19 M496 E10 H19 M497 E11 H19 M498 E12 H19 M499 E13 H19 M500 E14 H19 M501 E15 H19 M502 E16 H19 M503 E17 H19 M504 E18 H19 M505 E19 H19 M506 E20 H19 M507 E21 H19 M508 E22 H19 M509 E23 H19 M510 E24 H19 M511 E25 H19 M512 E26 H19 M513 E27 H19 M514 E1 H20 M515 E2 H20 M516 E3 H20 M517 E4 H20 M518 E5 H20 M519 E6 H20 M520 E7 H20 M521 E8 H20 M522 E9 H20 M523 E10 H20 M524 E11 H20 M525 E12 H20 M526 E13 H20 M527 E14 H20 M528 E15 H20 M529 E16 H20 M530 E17 H20 M531 E18 H20 M532 E19 H20 M533 E20 H20 M534 E21 H20 M535 E22 H20 M536 E23 H20 M537 E24 H20 M538 E25 H20 M539 E26 H20 M540 E27 H20 M541 E1 H21 M542 E2 H21 M543 E3 H21 M544 E4 H21 M545 E5 H21 M546 E6 H21 M547 E7 H21 M548 E8 H21 M549 E9 H21 M550 E10 H21 M551 E11 H21 M552 E12 H21 M553 E13 H21 M554 E14 H21 M555 E15 H21 M556 E16 H21 M557 E17 H21 M558 E18 H21 M559 E19 H21 M560 E20 H21 M561 E21 H21 M562 E22 H21 M563 E23 H21 M564 E24 H21 M565 E25 H21 M566 E26 H21 M567 E27 H21 M568 E1 H22 M569 E2 H22 M570 E3 H22 M571 E4 H22 M572 E5 H22 M573 E6 H22 M574 E7 H22 M575 E8 H22 M576 E9 H22 M577 E10 H22 M578 E11 H22 M579 E12 H22 M580 E13 H22 M581 E14 H22 M582 E15 H22 M583 E16 H22 M584 E17 H22 M585 E18 H22 M586 E19 H22 M587 E20 H22 M588 E21 H22 M589 E22 H22 M590 E23 H22 M591 E24 H22 M592 E25 H22 M593 E26 H22 M594 E27 H22 M595 E1 H23 M596 E2 H23 M597 E3 H23 M598 E4 H23 M599 E5 H23 M600 E6 H23 M601 E7 H23 M602 E8 H23 M603 E9 H23 M604 E10 H23 M605 E11 H23 M606 E12 H23 M607 E13 H23 M608 E14 H23 M609 E15 H23 M610 E16 H23 M611 E17 H23 M612 E18 H23 M613 E19 H23 M614 E20 H23 M615 E21 H23 M616 E22 H23 M617 E23 H23 M618 E24 H23 M619 E25 H23 M620 E26 H23 M621 E27 H23 M622 E1 H24 M623 E2 H24 M624 E3 H24 M625 E4 H24 M626 E5 H24 M627 E6 H24 M628 E7 H24 M629 E8 H24 M630 E9 H24 M631 E10 H24 M632 E11 H24 M633 E12 H24 M634 E13 H24 M635 E14 H24 M636 E15 H24 M637 E16 H24 M638 E17 H24 M639 E18 H24 M640 E19 H24 M641 E20 H24 M642 E21 H24 M643 E22 H24 M644 E23 H24 M645 E24 H24 M646 E25 H24 M647 E26 H24 M648 E27 H24 M649 E1 H25 M650 E2 H25 M651 E3 H25 M652 E4 H25 M653 E5 H25 M654 E6 H25 M655 E7 H25 M656 E8 H25 M657 E9 H25 M658 E10 H25 M659 E11 H25 M660 E12 H25 M661 E13 H25 M662 E14 H25 M663 E15 H25 M664 E16 H25 M665 E17 H25 M666 E18 H25 M667 E19 H25 M668 E20 H25 M669 E21 H25 M670 E22 H25 M671 E23 H25 M672 E24 H25 M673 E25 H25 M674 E26 H25 M675 E27 H25 M676 E1 H26 M677 E2 H26 M678 E3 H26 M679 E4 H26 M680 E5 H26 M681 E6 H26 M682 E7 H26 M683 E8 H26 M684 E9 H26 M685 E10 H26 M686 E11 H26 M687 E12 H26 M688 E13 H26 M689 E14 H26 M690 E15 H26 M691 E16 H26 M692 E17 H26 M693 E18 H26 M694 E19 H26 M695 E20 H26 M696 E21 H26 M697 E22 H26 M698 E23 H26 M699 E24 H26 M700 E25 H26 M701 E26 H26 M702 E27 H26 M703 E1 H27 M704 E2 H27 M705 E3 H27 M706 E4 H27 M707 E5 H27 M708 E6 H27 M709 E7 H27 M710 E8 H27 M711 E9 H27 M712 E10 H27 M713 E11 H27 M714 E12 H27 M715 E13 H27 M716 E14 H27 M717 E15 H27 M718 E16 H27 M719 E17 H27 M720 E18 H27 M721 E19 H27 M722 E20 H27 M723 E21 H27 M724 E22 H27 M725 E23 H27 M726 E24 H27 M727 E25 H27 M728 E26 H27 M729 E27 H27 M730 E1 H28 M731 E2 H28 M732 E3 H28 M733 E4 H28 M734 E5 H28 M735 E6 H28 M736 E7 H28 M737 E8 H28 M738 E9 H28 M739 E10 H28 M740 E11 H28 M741 E12 H28 M742 E13 H28 M743 E14 H28 M744 E15 H28 M745 E16 H28 M746 E17 H28 M747 E18 H28 M748 E19 H28 M749 E20 H28 M750 E21 H28 M751 E22 H28 M752 E23 H28 M753 E24 H28 M754 E25 H28 M755 E26 H28 M756 E27 H28 M757 E1 H29 M758 E2 H29 M759 E3 H29 M760 E4 H29 M761 E5 H29 M762 E6 H29 M763 E7 H29 M764 E8 H29 M765 E9 H29 M766 E10 H29 M767 E11 H29 M768 E12 H29 M769 E13 H29 M770 E14 H29 M771 E15 H29 M772 E16 H29 M773 E17 H29 M774 E18 H29 M775 E19 H29 M776 E20 H29 M777 E21 H29 M778 E22 H29 M779 E23 H29 M780 E24 H29 M781 E25 H29 M782 E26 H29 M783 E27 H29 M784 E1 H30 M785 E2 H30 M786 E3 H30 M787 E4 H30 M788 E5 H30 M789 E6 H30 M790 E7 H30 M791 E8 H30 M792 E9 H30 M793 E10 H30 M794 E11 H30 M795 E12 H30 M796 E13 H30 M797 E14 H30 M798 E15 H30 M799 E16 H30 M800 E17 H30 M801 E18 H30 M802 E19 H30 M803 E20 H30 M804 E21 H30 M805 E22 H30 M806 E23 H30 M807 E24 H30 M808 E25 H30 M809 E26 H30 M810 E27 H30 M811 E1 H31 M812 E2 H31 M813 E3 H31 M814 E4 H31 M815 E5 H31 M816 E6 H31 M817 E7 H31 M818 E8 H31 M819 E9 H31 M820 E10 H31 M821 E11 H31 M822 E12 H31 M823 E13 H31 M824 E14 H31 M825 E15 H31 M826 E16 H31 M827 E17 H31 M828 E18 H31 M829 E19 H31 M830 E20 H31 M831 E21 H31 M832 E22 H31 M833 E23 H31 M834 E24 H31 M835 E25 H31 M836 E26 H31 M837 E27 H31 M838 E1 H32 M839 E2 H32 M840 E3 H32 M841 E4 H32 M842 E5 H32 M843 E6 H32 M844 E7 H32 M845 E8 H32 M846 E9 H32 M847 E10 H32 M848 E11 H32 M849 E12 H32 M850 E13 H32 M851 E14 H32 M852 E15 H32 M853 E16 H32 M854 E17 H32 M855 E18 H32 M856 E19 H32 M857 E20 H32 M858 E21 H32 M859 E22 H32 M860 E23 H32 M861 E24 H32 M862 E25 H32 M863 E26 H32 M864 E27 H32 M865 E1 H33 M866 E2 H33 M867 E3 H33 M868 E4 H33 M869 E5 H33 M870 E6 H33 M871 E7 H33 M872 E8 H33 M873 E9 H33 M874 E10 H33 M875 E11 H33 M876 E12 H33 M877 E13 H33 M878 E14 H33 M879 E15 H33 M880 E16 H33 M881 E17 H33 M882 E18 H33 M883 E19 H33 M884 E20 H33 M885 E21 H33 M886 E22 H33 M887 E23 H33 M888 E24 H33 M889 E25 H33 M890 E26 H33 M891 E27 H33 M892 E1 H34 M893 E2 H34 M894 E3 H34 M895 E4 H34 M896 E5 H34 M897 E6 H34 M898 E7 H34 M899 E8 H34 M900 E9 H34 M901 E10 H34 M902 E11 H34 M903 E12 H34 M904 E13 H34 M905 E14 H34 M906 E15 H34 M907 E16 H34 M908 E17 H34 M909 E18 H34 M910 E19 H34 M911 E20 H34 M912 E21 H34 M913 E22 H34 M914 E23 H34 M915 E24 H34 M916 E25 H34 M917 E26 H34 M918 E27 H34 M919 E1 H35 M920 E2 H35 M921 E3 H35 M922 E4 H35 M923 E5 H35 M924 E6 H35 M925 E7 H35 M926 E8 H35 M927 E9 H35 M928 E10 H35 M929 E11 H35 M930 E12 H35 M931 E13 H35 M932 E14 H35 M933 E15 H35 M934 E16 H35 M935 E17 H35 M936 E18 H35 M937 E19 H35 M938 E20 H35 M939 E21 H35 M940 E22 H35 M941 E23 H35 M942 E24 H35 M943 E25 H35 M944 E26 H35 M945 E27 H35 M946 E1 H36 M947 E2 H36 M948 E3 H36 M949 E4 H36 M950 E5 H36 M951 E6 H36 M952 E7 H36 M953 E8 H36 M954 E9 H36 M955 E10 H36 M956 E11 H36 M957 E12 H36 M958 E13 H36 M959 E14 H36 M960 E15 H36 M961 E16 H36 M962 E17 H36 M963 E18 H36 M964 E19 H36 M965 E20 H36 M966 E21 H36 M967 E22 H36 M968 E23 H36 M969 E24 H36 M970 E25 H36 M971 E26 H36 M972 E27 H36 M973 E1 H37 M974 E2 H37 M975 E3 H37 M976 E4 H37 M977 E5 H37 M978 E6 H37 M979 E7 H37 M980 E8 H37 M981 E9 H37 M982 E10 H37 M983 E11 H37 M984 E12 H37 M985 E13 H37 M986 E14 H37 M987 E15 H37 M988 E16 H37 M989 E17 H37 M990 E18 H37 M991 E19 H37 M992 E20 H37 M993 E21 H37 M994 E22 H37 M995 E23 H37 M996 E24 H37 M997 E25 H37 M998 E26 H37 M999 E27 H37 M1000 E1 H38 M1001 E2 H38 M1002 E3 H38 M1003 E4 H38 M1004 E5 H38 M1005 E6 H38 M1006 E7 H38 M1007 E8 H38 M1008 E9 H38 M1009 E10 H38 M1010 E11 H38 M1011 E12 H38 M1012 E13 H38 M1013 E14 H38 M1014 E15 H38 M1015 E16 H38 M1016 E17 H38 M1017 E18 H38 M1018 E19 H38 M1019 E20 H38 M1020 E21 H38 M1021 E22 H38 M1022 E23 H38 M1023 E24 H38 M1024 E25 H38 M1025 E26 H38 M1026 E27 H38 M1027 E1 H39 M1028 E2 H39 M1029 E3 H39 M1030 E4 H39 M1031 E5 H39 M1032 E6 H39 M1033 E7 H39 M1034 E8 H39 M1035 E9 H39 M1036 E10 H39 M1037 E11 H39 M1038 E12 H39 M1039 E13 H39 M1040 E14 H39 M1041 E15 H39 M1042 E16 H39 M1043 E17 H39 M1044 E18 H39 M1045 E19 H39 M1046 E20 H39 M1047 E21 H39 M1048 E22 H39 M1049 E23 H39 M1050 E24 H39 M1051 E25 H39 M1052 E26 H39 M1053 E27 H39 M1054 E1 H40 M1055 E2 H40 M1056 E3 H40 M1057 E4 H40 M1058 E5 H40 M1059 E6 H40 M1060 E7 H40 M1061 E8 H40 M1062 E9 H40 M1063 E10 H40 M1064 E11 H40 M1065 E12 H40 M1066 E13 H40 M1067 E14 H40 M1068 E15 H40 M1069 E16 H40 M1070 E17 H40 M1071 E18 H40 M1072 E19 H40 M1073 E20 H40 M1074 E21 H40 M1075 E22 H40 M1076 E23 H40 M1077 E24 H40 M1078 E25 H40 M1079 E26 H40 M1080 E27 H40 M1081 E1 H41 M1082 E2 H41 M1083 E3 H41 M1084 E4 H41 M1085 E5 H41 M1086 E6 H41 M1087 E7 H41 M1088 E8 H41 M1089 E9 H41 M1090 E10 H41 M1091 E11 H41 M1092 E12 H41 M1093 E13 H41 M1094 E14 H41 M1095 E15 H41 M1096 E16 H41 M1097 E17 H41 M1098 E18 H41 M1099 E19 H41 M1100 E20 H41 M1101 E21 H41 M1102 E22 H41 M1103 E23 H41 M1104 E24 H41 M1105 E25 H41 M1106 E26 H41 M1107 E27 H41 M1108 E1 H42 M1109 E2 H42 M1110 E3 H42 M1111 E4 H42 M1112 E5 H42 M1113 E6 H42 M1114 E7 H42 M1115 E8 H42 M1116 E9 H42 M1117 E10 H42 M1118 E11 H42 M1119 E12 H42 M1120 E13 H42 M1121 E14 H42 M1122 E15 H42 M1123 E16 H42 M1124 E17 H42 M1125 E18 H42 M1126 E19 H42 M1127 E20 H42 M1128 E21 H42 M1129 E22 H42 M1130 E23 H42 M1131 E24 H42 M1132 E25 H42 M1133 E26 H42 M1134 E27 H42 M1135 E1 H43 M1136 E2 H43 M1137 E3 H43 M1138 E4 H43 M1139 E5 H43 M1140 E6 H43 M1141 E7 H43 M1142 E8 H43 M1143 E9 H43 M1144 E10 H43 M1145 E11 H43 M1146 E12 H43 M1147 E13 H43 M1148 E14 H43 M1149 E15 H43 M1150 E16 H43 M1151 E17 H43 M1152 E18 H43 M1153 E19 H43 M1154 E20 H43 M1155 E21 H43 M1156 E22 H43 M1157 E23 H43 M1158 E24 H43 M1159 E25 H43 M1160 E26 H43 M1161 E27 H43 M1162 E1 H44 M1163 E2 H44 M1164 E3 H44 M1165 E4 H44 M1166 E5 H44 M1167 E6 H44 M1168 E7 H44 M1169 E8 H44 M1170 E9 H44 M1171 E10 H44 M1172 E11 H44 M1173 E12 H44 M1174 E13 H44 M1175 E14 H44 M1176 E15 H44 M1177 E16 H44 M1178 E17 H44 M1179 E18 H44 M1180 E19 H44 M1181 E20 H44 M1182 E21 H44 M1183 E22 H44 M1184 E23 H44 M1185 E24 H44 M1186 E25 H44 M1187 E26 H44 M1188 E27 H44 M1189 E1 H45 M1190 E2 H45 M1191 E3 H45 M1192 E4 H45 M1193 E5 H45 M1194 E6 H45 M1195 E7 H45 M1196 E8 H45 M1197 E9 H45 M1198 E10 H45 M1199 E11 H45 M1200 E12 H45 M1201 E13 H45 M1202 E14 H45 M1203 E15 H45 M1204 E16 H45 M1205 E17 H45 M1206 E18 H45 M1207 E19 H45 M1208 E20 H45 M1209 E21 H45 M1210 E22 H45 M1211 E23 H45 M1212 E24 H45 M1213 E25 H45 M1214 E26 H45 M1215 E27 H45 M1216 E1 H46 M1217 E2 H46 M1218 E3 H46 M1219 E4 H46 M1220 E5 H46 M1221 E6 H46 M1222 E7 H46 M1223 E8 H46 M1224 E9 H46 M1225 E10 H46 M1226 E11 H46 M1227 E12 H46 M1228 E13 H46 M1229 E14 H46 M1230 E15 H46 M1231 E16 H46 M1232 E17 H46 M1233 E18 H46 M1234 E19 H46 M1235 E20 H46 M1236 E21 H46 M1237 E22 H46 M1238 E23 H46 M1239 E24 H46 M1240 E25 H46 M1241 E26 H46 M1242 E27 H46 M1243 E1 H47 M1244 E2 H47 M1245 E3 H47 M1246 E4 H47 M1247 E5 H47 M1248 E6 H47 M1249 E7 H47 M1250 E8 H47 M1251 E9 H47 M1252 E10 H47 M1253 E11 H47 M1254 E12 H47 M1255 E13 H47 M1256 E14 H47 M1257 E15 H47 M1258 E16 H47 M1259 E17 H47 M1260 E18 H47 M1261 E19 H47 M1262 E20 H47 M1263 E21 H47 M1264 E22 H47 M1265 E23 H47 M1266 E24 H47 M1267 E25 H47 M1268 E26 H47 M1269 E27 H47 M1270 E1 H48 M1271 E2 H48 M1272 E3 H48 M1273 E4 H48 M1274 E5 H48 M1275 E6 H48 M1276 E7 H48 M1277 E8 H48 M1278 E9 H48 M1279 E10 H48 M1280 E11 H48 M1281 E12 H48 M1282 E13 H48 M1283 E14 H48 M1284 E15 H48 M1285 E16 H48 M1286 E17 H48 M1287 E18 H48 M1288 E19 H48 M1289 E20 H48 M1290 E21 H48 M1291 E22 H48 M1292 E23 H48 M1293 E24 H48 M1294 E25 H48 M1295 E26 H48 M1296 E27 H48 M1297 E1 H49 M1298 E2 H49 M1299 E3 H49 M1300 E4 H49 M1301 E5 H49 M1302 E6 H49 M1303 E7 H49 M1304 E8 H49 M1305 E9 H49 M1306 E10 H49 M1307 E11 H49 M1308 E12 H49 M1309 E13 H49 M1310 E14 H49 M1311 E15 H49 M1312 E16 H49 M1313 E17 H49 M1314 E18 H49 M1315 E19 H49 M1316 E20 H49 M1317 E21 H49 M1318 E22 H49 M1319 E23 H49 M1320 E24 H49 M1321 E25 H49 M1322 E26 H49 M1323 E27 H49 M1324 E1 H50 M1325 E2 H50 M1326 E3 H50 M1327 E4 H50 M1328 E5 H50 M1329 E6 H50 M1330 E7 H50 M1331 E8 H50 M1332 E9 H50 M1333 E10 H50 M1334 E11 H50 M1335 E12 H50 M1336 E13 H50 M1337 E14 H50 M1338 E15 H50 M1339 E16 H50 M1340 E17 H50 M1341 E18 H50 M1342 E19 H50 M1343 E20 H50 M1344 E21 H50 M1345 E22 H50 M1346 E23 H50 M1347 E24 H50 M1348 E25 H50 M1349 E26 H50 M1350 E27 H50 M1351 E1 H51 M1352 E2 H51 M1353 E3 H51 M1354 E4 H51 M1355 E5 H51 M1356 E6 H51 M1357 E7 H51 M1358 E8 H51 M1359 E9 H51 M1360 E10 H51 M1361 E11 H51 M1362 E12 H51 M1363 E13 H51 M1364 E14 H51 M1365 E15 H51 M1366 E16 H51 M1367 E17 H51 M1368 E18 H51 M1369 E19 H51 M1370 E20 H51 M1371 E21 H51 M1372 E22 H51 M1373 E23 H51 M1374 E24 H51 M1375 E25 H51 M1376 E26 H51 M1377 E27 H51 M1378 E1 H52 M1379 E2 H52 M1380 E3 H52 M1381 E4 H52 M1382 E5 H52 M1383 E6 H52 M1384 E7 H52 M1385 E8 H52 M1386 E9 H52 M1387 E10 H52 M1388 E11 H52 M1389 E12 H52 M1390 E13 H52 M1391 E14 H52 M1392 E15 H52 M1393 E16 H52 M1394 E17 H52 M1395 E18 H52 M1396 E19 H52 M1397 E20 H52 M1398 E21 H52 M1399 E22 H52 M1400 E23 H52 M1401 E24 H52 M1402 E25 H52 M1403 E26 H52 M1404 E27 H52 M1405 E1 H53 M1406 E2 H53 M1407 E3 H53 M1408 E4 H53 M1409 E5 H53 M1410 E6 H53 M1411 E7 H53 M1412 E8 H53 M1413 E9 H53 M1414 E10 H53 M1415 E11 H53 M1416 E12 H53 M1417 E13 H53 M1418 E14 H53 M1419 E15 H53 M1420 E16 H53 M1421 E17 H53 M1422 E18 H53 M1423 E19 H53 M1424 E20 H53 M1425 E21 H53 M1426 E22 H53 M1427 E23 H53 M1428 E24 H53 M1429 E25 H53 M1430 E26 H53 M1431 E27 H53 M1432 E1 H54 M1433 E2 H54 M1434 E3 H54 M1435 E4 H54 M1436 E5 H54 M1437 E6 H54 M1438 E7 H54 M1439 E8 H54 M1440 E9 H54 M1441 E10 H54 M1442 E11 H54 M1443 E12 H54 M1444 E13 H54 M1445 E14 H54 M 1446 E15 H54 M1447 E16 H54 M1448 E17 H54 M1449 E18 H54 M1450 E19 H54 M1451 E20 H54 M1452 E21 H54 M1453 E22 H54 M1454 E23 H54 M1455 E24 H54 M 1456 E25 H54 M1457 E26 H54 M1458 E27 H54

[0120] The concentration of the host material of formula (1), as previously described or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is in the range of 5 wt.% to 90 wt.%, preferably in the range of 10 wt.% to 85 wt.%, more preferably in the range of 20 wt.% to 85 wt.%, even more preferably in the range of 30 wt.% to 80 wt.%, most preferably in the range of 20 wt.% to 60 wt.% and most preferably in the range of 30 wt.% to 50 wt.%, based on the entire mixture or based on the entire composition of the light-emitting layer.

[0121] The concentration of the host material of one of the formulas (6), (7), (8), (9), (10) or (11), as previously described or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is in the range of 10 wt.% to 95 wt.%, preferably in the range of 15 wt.% to 90 wt.%, more preferably in the range of 15 wt.% to 80 wt.%, even more preferably in the range of 20 wt.% to 70 wt.%, most preferably in the range of 40 wt.% to 80 wt.% and most preferably in the range of 50 wt.% to 70 wt.%, based on the entire mixture or based on the entire composition of the light-emitting layer.

[0122] The present invention also relates to a mixture which, in addition to the host materials of formula (1) mentioned above, hereinafter referred to as host material 1, and the host material of one of formulas (6), (7), (8), (9), (10) or (11), hereinafter referred to as host material 2, as previously described or preferably described, in particular mixtures M1 to M1458, contains at least one phosphorescent emitter.

[0123] The present invention also relates to an organic electroluminescent device as previously described or preferably described, wherein the light-emitting layer, in addition to the aforementioned host materials of formula (1) and one of formulas (6), (7), (8), (9), (10) or (11), as previously described or preferably described, in particular the material combinations M1 to M1458, contains at least one phosphorescent emitter.

[0124] The term phosphorescent emitters typically encompasses compounds in which light emission occurs through a spin-forbidden transition from an excited state with a higher spin multiplicity, i.e., a spin state > 1, for example, through a transition from a triplet state or a state with an even higher spin quantum number, such as a quintet state. A transition from a triplet state is preferred.

[0125] Suitable phosphorescent emitters (= triplet emitters) are compounds that, upon suitable excitation, emit light, 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, and particularly preferably greater than 56 and less than 80, especially a metal with this atomic number. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are preferred as phosphorescent emitters, especially compounds containing iridium or platinum. For the purposes of the present invention, all luminescent compounds containing the aforementioned metals are considered phosphorescent emitters.

[0126] In general, all phosphorescent complexes are suitable, such as those used in phosphorescent OLEDs according to the prior art and as are known to those skilled in the art in the field of organic electroluminescence devices.

[0127] Preferred phosphorescent emitters according to the present invention correspond to formula (IIIa), where the symbols and indices for this formula (Illa) have the following meanings: n+m is 3, n is 1 or 2, m is 2 or 1, X is N or CR, R is H, D or a branched or linear alkyl group with 1 to 10 C atoms or a partially or completely deuterated branched or linear alkyl group with 1 to 10 C atoms or a cycloalkyl group with 4 to 7 C atoms, which may be partially or completely substituted with deuterium.

[0128] Another object of the invention is therefore an organic electroluminescent device, as previously described or preferably described, characterized in that the light-emitting layer contains, in addition to the host materials 1 and 2, at least one phosphorescent emitter corresponding to formula (IIIa), as previously described.

[0129] In emitters of formula (Illa) n is preferably 1 and m is preferably 2.

[0130] In emitters of formula (IIIa) one X is preferably selected from N and the other Xs represent CR.

[0131] In emitters of formula (IIIa), at least one R is preferably different from H. In emitters of formula (IIIa), two R are preferably different from H and have one of the meanings previously given for the emitters of formula (IIIa).

[0132] Preferred phosphorescent emitters according to the present invention correspond to formulas (I), (II), (III), (IV) or (V), where the symbols and indices for these formulas (I), (II), (III), (IV) and (V) have the following meanings: R 1 is H or D, R 2 is H, D or a branched or linear alkyl group with 1 to 10 C atoms or a partially or completely deuterated branched or linear alkyl group with 1 to 10 C atoms or a cycloalkyl group with 4 to 10 C atoms which may be partially or completely substituted with deuterium.

[0133] Preferred phosphorescent emitters according to the present invention correspond to formulas (VI), (VII) or (VIII), where the symbols and indices for these formulas (VI), (VII) and (VIII) have the following meanings: R 1 is H or D, R 2 is H, D, F or a branched or linear alkyl group with 1 to 10 C atoms or a partially or completely deuterated branched or linear alkyl group with 1 to 10 C atoms or a cycloalkyl group with 4 to 10 C atoms which may be partially or completely substituted with deuterium.

[0134] Preferred examples of phosphorescent emitters are described in WO2019007867 on pages 120 to 126 in Table 5 and on pages 127 to 129 in Table 6. These emitters are included in the description by reference.

[0135] Particularly favored examples of phosphorescent emitters are listed in Table 5 below.

[0136] In the mixtures according to the invention or in the light-emitting layer of the device according to the invention, each mixture is preferably selected from the sum of the mixtures M1 to M1458 and combined with a compound of formula (IIIa) or a compound of formulas (I) to (VIII) or a compound from Table 5.

[0137] The light-emitting layer in the organic electroluminescent device according to the invention, comprising at least one phosphorescent emitter, is preferably an infrared-emitting, yellow, orange, red, green, blue or ultraviolet-emitting layer, particularly preferably a yellow or green-emitting layer, and most preferably a green-emitting layer.

[0138] A yellow-emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 540 to 570 nm. An orange-emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 570 to 600 nm. A red-emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 600 to 750 nm.

[0139] A green-emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 490 to 540 nm. A blue-emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 440 to 490 nm. The photoluminescence maximum of the layer is determined by measuring the photoluminescence spectrum of the layer with a thickness of 50 nm at room temperature, wherein the layer contains the inventive combination of the host materials of formula (1) and one of formulas (6), (7), (8), (9), (10) or (11) and the corresponding emitter.

[0140] The photoluminescence spectrum of the layer is recorded, for example, using a commercially available photoluminescence spectrometer.

[0141] The photoluminescence spectrum of the selected emitter is typically measured in an oxygen-free 10⁻⁵ molar solution at room temperature. Any solvent suitable for this purpose is solvent in which the emitter dissolves at the specified concentration. Particularly suitable solvents are usually toluene or 2-methyl-THF, but dichloromethane is also an option. Measurements are performed using a commercially available photoluminescence spectrometer. The triplet energy T₁ in eV is determined from the emitter's photoluminescence spectra. First, the peak maximum Pl₁ (in nm) of the photoluminescence spectrum is determined. The peak maximum Pl₁ (in nm) is then converted to eV using the formula: E(T₁ in eV) = 1240 / E(T₁ in nm) = 1240 / Pl₁ (in nm).

[0142] Preferred phosphorescent emitters are therefore yellow emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 5, whose triplet energy T 1 is preferably at -2.3 eV to ~2.1 eV.

[0143] Preferred phosphorescent emitters are therefore green emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 5, whose triplet energy T 1 is preferably at -2.5 eV to -2.3 eV.

[0144] Particularly preferred phosphorescent emitters are therefore green emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 5, as previously described, whose triplet energy T 1 is preferably at ~2.5 eV to -2.3 eV.

[0145] Particularly preferred are green emitters, preferably of formula (Illa), formulas (I) to (VIII) or from Table 5, as described above, selected for the mixture or emitting layer according to the invention.

[0146] The light-emitting layer of the device or mixture according to the invention may also contain fluorescent emitters. Preferred fluorescent emitting compounds are selected from the class of arylamines, wherein preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a condensed ring system, particularly preferably with at least 14 ring atoms. Preferred examples are aromatic anthracene amines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrenediamines, aromatic chrysene amines, or aromatic chrysenediamines. An aromatic anthracene amine is understood to be a compound in which a diarylamine group is directly bonded to an anthracene group, preferably at position 9. An aromatic anthracene diamine is understood to be a compound in which two diarylamine groups are directly bonded to an anthracene group, preferably at positions 9 and 10.Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, wherein the diarylamine groups on the pyrene are preferably bonded at the 1-position or the 1,6-position. Further preferred emitting compounds are indenofluorenamines or diamines, benzoindenofluorenamines or diamines, and dibenzoindenofluorenamines or diamines, as well as indenofluorene derivatives with fused aryl groups. Pyrene arylamines are also preferred. Benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives linked to furan or thiophene units are also preferred.

[0147] In a further preferred embodiment of the invention, the at least one light-emitting layer of the organic electroluminescent device can, in addition to the host materials 1 and 2 as previously described or preferably described, comprise further host materials or matrix materials, so-called mixed-matrix systems. The mixed-matrix systems preferably comprise three or four different matrix materials, particularly preferably three different matrix materials (i.e., one further matrix component in addition to the host materials 1 and 2 as previously described). Particularly suitable matrix materials that can be used in combination as a matrix component of a mixed-matrix system are selected from wide-band gap materials, bipolar host materials, electron transport materials (ETM) and hole transport materials (HTM).

[0148] Preferably, the mixed matrix system is optimized for an emitter of formula (Illa), formulas (I) to (VIII) or from Table 5.

[0149] According to one embodiment of the present invention, the mixture contains, in addition to the components of the host material of formula (1) and the host material 2 as described above, no further components, i.e., no functional materials. These are material mixtures that are used as such for the production of the light-emitting layer. These mixtures are also referred to as premix systems, which are used as the sole material source during the deposition of the host materials for the light-emitting layer and which have a constant mixing ratio during deposition. This allows for the simple and rapid deposition of a layer with a uniform distribution of components without the need for precise control of a multitude of material sources.

[0150] According to an alternative embodiment of the present invention, the mixture contains, in addition to the components of the host material of formula (1) and the host material 2 as described above, a phosphorescent emitter as described above. With a suitable mixing ratio during evaporation, this mixture can also be used as the sole material source, as described above.

[0151] The components of the light-emitting layer of the device according to the invention can thus be processed by vapor deposition or from solution. The material combination of the host materials 1 and 2, as previously or preferably described, optionally with the phosphorescent emitter, as previously or preferably described, is provided for this purpose in a formulation containing at least one solvent. Suitable formulations have been previously described.

[0152] The light-emitting layer in the device according to the invention, according to the preferred embodiments, and the emitting compound preferably contains between 99.9 and 1 vol%, more preferably between 99 and 10 vol%, particularly preferably between 98 and 60 vol%, and most preferably between 97 and 80 vol% of matrix material consisting of at least one compound of formula (1) and at least one compound of one of formulas (6), (7), (8), (9), (10), or (11) according to the preferred embodiments, based on the total composition of emitter and matrix material. Correspondingly, the light-emitting layer in the device according to the invention preferably contains between 0.1 and 99 vol%, more preferably between 1 and 90 vol%, particularly preferably between 2 and 40 vol%, and most preferably between 3 and 20 vol% of the emitter, based on the total composition of the light-emitting layer consisting of emitter and matrix material.If the compounds are processed from solution, the corresponding amounts in wt.% are preferably used instead of the amounts given above in vol.%.

[0153] The light-emitting layer in the device according to the preferred embodiments and the emitting compound preferably contains the host material 1 and the host material 2 in a volume percent ratio between 3:1 and 1:3, preferably between 1:2.5 and 1:1, and particularly preferably between 1:2 and 1:1. If the compounds are processed from solution, the corresponding ratio in wt.% is preferably used instead of the ratio in vol.% specified above.

[0154] The present invention also relates to an organic electroluminescent device as previously or preferably described, wherein the organic layer comprises a hole injection layer (HIL) and / or a hole transport layer (HTL), the hole-injecting material and hole-transporting material of which belong to the class of arylamines. Preferred compounds with hole transport functionality, which do not correspond to any of the formulas for the host material 2, preferably for use in a hole injection layer, a hole transport layer, an electron blocking layer, and / or as an additional matrix material in the emitting layer according to the invention, are shown in Table 6 below. The compounds in Table 6 are, as the structures show, non-deuterated compounds. Table 6: HT-1 HT-2 HT-3 HT-4 HT-5 HT-6 HT-7 HT-8 HT-9 HT-10 HT-11 HT-12 HT-13 HT-14 HT-15 HT-16 HT-17 HT-18 HT-19 HT-20 HT-21 HT-22 HT-23 HT-24 HT-25 HT-26 HT-27 HT-28 HT-29 HT-30 HT-31 HT-32 HT-33 HT-34 HT-35 HT-36 HT-37 HT-38 HT-39 HT-40 HT-41 HT-42 HT-43 HT-44 HT-45 HT-46 HT-47 HT-48 HT-49 HT-50 HT-51 HT-52 HT-53 HT-54 HT-55 HT-56 HT-57 HT-58 HT-59 HT-60 HT-61 HT-62 HT-63 HT-64 HT-65 HT-66 HT-67 HT-68 HT-69 HT-70 HT-71 HT-72 HT-73 HT-74 HT-75 HT-76 HT-77 HT-78 HT-79 HT-80 HT-81 HT-82 HT-83 HT-84 HT-85 HT-86 HT-87 HT-88 HT-89 HT-90 HT-91 HT-92 HT-93 HT-94 HT-95 HT-96 HT-97 HT-98 HT-99 HT-100 HT-101 HT-102 HT-103 HT-104 HT-105 HT-106 HT-107 HT-108 HT-109 HT-110.

[0155] The sequence of layers in the organic electroluminescence device according to the invention is preferably the following: anode / hole injection layer / hole transport layer / emitting layer / electron transport layer / electron injection layer / cathode.

[0156] This sequence of layers is a preferred sequence.

[0157] It should be noted again that not all of the mentioned layers need to be present, and / or that additional layers may be present.

[0158] Any materials used as electron transport materials in electron transport layers according to the prior art can be used as materials for the electron transport layer. In particular, suitable materials include aluminum complexes, for example Alq 3, zirconium complexes, for example Zrq 4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives.

[0159] Suitable cathodes for the device according to the invention include metals with low work function, metal alloys, or multilayer structures made of different metals, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys of an alkali or alkaline earth metal and silver are also suitable, for example, a magnesium-silver alloy. In multilayer structures, additional metals with relatively high work functions, such as Ag or Al, can be used, typically in combinations of these metals, such as Ca / Ag, Mg / Ag, or Ba / Ag. It may also be advantageous to insert 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, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.). Lithium quinolinate (LiQ) can also be used. The thickness of this layer is preferably between 0.5 and 5 nm.

[0160] Materials with a high work function are preferred as anodes. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Alternatively, metal / metal oxide electrodes (e.g., Al / Ni / NiO₂X₅, Al / PtO₂X₅) may also be preferred. For some applications, at least one of the electrodes must be transparent or semi-transparent to allow either the irradiation of the organic material (organic solar cell) or the extraction of light (OLED, O-LASER). Conductive mixed metal oxides are preferred anode materials in this context. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Conductive doped organic materials, especially conductive doped polymers, are also preferred.Furthermore, the anode can also consist of several layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0161] The organic electroluminescent device according to the invention is structured, contacted and finally sealed accordingly during its manufacture (depending on the application), since the lifetime of the devices according to the invention is shortened in the presence of water and / or air.

[0162] The manufacture of the device according to the invention is not limited in this respect. It is possible to coat one or more organic layers, including the light-emitting layer, using a sublimation process. In this process, the materials are deposited in vacuum sublimation systems at an initial pressure of less than 10⁻⁵ mbar, preferably less than 10⁻⁶ mbar. However, it is also possible for the initial pressure to be even lower, for example, less than 10⁻⁷ mbar.

[0163] The organic electroluminescence device according to the invention is preferably characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or with the aid 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 (e.g., BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0164] A further preferred feature of the organic electroluminescent device according to the invention is that one or more organic layers containing the composition according to the invention are produced from solution, e.g., by spin coating, or by any printing process, e.g., screen printing, flexographic printing, nozzle printing, or offset printing, but particularly preferably LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. Soluble host materials 1 and 2 and phosphorescent emitters are required for this purpose. Processing from solution has the advantage that, for example, the light-emitting layer can be applied very easily and cost-effectively. This technique is particularly suitable for the mass production of organic electroluminescent devices.

[0165] Hybrid processes are also possible, in which, for example, one or more layers of solution are applied and one or more further layers are vapor-deposited.

[0166] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices.

[0167] A further object of the invention is therefore a method for producing the organic electroluminescent device according to the invention, as previously described or preferably described, characterized in that the organic layer, preferably the light-emitting layer, the hole injection layer and / or hole transport layer, is applied by vapor phase deposition, in particular with a sublimation process and / or with an OVPD (Organic Vapor Phase Deposition) process and / or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing process.

[0168] In the production process using vapor deposition, there are fundamentally two ways in which the organic layer according to the invention, preferably the light-emitting layer, can be applied or evaporated onto any substrate or the previous layer. Firstly, the materials used can each be placed in a separate material source and then evaporated from the various material sources ("co-evaporation"). Secondly, the various materials can be premixed ("premix systems") and the mixture placed in a single material source from which it is then evaporated ("premix evaporation"). This allows for the simple and rapid deposition of the light-emitting layer with a uniform distribution of the components, without the need for precise control of numerous material sources.

[0169] Another object of the invention is therefore a method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of formula (1) together with the other materials forming the light-emitting layer are deposited successively or simultaneously from at least two material sources from the gas phase.

[0170] In a preferred embodiment of the present invention, the light-emitting layer is applied by means of gas phase deposition, wherein the components of the composition are premixed and evaporated from a single material source.

[0171] Another object of the invention is therefore a method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of formula (1) together with at least one further matrix material as a premix, are deposited from the gas phase successively or simultaneously with the light-emitting materials selected from the group of phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0172] The devices according to the invention are characterized by the following surprising advantages over the prior art: The use of the described material combination of the host materials 1 and 2, as described above, leads in particular to an increase in the lifetime of the devices and / or to a higher stability of the devices due to the substitution with two cyano groups and a specific substitution pattern in the host material 1.

[0173] The other electronic properties of the electroluminescent devices, such as efficiency or operating voltage, remain at least as good. In a further embodiment, the compounds and organic electroluminescent devices according to the invention are distinguished from the prior art in particular by improved efficiency and / or operating voltage and longer lifetime and / or higher stability. This applies especially to similar compounds containing two cyano groups which have a different substitution pattern on the azadibenzofuran or azadibenzothiene backbone.

[0174] The electronic devices according to the invention, in particular organic electroluminescence 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 according to formula (1) or the preferred embodiments described above and below, especially as matrix materials or as electron-conducting materials, exhibit a very good lifetime. These compounds, in particular, result in a low roll-off, i.e., a low decrease in the power efficiency of the device at high luminance levels. 2. Electronic devices, in particular organic electroluminescent devices containing compounds according to formula (1) or the preferred embodiments described above and below as electron-conducting materials and / or matrix materials, exhibit excellent efficiency. The compounds according to formula (1) or the preferred embodiments described above and below result in a low roll-off, i.e., a low decrease in the power efficiency of the device at high luminance levels.The previously and subsequently described preferred embodiments exhibit a low operating voltage when used in electronic devices. 3. The compounds according to formula (1) or the previously and subsequently described preferred embodiments show very high stability and lifetime. 4. With compounds according to formula (1) or the previously and subsequently described preferred embodiments, the formation of optical loss channels can be avoided in electronic devices, in particular organic electroluminescent devices. This results in these devices having a high PL and thus high EL efficiency of emitters or excellent energy transfer from the matrices to dopants. 5. The use of compounds according to formula (1) orThe previously and subsequently described preferred embodiments in layers of electronic devices, in particular organic electroluminescent devices, lead to high mobility of the electron conductor structures. 6. Compounds according to formula (1) or the previously and subsequently described preferred embodiments exhibit excellent glass film formation. 7. Compounds according to formula (1) or the previously and subsequently described preferred embodiments form very good films from solutions. 8. The compounds according to formula (1) or the previously and subsequently described preferred embodiments exhibit a low triplet level T1, which can be, for example, in the range of 2.40 eV to 2.90 eV.

[0175] These aforementioned advantages do not come at the cost of an excessively high deterioration of other electronic properties.

[0176] It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Unless explicitly excluded, each feature disclosed in the present invention may be replaced by alternative features serving the same, an equivalent, or a similar purpose. Thus, unless otherwise stated, each feature disclosed in the present invention is to be considered as an example of a generic series or as an equivalent or similar feature.

[0177] All features of the present invention can be combined with one another 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 can be used separately (and not in combination).

[0178] The teaching on technical action disclosed in the present invention can be abstracted and combined with other examples.

[0179] The invention is further explained by the following examples, without thereby limiting it. Examples General methods:

[0180] All quantum chemical calculations use the Gaussian16 (Rev. B.01) software package. The neutral singlet ground state is optimized at the B3LYP / 6-31G(d) level. HOMO and LUMO values ​​are determined at the B3LYP / 6-31G(d) level for the ground state energy optimized with B3LYP / 6-31G(d). Subsequently, TD-DFT singlet and triplet excitations (vertical excitations) are calculated using the same method (B3LYP / 6-31G(d)) and the optimized ground state geometry. The default settings for SCF and gradient convergence are used.

[0181] From the energy calculation, the HOMO is obtained as the last orbital occupied by two electrons (alpha occult eigenvalues) and the LUMO as the first unoccupied orbital (alpha virtual eigenvalues) in Hartree units, where HEh and LEh represent the HOMO energy in Hartree units and the LUMO energy in Hartree units, respectively. The HOMO and LUMO values, calibrated using cyclic voltammetry measurements, are then determined in electron volts as follows: HOMOcorr = 0.90603 * HOMO − 0.84836 LUMOcorr = 0.99687 * LUMO − 0.72445

[0182] The triplet level T1 of a material is defined as the relative excitation energy (in eV) of the triplet state with the lowest energy, which results from the quantum chemical energy calculation.

[0183] The singlet level S1 of a material is defined as the relative excitation energy (in eV) of the singlet state with the second lowest energy, which results from the quantum chemical energy calculation.

[0184] The lowest energy singlet state is called S0.

[0185] The method described herein is independent of the software package used and always yields the same results. Examples of frequently used programs for this purpose are "Gaussian09" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.). Here, the program package "Gaussian16 (Rev. B.01)" is used to calculate the energies. Synthesebeispiele

[0186] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be obtained, for example, from Sigma-Aldrich or ABCR. The information in square brackets and the numbers given for individual compounds refer to the CAS numbers of the compounds known from the literature. Synthesis example 1: a) Benzofuro[3,2-d]pyrimidine-2,4-dicarbonitrile

[0187]

[0188] 22.4 g (94.5 mmol) of 2,4-dichlorobenzofuro[3,2-d]pyrimidine, 16.9 g (189 mmol) of copper(I) cyanide, and 13.5 g (208 mmol) of sodium carbonate are suspended in 20 mL of N,N-dimethylformaldehyde, and the reaction mixture is heated under reflux to 170 °C for 6 h. After cooling, the mixture is treated with dichloromethane and filtered through silica gel, then concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane / heptane. Yield: 13.5 g (61 mmol), 65% of theory.

[0189] Similarly, the following connections are made: Edukt 1 Edukt 2 Ausbeute 1a 81% 2a 85% 3a 79% 4a 78% 5a 70% 6a 76% 7a 80% 8a 77% 9a 64% 10a 66% 11a 815 12a 66% 13a 73% 14a 70% 15a 61% 16a 70% 17a 78% b) 2-Chlorobenzofuro[3,2-d]pyrimidine-4-carbonitrile

[0190]

[0191] 22.4 g (94.5 mmol) of 2,4-dichlorobenzofuro[3,2-d]pyrimidine, 16.9 g (189 mmol) of copper(I) cyanide, and 6.3 g (95 mmol) of sodium carbonate are suspended in 20 mL of N,N-dimethylformaldehyde, and the reaction mixture is heated under reflux to 170 °C for 6 h. After cooling, the mixture is treated with dichloromethane and filtered through silica gel, then concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane / heptane. Yield: 14 g (75 mmol), 65% of theory.

[0192] Similarly, the following connections are established: Reagent 1 Reagent 2 yield 1b 77% 2b 57% 3b 73% 4b 73% 5b 76% 6b 79% 7b 70% 8b 65% 9b 64% 10b 73% 11b 70% 12b 65% c) 8-Bromobenzofuro[3,2-d]pyrimidine-2,4-dicarbonitrile

[0193]

[0194] 51.5 g (190.0 mmol) of benzofuro[3,2-d]pyrimidine-2,4-dicarbonitrile are suspended in 2000 mL of acetic acid (100%) and 2000 mL of sulfuric acid (95-98%). 34 g (190 mmol) of NBS (N-bromsuccinimide) are added portionwise to this suspension and stirred in the dark for 2 hours. The mixture is then treated with water / ice, and the solid is separated and washed with ethanol. The residue is recrystallized in toluene. The yield is 34.2 g (115 mmol), corresponding to 82% of the theoretical yield.

[0195] Similarly, the following connections are made: Reagent 1 product yield 1c 86% 2c 71% 3c 69% d) 8-[(4-phenyl)phenyl]benzofuro[3,2-d]pyrimidine-2,4-dicarbonitrile

[0196]

[0197] 21.7 g (110.0 mmol) of biphenylboronic acid, 29.8 g (100 mmol) of 8-bromobenzofuro[3,2-d]pyrimidine-2,4-dicarbonitrile, and 21 g (210.0 mmol) of sodium carbonate are suspended in 500 mL of ethylene glycol diamine ether and 500 mL of water. To this suspension, 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate are added, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated, filtered over silica gel, and then concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane / heptane. Yield: 30 g (81 mmol), 81% of theory.

[0198] Similarly, the following connections are made: Reagent 1 Reagent 2 product yield 1d 66% 2d 72% 3d 79% 4d 63% 5d 65% 6d 73% 7d 71% 8d 67% 9d 67% 10d 59% 11d 63% 12d 60% 13d 71% 14d 75% 15d 68% 16d 65% 17d 78% 18d 60% 19d 65% 20d 69% 21d 78% 22d 74% 23d 62% 24d 80% 25d 77% 26d 74% 27d 64% 28d 61% 29d 64% 30d 63% 31d 62% 32d 64% Synthesis example 2: General interpretation:

[0199] The starting compound is dissolved in a mixture of deuterated water (99% deuterium atom) and toluene-d8 (99% deuterium atom) and heated under pressure at 160°C for 96 hours in the presence of dry platinum on carbon (5%) as a catalyst. After cooling the reaction mixture, the phases are separated, and the aqueous phase is extracted twice with the tetrahydrofuran-toluene mixture. The recombined organic phases are washed with a sodium chloride solution, dried over sodium sulfate, and filtered. The solvent is removed under vacuum to yield the crude deuterated compound as a solid. The compound is further purified by extraction, crystallization, and sublimation. Example A: 1,1',2',3',4',5',6,6',7',8,8'-Undecadeuterio-N-(2,3,6,7,8-pentadeuterio-9,9- dimethyl-fluoren-4-yl)-N-(3,4,6,7,8-pentadeuterio-9,9-dimethyl-fluoren-2-yl)-9,9'-spirobi[fluoren]-4-amine

[0200]

[0201] N-(9,9-Dimethylfluoren-2-yl)-N-(9,9-dimethylfluoren-4-yl)-9,9'-spirobi[fluoren]-4'-amine (22.8 g, 32 mmol), toluene-d8 (231 g, 2.31 mol), deuterated water (1300 g, 64.9 mol), and dry platinum on charcoal (5%) (30 g) are stirred for 24 h at 130°C. The crude product is further purified by two extractions with a mixture of heptane and toluene (4:1) and two sublimation processes.

[0202] Yield: 21.2 g (28 mmol, 90%) with a purity of > 99.9%. The identity is confirmed by HPLC-MS and 1H-NMR. Example B: 1,2,3,5,6,7,8-Heptadeuterio-N-[1,2,3,5,6,7,8-heptadeuterio-9,9-bis(trideuteriomethyl)fluoren-4-yl]-9,9-bis(trideuteriomethyl)-N-[2,3,5-trideuterio-4-(2,3,4,5,6-pentadeuteriophenyl)phenyl]fluoren-4-amine

[0203]

[0204] N-(9,9-dimethylfluoren-2-yl)-N-(9,9-dimethylfluoren-4-yl)-9,9'-spirobi[fluoren]-4'-amine (22.8 g, 31.8 mmol), toluene-d8 (231 g, 2.31 mol), deuterated water (1300 g, 64.9 mol), and dry platinum on 5% charcoal (30 g) are stirred for 96 h at 160°C. The crude product is further purified by two extractions with a mixture of heptane and toluene (4:1) and two sublimation reactions.

[0205] Yield: 21.9 g (28.9 mmol, 95%) with a purity of > 99.9%. The identity is confirmed by HPLC-MS. Manufacturing of OLEDs

[0206] The following examples V1 to V7 and B1 to B24 (see Tables 7 and 8) present the data of various OLEDs.

[0207] Pretreatment for examples V1-V7 and B1-B24:Glass platelets coated with 50 nm thick structured ITO (indium tin oxide) are treated with an oxygen plasma followed by an argon plasma before coating. These plasma-treated glass platelets form the substrates onto which the OLEDs are applied.

[0208] The 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 8. The materials required for the fabrication of the OLEDs are shown in Table 9, unless described earlier.

[0209] All materials are thermally vapor-deposited in a vacuum chamber. The emission layer always consists of at least one matrix material (host material) and an emitting dopant, which is added to the matrix material(s) by cover vapor deposition in a specific volume fraction. A specification such as VG1:H2:TEG1 (33%:60%:7%) means that material VG1 is present in the layer at a volume fraction of 33%, material H2 at a fraction of 60%, and the emitter TEG1 at a fraction of 7%. Similarly, the electron transport layer can also consist of a mixture of two materials.

[0210] The OLEDs are characterized according to standard procedures. This involves determining the electroluminescence spectra, the voltage, and the external quantum efficiency (EQE, measured in percent) as a function of luminance, calculated from current-voltage-luminance curves (IUL curves) assuming a Lambertian emission characteristic, as well as the lifetime. 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. The value U1000 in Table 8 denotes the voltage required for a luminance of <1000 cd / m². SE1000 denotes the current efficiency achieved at <1000 cd / m². Finally, EQE1000 denotes the external quantum efficiency at an operating luminance of <1000 cd / m². Lifetime LT is defined as the time after which the luminance decreases from the initial luminance to a certain proportion L1 when operating with constant current density j 0.An entry L1=80% in Table 9 means that the lifetime specified in column LT corresponds to the time after which the luminance drops to 80% of its initial value.

[0211] The data for the various OLEDs are summarized in Table 8. Examples V1 to V7 are comparative examples according to the prior art, while examples B1 to B24 show data for OLEDs according to the invention. Table 7: Example. HIL Thickness HTL Thickness EBL Thickness EML thickness HBL thickness ETL Thickness UR Thickness V1 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm VG1:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B1 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E1:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm V2 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm VG2:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B2 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E2:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm V3 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm VG3:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B3 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E3:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm V4 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm VG4:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B4 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E4:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm V5 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm VG5:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B5 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E5:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm V6 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm VG6:H1 :TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B6 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E6:H1: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm V7 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm VG7:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B7 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E7:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B8 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E8:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B9 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E9:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B10 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E10:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B11 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E11:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B12 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E12:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B13 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E14:H2: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B14 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E13:H16: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B15 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E13:H1: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B16 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E13:H3: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B17 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E13:H47: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B18 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E13:H8: TEG1 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B19 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E13:H9: TEG2 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B20 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E15:H6: TEG2 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B21 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E13:H5: TEG3 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B22 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E15:H8: TEG3 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm B23 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E13:H3: TEG1 (33%:60%:7%) 30nm ST2 10nm E4:LiQ (50%:50%) 30nm LiQ 1nm B24 SpMA1:P D1 (95%:5%) 20nm SpMA1 215nm SpMA2 20nm E27:H8: TEG3 (33%:60%:7%) 30nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm Table 8: Ex. U1000 (V) SE1000 (cd / A) EQE1000 (%) CIE x / y at 1000 cd / m2 j 0 (mA / cm²< ) L1 (%) LT (h) V1 4.2 71 16 0.34 / 0.64 20 80 120 B1 3.8 76 17 0.35 / 0.62 20 80 165 V2 3.6 71 16 0.34 / 0.61 20 80 75 B2 3.4 72 17.5 0.32 / 0.62 20 80 175 V3 3.8 69 17 0.35 / 0.62 20 80 130 B3 3.4 72 18.5 0.33 / 0.63 20 80 170 V4 3.6 68 18 0.32 / 0.62 20 80 125 B4 3.2 70 19 0.34 / 0.61 20 80 180 V5 4.2 71 17 0.34 / 0.61 20 80 95 B5 3.4 75 18 0.33 / 0.63 20 80 175 V6 3.5 70 17 0.35 / 0.62 20 80 130 B6 3.3 75 19 0.33 / 0.63 20 80 155 V7 3.5 68 17.5 0.33 / 0.63 20 80 135 B7 3.2 75 18.5 0.33 / 0.63 20 80 185 B8 3.4 71 18 0.33 / 0.62 20 80 200 B9 3.4 76 18 0.35 / 0.62 20 80 215 B10 3.5 69 16.5 0.35 / 0.62 20 80 220 B11 3.5 75 18.5 0.33 / 0.63 20 80 210 B12 3.4 67 18.5 0.33 / 0.63 20 80 235 B13 3.6 75 18 0.32 / 0.63 20 80 145 B14 4.1 68 16 0.35 / 0.62 20 80 170 B15 3.3 76 18.5 0.35 / 0.62 20 80 235 B16 3.4 65 18 0.35 / 0.62 20 80 240 B17 3.3 76 19 0.35 / 0.62 20 80 245 B18 3.2 70 17 0.34 / 0.61 20 80 280 B19 3.4 76 19 0.35 / 0.62 20 80 295 B20 3.3 69 18.5 0.35 / 0.62 20 80 280 B21 3.2 76 18.5 0.34 / 0.61 20 80 275 B22 3.1 76 19 0.35 / 0.62 20 80 260 B23 3.7 70 18.5 0.34 / 0.61 20 80 240 B24 3.6 76 17.9 0.35 / 0.63 20 80 158 Table 9: Materials used, unless otherwise described PD1 (CAS Reg. No. 1224447-88-4) SpMA1 SpMA2 ST2 LiQ TEG1 TEG2 TEG3 VG1 WO2019160315 VG2 WO2014097866 VG3 KR20170068927 VG4 KR20170068927 VG5 WO2019160315 VG6 WO2018060218

Claims

1. Compound according to formula (1), wherein applies to the symbols and indices used: Ring A1 in formula (1) corresponds to formula (1A) Y in each occurrence is independently N, C or CR+, wherein at least one Y is N and at least two Ys are C to which the CN group is attached; if two Ys are N, they are separated from each other by at least one C-CN group; V is O or S; L is a single bond or an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, which may be unsubstituted or partially or completely substituted with D, with the condition that the heteroaromatic ring system excludes a carbazole group bonded via the N atom; Rx is an aromatic ring system having 6 to 30 ring atoms, which may be substituted by one or more radicals R2, or a heteroaromatic ring system having 5 to 30 ring atoms, which may be substituted by one or more radicals R2, with the proviso that the ring system and substituents bonded thereto do not contain an N-bonded carbazole group; R+ is an aromatic ring system with 6 to 30 ring atoms, which may be substituted with one or more radicals R2 or a heteroaromatic ring system with 5 to 30 ring atoms, which may be substituted with one or more radicals R2; R# in each occurrence is, identically or differently, an aromatic ring system having 6 to 30 ring atoms, which may be substituted by one or more radicals R2, or a heteroaromatic ring system having 5 to 30 ring atoms, which may be substituted by one or more radicals R2, with the proviso that the ring system and substituents attached thereto do not contain an N-linked carbazole group; R2 in each occurrence is the same or different and is selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S and wherein one or more H atoms may be replaced by D, F, or CN or an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, in which one or more H atoms can be replaced by D, F, Cl, Br, I or CN and which can be substituted by one or more alkyl groups with 1 to 4 carbon atoms each; two or more neighbouring substituents R2 may together form a mono- or polycyclic aliphatic ring system; b is 0 or 1; n is 0, 1, 2 or 3.

2. The compound according to claim 1, selected from the compounds of formulae (1a), (1b), (1c), (1d), (1e) or (1f), wherein the symbols used V, R+, L, b, Rx, R# and n have a meaning as in claim 1.

3. The compound according to claim 1 or 2, wherein V is O.

4. A mixture containing at least one compound according to one or more of claims 1 to 3 and at least one further compound selected from the group consisting of the matrix materials, the phosphorescent emitters, the fluorescent emitters and / or the emitters which exhibit TADF (thermally activated delayed fluorescence).

5. A formulation containing at least one compound according to one or more of claims 1 to 3 or a mixture according to claim 4 and at least one solvent.

6. An organic electroluminescent device comprising an anode, a cathode and at least one organic layer containing at least one compound according to one or more of claims 1 to 3.

7. The organic electroluminescent device according to claim 6, wherein the organic layer contains at least one light-emitting layer containing the compounds according to any one of claims 1 to 3.

8. Organic electroluminescent device according to claim 6 or 7, characterised in that the light-emitting layer contains a further matrix material.

9. The organic electroluminescent device according to claim 8, characterised in that the second matrix material corresponds to a compound of the formulae (6), (7), (8), (9) or (10), wherein the following applies to the symbols and indices used A1 is C(R7)2, NR7, O or S; A is a group of formula (3) or (4) for each occurrence independently of each other, X2 is the same or different CH, CR6 or N for each occurrence, wherein a maximum of 2 symbols X2 can mean N; * indicates the binding site to the formula (9); R6 in each occurrence is the same or different D, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group is identical or different, alkenyl or alkynyl group may in each case be substituted by one or more radicals R7 and wherein one or more non-adjacent CH2 groups may be replaced by Si(R7)2, C=O, NR7, O, S or CONR7, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R7; two radicals R6 can also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system together; Ar is an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be substituted with one or more radicals R7; Ar5 is identical or different in each occurrence for an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which can be substituted with one or more radicals R7; R7 is the same or different in each occurrence D, F, Cl, Br, I, N(R8)2, CN, NO2, OR8, SR8, Si(R8)3, B(OR8)2, C(=O)R8, P(=O)(R8)2, S(=O)R8, S(=O)2R8, OSO2R8, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may each be substituted by one or more radicals R8, wherein one or more non-adjacent CH2 groups are substituted by Si(R8)2, C=O, NR8, O, S or CONR8, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which may be substituted by one or more radicals R8; two or more radicals R7 can together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R7 do not form such a ring system; R8 in each occurrence is identical or different H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 carbon atoms, in which one or more H atoms may also be replaced by F; c, c1, c2 are each independently 0 or 1 at each occurrence, wherein the sum of the indices at each occurrence c+c1+c2 is 1; d, d1, d2 each mean 0 or 1 independently of each other at each occurrence, wherein the sum of the indices at each occurrence d+d1+d2 means 1; q, q1, q2 each mean 0 or 1 independently for each occurrence; s is the same or different for each occurrence 0, 1, 2, 3 or 4; t is the same or different 0, 1, 2 or 3 for each occurrence; u is the same or different 0, 1 or 2 for each occurrence; and v is 0 or 1.

10. The organic electroluminescent device according to claim 8, characterised in that the second matrix material corresponds to a compound of the formula (11) wherein the symbols and indices used are W is O, S, C(R)2, N-Ar1; R is, in each case independently of one another, a straight-chain or branched alkyl group having 1 to 4 carbon atoms, which may be partially or completely deuterated, or an unsubstituted or partially or completely deuterated aromatic ring system having 6 to 18 carbon atoms, wherein two substituents R with the carbon atom to which they are bonded form a mono- or di-substituted ring system, to which they are bonded may form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic unsubstituted, partially deuterated or completely deuterated ring system which may be substituted by one or more substituents R5; Ar1 is in each occurrence the same or different an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, which can be substituted with one or more radicals R5; two radicals Ar1, which bind to the same N atom, P atom or B atom, can also be bridged together by a single bond or a bridge selected from C(R5)2, O or S; R1 in each occurrence is the same or different selected from the group consisting of F, Cl, Br, I, CN, NO2, C(=O)R', P(=O)(Ar1)2, P(Ar1)2, B(Ar1)2, Si(Ar1)3, Si(R')3, a straight-chain alkyl, alkoxy or thioalkyl group with 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 1 to 20 C atoms, alkoxy or thioalkyl group with 3 to 20 C atoms or an alkenyl group with 2 to 20 C atoms, each of which may be substituted with one or more radicals R', wherein one or more non-adjacent CH2 groups are replaced by R'C=CR', Si(R')2, C=O, C=S, C=NR', P(=O)(R'), SO, SO2, NR', O, S or CONR' and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2; R' in each occurrence is, identically or differently, an aliphatic, aromatic or heteroaromatic organic radical; R4 is, in each occurrence, identically or differently selected from the group consistingof F, Cl, Br, I, CN, NO2, N(Ar1)2, NH2, N(R5)2, C(=O)Ar1, C(=O)H, C(=O)R5, P(=O)(Ar1)2, a straight-chain alkyl, alkoxy or thioalkyl group with 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 1 to 40 C atoms, alkoxy or thioalkyl group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more radicals R5, wherein one or more non-adjacent CH2 groups are substituted by HC=CH, R5C=CR5, C≡C, Si(R5)2, Ge(R5)2, Sn(R5)2, C=O, C=S, C=Se, C=NR5, P(=O)(R5), SO, SO2, NH, NR5, O, S, CONH or CONR5 and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having from 5 to 60 ring atoms, each of which may be substituted by one or more radicals R5, an aryloxy or heteroaryloxy group having from 5 to 60 ring atoms, which may be substituted with one or more radicals R5, or a combination of these systems, wherein optionally two or more neighbouring substituents R4 may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more radicals R5; R5 in each occurrence is the same or different and is selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by O or S and wherein one or more H atoms may be replaced by D, F, or CN or an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, in which one or more H atoms can be replaced by D, F, Cl, Br, I or CN and which can be substituted by one or more alkyl groups with 1 to 4 carbon atoms each; two or more neighbouring substituents R5 may together form a mono- or polycyclic aliphatic ring system; x, x1 are independently 0, 1, 2, 3 or 4 at each occurrence; y, z are each independently 0, 1 or 2; a1, a2 are each independently 0, 1, 2, 3, 4 or 5; a3 is 0, 1, 2 or 3; a4 is 0, 1, 2, 3 or 4.

11. An organic electroluminescent device according to one or more of claims 6 to 9, characterised in that the light-emitting layer contains a phosphorescent emitter.

12. The organic electroluminescent device according to one or more of claims 6 to 10, characterised in that it is an electroluminescent device selected from organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic light-emitting diodes (OLEDs).

13. A method of manufacturing a device according to one or more of claims 6 to 11, characterised in that the organic layer is applied by vapour deposition or from solution.

14. Process according to claim 13, characterised in that the light-emitting layer of the organic layer is applied by vapour phase deposition, wherein the at least one compound of formula (1) together with the further materials forming the light-emitting layer are deposited from the vapour phase successively or simultaneously from at least two material sources.

15. Process according to claim 13 or 14, characterised in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of formula (1) together with at least one further matrix material as premix is deposited from the gas phase successively or simultaneously with the light-emitting materials selected from the group consisting of the phosphorescent emitters, the fluorescent emitters and / or the emitters which exhibit TADF (thermally activated delayed fluorescence).