Materials for organic electroluminescent devices

Abstract

The present invention relates to specific deuterated spirocarbazole-triazine derivatives, mixtures and formulations containing them, and to electronic devices containing these compounds, in particular organic electroluminescent devices containing these compounds as matrix materials, electron-transport materials or hole-blocking materials.

Description

[0001] Materials for organic electroluminescent devices Technical field The present invention relates to specific deuterated spirocarbazole triazine derivatives, mixtures and formulations containing them, and electronic devices containing these compounds, in particular organic electroluminescent devices containing these compounds as matrix materials, electron-transport materials or hole-blocking materials. State of the art Phosphorescent organometallic complexes are frequently used in organic electroluminescent devices (OLEDs). In general, there is still room for improvement in OLEDs, for example with regard to efficiency, operating voltage and lifetime. The properties of phosphorescent OLEDs are determined not only by the triplet emitters used. The other materials used, such as matrix materials, are also of particular importance here.Improvements to these materials can therefore also lead to significant improvements in OLED properties. WO 2014 / 094963 A1 describes special non-deuterated spirocarbazole triazine derivatives and their suitability for organic electronic devices. In general, there is still room for improvement with these materials, particularly for use as matrix materials. The object of the present invention is therefore to provide compounds which are particularly suitable for use as matrix material, electron transport material, electron injection material, or hole blocking material in a phosphorescent OLED. In particular, the object of the present invention is to provide matrix materials which lead to an improved lifetime. This applies in particular to the use of a low to medium emitter concentration, i.e.Emitter concentrations in the order of magnitude of 3 to 20%, in particular 3 to 15%, since the device lifetime is limited here in particular. In particular, the object of the present invention is to provide electron-transport materials which lead to an improved lifetime. It has now been found that electroluminescent devices which contain compounds according to the following formula (1) or formula (1A) exhibit improvements over the prior art, in particular when using the compounds as matrix material for phosphorescent dopants. It has further been found that the combination of at least one compound of the formula (1) orFormula (1A) as the first host material and at least one hole-transporting compound, for example in combination with one or more compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), as a further host material or further host materials in a light-emitting layer of an organic electronic device, in particular an organic electroluminescent device, achieve this object and eliminate the disadvantages of the prior art. Summary of the invention A first subject of the present invention is a compound according to formula (1) or formula (1A). where the following applies to the symbols and indices used: Y is the same or different for each occurrence CR 1 or N, with the proviso that at least one group Y is N; X is the same or different at each occurrence CR 1 or N; or two adjacent Xs represent S, O or NR 1, so that a five-membered ring is formed; or two adjacent X represent a group of the following formula (2), (3) or (4), where ^ denotes the corresponding adjacent groups X in formula (1) or formula (1A); V is at each occurrence, the same or different from C(R 1 )2, NR 1 , O, S, BR 1 , Si(R 1 )2or C=O; Z is the same or different at each occurrence CR 1 or N; Ar is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is substituted by one or more radicals R 1 may be substituted; R is at each occurrence, identically or differently, selected from the group consisting of H, D, F, Cl, Br, I, CN, N(Ar 1 )2, a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, each of which is substituted by one or more radicals R 2may be substituted, with one or more non-adjacent CH2 groups being substituted by R 2 C=CR 2 , C≡C or O and where one or more H atoms can be replaced by D or F, or an aromatic ring system with 6 to 60 aromatic ring atoms, which is substituted with one or more radicals R 2 may be substituted; two adjacent substituents R may form a monocyclic or polycyclic, aliphatic or aromatic ring system which may be substituted with one or more radicals R 2 may be substituted; R 1 is selected at each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO2, N(Ar 1 )2, N(R 2 )2, C(=O)Ar 1 , C(=O)R 2 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, Si(Ar 1 )3, Si(R 2)3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, with one or more non-adjacent CH2 groups being substituted by R 2 C=CR 2 , C≡C, Si(R 2 )2, C=O, C=S, C=NR 2 , P(=O)(R 2 ), SO, SO2, NR 2 , O, S or CONR 2 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 with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted with one or more radicals R 2may be substituted; optionally two adjacent substituents R 1 form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which, with one or more radicals R 2 can be substituted; Ar 1 is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is substituted by one or more non-aromatic radicals R 2 can be substituted; two residues Ar 1 which bind to the same N-atom or P-atom, also by a single bond or a bridge, selected from N(R 2 ), C(R 2 )2, O or S, may be bridged together; R 2is selected, identically or differently at each occurrence, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN, where two or more adjacent substituents R 2can form a mono- or polycyclic, aliphatic ring system with one another; m, n is the same or different on each occurrence and is 0 or 1, with the proviso that m + n ≥ 1; p is the same or different on each occurrence and is 0, 1, 2, 3 or 4; q is 0, 1 or 2, characterized in that the compound of the formula (1) or of the formula (1A) contains at least one deuterium atom as a substituent. The present invention further provides a mixture comprising at least one compound of the formula (1) or of the formula (1A) as described above or preferably described later and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters which exhibit TADF (thermally activated delayed fluorescence) and / or a solvent. The present invention further provides a mixture comprising at least one compound of the formula (1) or of the formula (1A)Formula (1A) as described above or preferably described later, and at least one further compound selected from the group of electron-transport materials, electron-injection materials, hole-blocking materials, materials having a high dielectric constant, and / or a solvent. The present invention further provides an organic electronic, preferably electroluminescent, device comprising an anode, a cathode, and at least one organic layer containing at least one compound according to formula (1) or formula (1A), as described above or preferably described later.The present invention further provides a process for producing an organic electronic, preferably electroluminescent, device, as described above or preferably described below, characterized in that the organic layer is applied by vapor deposition or from solution. Description of the invention In the present patent application, "D" or "D atom" denotes deuterium. The degree of deuteration, given in mol%, means the proportion of H atoms replaced by deuterium. Since the deuterated compounds are often a mixture of compounds that differ in the exact position and the exact proportion of the D atoms, the degree of deuteration denotes the average proportion of H atoms replaced by D.With a degree of deuteration of 50 mol%, an average of 50 mol% of the H atoms in the compound are replaced by D, resulting in a medium degree of deuteration. In a first preferred embodiment, the spirocarbazole skeleton has at least one D atom. The spirocarbazole skeleton comprises the spirobifluorene group and the fused carbazole group, including the 6-membered ring formed from the X groups. Thus, at least one of the R radicals is the spirobifluorene group and / or one of the R radicals. 1 of the 6-membered ring formed from the X groups is a D atom. In a second preferred embodiment, at least one of the radicals R 1 of the aromatic or heteroaromatic ring system Ar and / or the 6-membered ring formed from the Y groups is a D atom. In a third preferred embodiment, at least one of the R radicals of the spirobifluorene group and / or one of the R radicals 1of the 6-membered ring formed from the X groups has a D atom and at least one of the radicals R 1 of the aromatic or heteroaromatic ring system Ar and / or the 6-membered ring formed from the Y groups, a D atom. If the deuterated compounds of formula (1) or formula (1A) contain at least one radical R 2 contain, in addition to the above-mentioned three preferred embodiments, at least one of the radicals R 2be a D atom. In general, the degree of deuteration of the compounds of formula (1) or formula (1A) is in the range from 1 to 100 mol%, preferably in the range from 10 to 100 mol%, particularly preferably in the range from 50 to 95 mol%, and very particularly preferably in the range from 70 to 90 mol%. An aryl group within the meaning of the present invention contains 6 to 40 ring atoms, preferably C atoms. A heteroaryl group within the meaning of the present invention contains 5 to 40 ring atoms, where the ring atoms comprise C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e. phenyl, derived from benzene, or a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene, or a condensed aryl or heteroaryl group,for example, derived from naphthalene, anthracene, phenanthrene, quinoline, or isoquinoline. An aryl group having 6 to 18 C 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 within the meaning of the present invention can carry one or more radicals, the suitable radical being described below. If no such radical is described, the aryl group or heteroaryl group is unsubstituted. An aromatic ring system within the meaning of the present invention contains 6 to 40 C atoms in the ring system. The aromatic ring system also includes aryl groups, as described above. An aromatic ring system having 6 to 18 C atoms is preferably formed from phenyl, fully deuterated phenyl, biphenyl, naphthyl,Phenanthryl and triphenylenyl are selected. A heteroaromatic ring system within the meaning of the present 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 described above. The heteroatoms in the heteroaromatic ring system are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system within the meaning of the present invention is understood to mean a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be interrupted by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as a C or O atom or a carbonyl group. For example, systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene,Diaryl ethers, stilbene, etc. are understood as aromatic or heteroaromatic ring systems within the meaning of the present invention, as are systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group. Furthermore, systems in which two or more aryl or heteroaryl groups are directly bonded to one another, such as biphenyl, terphenyl, quaterphenyl or bipyridine, are also encompassed by the definition of the aromatic or heteroaromatic ring system. An aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which can be linked via any positions to the aromatic or heteroaromatic ring, is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl,Terphenylen, Fluoren, Spirobifluoren, Dihydro- phenanthren, Dihydropyren, Tetrahydropyren, cis- oder trans-Indenofluoren, cis- oder trans-Monobenzoindenofluoren, cis- oder trans-Dibenzoindenofluoren, Truxen, Isotruxen, Spirotruxen, Spiroisotruxen, Furan, Benzofuran, Isobenzofuran, Dibenzofuran, Thiophen, Benzothiophen, Isobenzothiophen, Dibenzothiophen, Pyrrol, Indol, Isoindol, Carbazol, Indolocarbazol, Indenocarbazol, Pyridin, Chinolin, Isochinolin, Acridin, Phenanthridin, Benzo-5,6-chinolin, Benzo-6,7-chinolin, Benzo-7,8-chinolin, Phenothiazin, Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1,2-Thiazol, 1,3-Thiazol, Benzothiazol, Pyridazin, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1,5-Diazaanthracen, 2,7- Diazapyren, 2,3-Diazapyren, 1,6-Diazapyren, 1,8-Diazapyren, 4,5-Diazapyren, 4,5,9,10-Tetraazaperylen,Pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-Tetrazine, purine, pteridine, indolizine, and benzothiadiazole. The abbreviations Ar and Ar, 1 mean at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which, with one or more radicals R 1 may be substituted, where the radical R 1 or the substituents R 1has / have a meaning as described above or below. The phrase "two or more residues can form a ring" is understood, for the purposes of this description, to mean, among other things, that the two residues are linked by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme: Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring. This is illustrated by the following scheme: . A cyclic alkyl, alkoxy or thioalkyl group within the meaning of the present invention is understood to mean a monocyclic, a bicyclic or a polycyclic group. In the context of the present invention, a straight-chain, branched or cyclic C1 to C20 alkyl group is understood to mean, for example, the radicals methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-Octyl, 2-Ethylhexyl, Cyclooctyl, 1-Bicyclo[2,2,2]octyl, 2-Bicyclo[2,2,2]octyl, 2-(2,6-Dimethyl)octyl, 3-(3,7-Dimethyl)octyl, Adamantyl, Trifluoromethyl, Pentafluoroethyl, 2,2,2-Trifluoroethyl, 1,1-Dimethyl-n-hex-1-yl-, 1,1-Dimethyl-n-hept-1-yl-, 1,1-Dimethyl-n-oct-1-yl-, 1,1-Dimethyl-n-dec-1-yl-, 1,1-Dimethyl-n-dodec-1-yl-, 1,1-Dimethyl-n-tetradec-1-yl-, 1,1-Dimethyl-n-hexadec-1-yl-, 1,1-Dimethyl-n-octadec-1-yl-, 1,1-Diethyl-n-hex-1-yl-, 1,1-Diethyl-n-hept-1-yl-, 1,1-Diethyl-n-oct-1-yl-, 1,1-Diethyl-n-dec-1-yl-, 1,1-Diethyl-n-dodec-1-yl-, 1,1-Diethyl-n-tetradec-1-yl-, 1,1-Diethyln-n-hexadec-1-yl-, 1,1-Diethyl-n-octadec-1-yl-, 1-(n-propyl)-cyclohex-1-yl-, 1-(n-butyl)-cyclohex-1-yl-, 1-(n-hexyl)-cyclohex-1-yl-, 1-(n-octyl)-cyclohex-1-yl-, and 1-(n-decyl)-cyclohex-1-yl-. The compounds of formula (1) and formula (1A) and their preferred embodiments are described below. The preferred embodiments also apply to the mixture according to the invention.formulation according to the invention and organic electronic or electroluminescent device according to the invention. Preferred embodiments of the compounds according to formula (1) are the compounds of the following formulas (5) to (11) and preferred embodiments of the compounds according to formula (1A) are the compounds of the following formula (12),

[0002] where the symbols and indices used have the meanings given above. V preferably stands for NR 1 , C(R 1 )2, O or S. It may be preferred if V = C(R 1 )2the two residues R 1together form a ring and thus span a spiro system. In a preferred embodiment of the present invention, p is, identically or differently, 0, 1 or 2 at each occurrence, particularly preferably 0 or 1 and most preferably 0. Furthermore, q is preferably 0 or 1, particularly preferably 0. Particularly preferred embodiments of the structures according to formulas (5) to (12) are the structures of formulas (5a) to (12a),

[0003]

[0004] where the symbols and indices used have the meanings given above. In a preferred embodiment of the present invention, R is the same or different on each occurrence and is selected from the group consisting of H, D, F, CN, N(Ar 1)2, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic ring system having 6 to 30 aromatic ring atoms which is substituted by one or more non-aromatic radicals R 2 may be substituted. In a particularly preferred embodiment of the present invention, R is the same or different on each occurrence and is selected from the group consisting of H, a straight-chain alkyl group having 1 to 4 C atoms or a branched or cyclic alkyl group having 3 to 8 C atoms, in particular H. If the compound according to the invention is used as a monomer for producing a polymer, it may also be preferred if two substituents R are Br or I and the polymerization is carried out via these groups. In a further preferred embodiment of the present invention, R 1identically or differently at each occurrence selected from the group consisting of H, D, F, Br, CN, N(Ar 1 )2, C(=O)Ar 1 , P(=O)(Ar 1 )2, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, where one or more non-adjacent CH2 groups may be replaced by O and where one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R 2 may be substituted. R is particularly preferably 1 identically or differently at each occurrence selected from the group consisting of H, N(Ar 1)2, a straight-chain alkyl group having 1 to 4 C atoms or a branched or cyclic alkyl group having 3 to 8 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, or an aromatic or heteroaromatic ring system with 5 to 18 aromatic ring atoms, each substituted with one or more radicals R 2 may be substituted. If R represents an aromatic ring system or if R 1 represents an aromatic or heteroaromatic ring system, then this R or R 1are preferably selected, identically or differently on each occurrence, from the same groups as indicated below as suitable groups for Ar. In compounds that are processed by vacuum evaporation, the alkyl groups preferably have no more than five C atoms, more preferably no more than 4 C atoms, most preferably no more than 1 C atom. For compounds that are processed from solution, compounds that are substituted by alkyl groups, in particular branched alkyl groups, having up to 10 C atoms or that are substituted by oligoarylene groups, for example ortho-, meta-, para- or branched terphenyl or quaterphenyl groups, are also suitable. In a preferred embodiment of the present invention, n = 1 and m = 0. In a further preferred embodiment of the present invention, n = 0 and m = 1. In yet another preferred embodiment of the present invention, n = m = 1.Preferred groups Ar are aromatic or heteroaromatic ring systems with 5 to 24 aromatic ring atoms, each of which is substituted by one or more radicals R. 1 can be substituted. Suitable groups Ar are selected from benzene, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched quaterphenyl, 1-, 2- or 3-fluorenyl, 1-, 2-, 3- or 4-spiro-bifluorenyl, 1- or 2-naphthyl, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, 1-, 2- or 3-carbazole, 1-, 2- or 3-dibenzofuran, 1-, 2- or 3-dibenzothiophene, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2-, 4- or 5-pyrimidine, pyrazine, pyridazine, triazine, anthracene, phenanthrene, Triphenylene, pyrene, benzanthracene or combinations of two or three of these groups, each of which is substituted by one or more radicals R 1may be substituted. Particularly preferably, Ar represents an aromatic ring system, in particular selected from the groups consisting of benzene, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl and ortho-, meta-, para- or branched quaterphenyl. If a group (Het-Ar), as described in more detail below, is bonded to the group Ar, i.e., if n = m = 1, then the group (Het-Ar) is bonded to Ar at any desired position. In a preferred embodiment of the present invention, Ar is an aromatic ring system, i.e., it does not contain any heteroaryl groups. This applies both when n = 1 and a group (Het-Ar), as described below, is bonded to Ar, and also for n = 0. In a further preferred embodiment of the present invention, the aromatic groups in the group Ar, if Ar contains more than one aryl group, are not para-linked, i.e.,It is preferably not para-biphenyl, para-terphenyl, or para-quaterphenyl, but rather, for example, the respective ortho- or meta-linked structures. Furthermore, if Ar contains a carbazole, pyrrole, imidazole, or benzimidazo group, it is preferred that this group is linked to the other aromatic units of Ar or to the nitrogen atom not via a nitrogen atom, but via a carbon atom. For n = 1, the compound according to the invention contains a heteroaryl group of the following formula, which is abbreviated below as (Het-Ar):. This group is present in the compound according to the invention for n = 1 and is bonded to Ar for m = 1 or to the nitrogen for m = 0. In the group (Het-Ar), at least one group Y and preferably a maximum of three groups Y represent N, and the other groups Y represent CR 1 . Preferred embodiments are the groups of the following formulas (Het-Ar-1) to (Het-Ar-10), where the dashed bond represents the bond to Ar or, for m = 0, the bond to the nitrogen, and the symbols used have the meanings given above. Particular preference is given to the groups of the following formulae (Het-Ar-1a) to (Het-Ar-10b), where the dashed bond represents the bond to Ar or, for m = 0, the bond to the nitrogen, and the symbols used have the meanings given above. If (Het-Ar) represents a group (Het-Ar-1) or (Het-Ar-1a), then the two substituents R 1 in this group preferably represents an aromatic or heteroaromatic ring system with 5 to 24 aromatic ring atoms, which is substituted by one or more radicals R 2may be substituted, in particular for phenyl, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched quaterphenyl, 1-, 2-, 3- or 4-fluorene, 1-, 2-, 3- or 4-spirobifluorene, 1-, 2-, 3- or 4-dibenzofuran or 1-, 2-, 3- or 4-carbazole. If (Het-Ar) represents a group (Het-Ar-2) to (Het-Ar-10) or (Het-Ar-2a) to (Het-Ar-10a), then R 1 in these groups, preferably identically or differently at each occurrence, represents H, D or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which is substituted by one or more radicals R 2may be substituted, in particular for H or phenyl, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl or ortho-, meta-, para- or branched quaterphenyl. The above-mentioned preferred embodiments can be combined with one another as desired. In a particularly preferred embodiment of the invention, the above-mentioned preferences occur simultaneously. If the compounds of formula (1) or formula (1A) and the preferred embodiments are used as matrix material for a phosphorescent emitter or in a layer directly adjacent to a phosphorescent layer, it is further preferred if the compound does not contain any condensed aryl or heteroaryl groups in which more than two six-membered rings are directly condensed to one another. In particular, it is preferred if the radicals R, R 1 , R 2and Ar do not contain a condensed aryl or heteroaryl group in which two or more six-membered rings are directly fused to one another, and if two adjacent groups X do not represent a group of the formula (2). If the compounds of the formulas (1) or (1A) are deuterated compounds, it is possible during their preparation, provided that the preparation is chosen by reacting a non-deuterated compound of one of the formulas (1) or (1A) with a deuteration source, or provided that deuterated starting compounds are chosen during the preparation which are a mixture of deuterated starting compounds, that a mixture of deuterated products of the same basic chemical structure is formed which differ only in the degree of deuteration and / or the deuteration patterns. Such mixtures of deuterated compounds of the same basic chemical structure of the formula (1) or(1A) or the basic structure of the preferred embodiments, which differ only in the degree of deuteration and / or the deuteration patterns, are understood by the term "at least one compound of formula (1)" within the meaning of the invention. In one embodiment of the invention, (D) are represented. a , (D) b , (D) c , (D) d and (D) e for no substitution. In one embodiment of the invention, (D) a , (D) b , (D) c , (D) d and (D) efor maximum substitution. In a preferred embodiment of the at least one compound of formula (1) or (1A), as described above or preferably described, the average degree of deuteration is at least 10 mol% to 100 mol%, preferably 50 mol% to 95 mol%, particularly preferably 70 mol% to 90 mol%. Corresponding deuteration methods are known to the person skilled in the art and are described, for example, in KR2016041014, WO2017 / 122988, KR202005282, KR101978651 and WO2018 / 110887 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. A suitable method for deuterating a compound by exchanging one or more H atoms for D atoms is to treat the compound to be deuterated in the presence of a platinum catalyst or palladium catalyst and a deuterium source.The term "deuterium source" means any compound containing one or more D atoms and capable of releasing them under suitable conditions. 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-d3, 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, although the fully deuterated solvent is not limited 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 with heating, more preferably with heating to temperatures between 100°C and 200°C. Furthermore, the reaction is preferably carried out under pressure. Examples of preferred compounds according to the above-mentioned embodiments are the compounds listed in Table 1 below. Table 1:.

[0005] Particularly preferred compounds of formula (1) or formula (1A) are compounds E1 to E36 of the following Table 2. Table 2:

[0006] The compounds of the invention can be prepared by synthesis steps known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc. In the following synthesis schemes, the compounds are shown with a small number of substituents to simplify the structures. This does not exclude the presence of any other substituents in the processes. The processes shown for the synthesis of the compounds of the invention are to be understood as examples. The skilled person can develop alternative synthesis routes within the scope of their general technical knowledge. The basic structure of the compounds of the invention can be prepared by the route outlined in Scheme 1. Functionalization can be carried out according to Scheme 2. Scheme 1: Scheme 2: The synthesis is usually carried out starting from 4-bromospirobifluorene known from the literature (Organic Letters 2009, 11(12), 2607-2610) or a correspondingly substituted 4-bromospirobifluorene. This is reacted with an ortho-haloaminobenzene in a CN coupling reaction, for example, under Pd or Cu catalysis, where the halogen is preferably Cl, Br, or I. A naphthalene, fluorene, dibenzofuran, or dibenzothiophene derivative can be used in a completely analogous manner, leading to compounds containing groups of formula (2) or (3). Ring closure to the corresponding carbazole derivative occurs through an intramolecular Pd-catalyzed coupling reaction. The synthesis of compounds of formula (1A) can be carried out completely analogously starting from 4,4'-dibromospirobifluorene known from the literature.Compounds of formula (1) with n = 0 and m = 1 are obtained by a coupling reaction, for example Hartwig-Buchwald coupling or Ullmann coupling, with an appropriately functionalized aromatic or heteroaromatic compound, wherein the reactive group is preferably Cl, Br or I. Compounds of formula (1) with n = 1 and m = 0 are obtained by a nucleophilic aromatic substitution reaction or by a Pd-catalyzed coupling reaction with a group (Het-Ar) substituted with an appropriate leaving group, in particular Cl or Br.Compounds of formula (1) with n = 1 and m = 1 are obtained by a coupling reaction, for example a Hartwig-Buchwald coupling or Ullmann coupling, with a difunctionalized aromatic or heteroaromatic, where the reactive groups are preferably a bromine and an iodine group, followed by a Pd-catalyzed coupling reaction, for example a Suzuki, Negishi, Yamamoto, Grignard Cross or Stille coupling, optionally after conversion of a halogen group into a boronic acid derivative. The present invention further provides a process for preparing a compound according to formula (1) or formula (1A), comprising the reaction steps: a) synthesis of the basic structure of the compound (1) or (1A), which does not yet contain a group (Het-Ar) and / or Ar; and b) conversion of the basic skeleton from a) into a CC coupling, such as Suzuki, Negishi, Yamamoto, Grignard Cross or Stille coupling, etc., or CN coupling, such as Buchwald or Ullmann coupling.Detailed reaction conditions are known from the prior art or are described in the examples. By these processes, optionally followed by purification, such as recrystallization or sublimation, the compounds of formula (1) or formula (1A) can be obtained in high purity, preferably more than 99% (determined by chromatography). 1H-NMR and / or HPLC). For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention or mixtures of compounds of the invention with other 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 are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone,3-Methylanisole, 4-Methylanisole, 3,4-Dimethylanisole, 3,5-Dimethylanisole, Acetophenone, α-Terpineol, Benzothiazole, Butyl Benzoate, Cumene, Cyclohexanol, Cyclohexanone, Cyclohexylbenzene, Decalin, Dodecylbenzene, Ethyl Benzoate, Indane, NMP, p-Cymene, Phenetol, 1,4-Diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, Heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-Methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents. The compounds of formula (1) or formula (1A) according to the invention, as described above or preferably described,are suitable for use in an organic electroluminescent device, in particular as a matrix material. If the compound according to the invention is used as a matrix material or synonymously as a host material in an emitting layer, it is preferably used in combination with another compound. The invention therefore further provides a mixture comprising at least one compound of formula (1) or formula (1A) or at least one preferred compound of one of formulas (5), (6), (7), (8), (9), (10), (11) and (12), or a compound of Table 1 or one of the compounds E1 to E36 and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence) and / or a solvent. Suitable matrix materials and emitters that can be used in this mixture according to the invention,are described below. If the further material is a solvent, the mixture is synonymously a formulation comprising at least one compound according to the invention, as described above, and at least one solvent. The solvent can be an above-mentioned solvent or a mixture of these solvents. The present invention further provides an organic electronic device comprising an anode, a cathode, and at least one organic layer comprising at least one compound of formula (1) or formula (1A) or at least one preferred compound of one of formulas (5), (6), (7), (8), (9), (10), (11), and (12), or a compound of Table 1 or one of compounds E1 to E36. The organic electronic device can, for example, consist of organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic electroluminescent devices,organic solar cells (OSCs), organic optical detectors, organic photoreceptors. The organic electronic device is preferably an organic electroluminescent device. The organic electroluminescent device according to the invention (synonymously organic electroluminescent device) is, for example, an organic light-emitting transistor (OLET), an organic field quench device (OFQD), an organic light-emitting electrochemical cell (OLEC),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. The device according to the invention is particularly preferably an OLED. The organic layer of the device according to the invention preferably contains, 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 can also contain several layers from this group, preferably selected from EML, HIL, HTL, ETL, EIL and HBL.Interlayers can also be introduced between two emitting layers, which, for example, have an exciton-blocking function. If multiple emitting layers are present, they preferably have a total of several emission maxima between 380 nm and 750 nm, resulting in an overall white emission, i.e., different emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. One emitting layer can also contain several fluorescent and / or phosphorescent compounds. Systems with three emitting layers are particularly preferred, with the three layers exhibiting blue, green, and orange or red emission. As an alternative to the combination as described above,An emitting layer can also exhibit yellow emission. Such combinations are known to the person skilled in the art. The organic electroluminescent device according to the invention can also be a tandem electroluminescent device, in particular for white-emitting OLEDs. The device can also contain inorganic materials or layers composed entirely of inorganic materials. It is not difficult for the person skilled in the art to resort to 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 common considerations regarding the chemical and physical properties of the materials, since it is known to themthat the materials in an organic electroluminescent device interact with one another. This applies, for example, to the energy positions of the orbitals (HOMO, LUMO) or the position of triplet and singlet energies, but also to other material properties. The compound of formula (1) or formula (1A) according to the invention, as described above or preferably described, can be used in different layers, depending on the precise structure. An organic electroluminescent device comprising a compound according to formula (1) or formula (1A) and the preferred embodiments described above in an emitting layer as a matrix material for fluorescent emitters, phosphorescent emitters, or for emitters exhibiting TADF (thermally activated delayed fluorescence) is preferred.in particular 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 in an electron-transport layer. The present invention further provides an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer which comprises at least one compound of formula (1) or formula (1A) or which comprises at least one preferred compound of one of formulas (5), (6), (7), (8), (9), (10), (11) and (12),or a compound of Table 1 or one of the compounds E1 to E36. In one embodiment of the present invention, at least one further matrix material is selected for the device according to the invention in the light-emitting layer, which is used with compounds of the formula (1) or of the formula (1A), as described above or preferably described, or with the compounds of Table 1 or the compounds E1 to E36. The present invention accordingly further provides an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer which contains at least one compound of the formula (1) or of the formula (1A) or which contains at least one preferred compound of one of the formulas (5), (6), (7), (8), (9), (10), (11) and (12),or a compound of Table 1 or one of the compounds E1 to E36 and at least one further matrix material. The present invention accordingly further provides an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer which contains at least one compound of formula (1) or formula (1A) or at least one preferred compound of one of the formulas (5), (6), (7), (8), (9), (10), (11) and (12), or a compound of Table 1 or one of the compounds E1 to E36 and two further matrix materials. Suitable matrix materials which 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,Azaboroles or boronate esters, triazine derivatives, zinc complexes, diazasilole or tetraazasilole derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or dibenzofuran derivatives. Likewise, another phosphorescent emitter that emits at shorter wavelengths 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 significantly, in charge transport, such as a wide-band-gap compound. In the present application, a wide-band-gap material is understood to mean a material within the meaning of the disclosure of US Pat. No. 7,294,849, which is characterized by a band gap of at least 3.5 eV, where the band gap is understood to be the difference between the HOMO and LUMO energy of a material. Particularly suitable hole-transporting matrix materials which advantageously react with compounds of the formulas (5), (6), (7), (8), (9), (10), (11) and (12),as described above or as preferred, can be combined in a mixed matrix system, can be selected from the compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), as described below. Accordingly, a further subject of the present invention is an organic electronic 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 contains at least one compound of the formula (1) or of the formula (1A) as matrix material 1, as described above or as preferred, and at least one compound of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) as matrix material 2, where the symbols and indices used are: A 1 is C(R 7 )2, NR 7 , O or S; L is a bond, O, S, C(R 7 )2or NR7 ; A is at each occurrence independently a group of the formula (HH-4-1) or (HH-4-2), X2is the same or different at each occurrence CH, CR 6 or N, where a maximum of 2 symbols can represent X2N; * indicates the binding site to the formula (HH-4); U 1 , U 2 are a bond, O, S, C(R 7 )2or NR 7 ; R 6 is, identically or differently at each occurrence, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; two radicals R 6 also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar5, identically or differently at each occurrence, independently represents an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is reacted with one or more radicals R 7 may be substituted; R 7 is the same or different at each occurrence D, F, Cl, Br, I, N(R 8 )2, CN, NO2, 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)2R 8 , OSO2R 8, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 8 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted; two or more radicals R 7 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R 7 no such ring system; R 8is, on each occurrence, the same or different, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may also be replaced by F; c, c1, c2 each independently denote 0 or 1 on each occurrence, where the sum of the indices on each occurrence is c+c1+c2 = 1; d, d1, d2 each independently denote 0 or 1 on each occurrence, where the sum of the indices on each occurrence is d+d1+d2 = 1; q, q1, q2 each independently denote 0, 1, 2, 3 or 4 on each occurrence; s is, on each occurrence, the same or different, 0, 1, 2, 3 or 4; t is, on each occurrence, the same or different, 0, 1, 2, or 3; u is the same or different at each occurrence: 0, 1, or 2; u1, u2 each independently mean 0 or 1 at each occurrence, where the sum u1 + u2 = 1; and v is 0, 1, 2, or 3.Particularly preferred compounds are those of formula (HH-1) and formula (HH-5). Preferred compounds of formula (HH-4) are compounds of formula (HH-4-A).

[0007] where X2 is independently CH or CR 6 means and Ar5, R 6 , q, q1, q2 and v have a previously indicated or preferred meaning. Preferred compounds of formula (HH-5) are compounds of formulas (HH-5-A) to (HH-5-E),

[0008] where Ar5, R 6 , s and u have a previously indicated or preferred meaning. In compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-5) or (HH-6) or their preferred structures, s is preferably 0 or 1 when the radical R 6 is different from D, or particularly preferably 0. In compounds of the formulas (HH-1), (HH-2) or (HH-3), t is preferably 0 or 1 if the radical R 6is different from D, or particularly preferably 0. In compounds of the formulas (HH-1), (HH-2), (HH-3) or (HH-5) or their preferred structures, u is preferably 0 or 1 when the radical R 6 is different from D, or particularly preferably 0. The sum of the indices s, t and u in compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-5), (HH-6) or their preferred structures is preferably at most 6, particularly preferably at most 4 and particularly preferably at most 2. This preferably applies when R 6 is different from D. In compounds of the formula (HH-4) or their preferred structure, c, c1, c2 each independently of one another at each occurrence is 0 or 1, where the sum of the indices at each occurrence is c+c1+c21. Preferably, c2 has the meaning 1. In compounds of the formula (HH-4) or their preferred structure, L is preferably a single bond or C(R 7 )2, where R 7has a meaning mentioned above, particularly preferably L is a single bond. In formula (HH-4-1), v is preferably 0 or 1 when the radical R 6 is different from D. In formula (HH-4-2) U 1 or U 2 when occurring, preferably a single bond or C(R 7 )2, where R 7 has a meaning mentioned above, particularly preferred are U 1 or U 2 a single bond when occurring. In formula (HH-4-2), q, q1, q2 are preferably 0 or 1 when the radical R 6 is different from D. In a preferred embodiment of the compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-6) or their preferred structures, which can be combined according to the invention with compounds of the formula (1) or the formula (1A) or preferred compounds of the formula (1) or the formula (1A), as described above, R 6identically or differently on each occurrence 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, where the alkyl group is in each case substituted with one or more radicals R 7 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, preferably having 5 to 40 ring atoms, each substituted by one or more radicals R 7 may be substituted. In a preferred embodiment of the compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-6) or their preferred structures, which can be combined according to the invention with compounds of the formula (1) or the formula (1A) or preferred compounds of the formula (1) or the formula (1A), as described above, R 6identically or differently on each occurrence selected from the group consisting of D or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which is reacted with one or more radicals R 7can be substituted. Preferably, Ar5in compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-5), (HH-6) or their preferred structures are 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 can be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline,Quinazoline, quinoxaline, phenanthrene or triphenylene, each of which is substituted with one or more radicals R, 7 may be substituted. Preferably, Ar5 is unsubstituted. If A 1 in formula (HH-2) or (HH-3) or (HH-6) for NR 7 the substituent R 7 which is bonded to the nitrogen atom, preferably represents an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more radicals R 8 In a particularly preferred embodiment, this substituent R 7 identical or different on each occurrence, represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 18 aromatic ring atoms. Preferred embodiments for R 7are phenyl, biphenyl, terphenyl and quaterphenyl, which are preferably unsubstituted, as well as radicals derived from triazine, pyrimidine and quinazoline, which are substituted by one or more radicals R 8 can be substituted. If A 1 in formula (HH-2) or (HH-3) or (HH-6) for C(R 7 )2, the substituents R 7 which are bonded to this carbon atom, preferably identically or differently on each occurrence, represent a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 8 R is particularly preferably 7 represents a methyl group or a phenyl group. The radicals R 7also form a ring system with each other, resulting in a spiro system. In a preferred embodiment of the compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-6) and their preferred structures, these compounds are partially or fully deuterated, particularly preferably fully deuterated. The preparation of the compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-6) and their preferred structures are generally known, and some of the compounds are commercially available. Compounds of the formula (HH-4) or their preferred structure are disclosed, for example, in WO 2021 / 180614 A1, pages 110 to 119, in particular as examples on pages 120 to 127. Their preparation is disclosed in WO 2021 / 180614 A1 on page 128 and in the synthesis examples on pages 214 to 218. The preparation of the triarylamines of formula (HH-6) is known to the person skilled in the art and some of the compounds are commercially available.If the at least one further matrix material is a deuterated compound, it is possible for this at least one matrix material to be a mixture of deuterated compounds of the same basic chemical structure, which differ only in the degree of deuteration. In a preferred embodiment of the at least one further matrix material, this is a mixture of deuterated compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-6) or their preferred structures, as described above, wherein the degree of deuteration of these compounds is at least 50% to 90%, preferably 70% to 100%. The statements regarding deuterated mixtures and the preparation of deuterated materials, as described above for compounds of the formula (1) or (1A), apply here accordingly.In a preferred embodiment of the at least one further matrix material, this is a mixture of deuterated compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-6) and / or their preferred structures, as described above, wherein the degree of deuteration of these compounds is at least 50% to 90%, preferably 70% to 100%. Examples of suitable further matrix materials for a combination with compounds of the formula (1) or the formula (1A), as described above or preferably described, are the compounds described in WO2019 / 229011 A1, Table 3, pages 137 to 203, which can also be partially or fully deuterated. Examples of suitable further matrix materials for a combination with compounds of the formula (1) or the formula (1A) or preferred compounds of the formula (1) orof formula (1A), as previously described or preferably described, are the compounds described in WO 2021 / 180625 A1, Table 3, pages 131 to 137 and in Table 4, pages 137 to 139, which may also be partially or fully deuterated. Examples of suitable further matrix materials for combination with compounds of formula (1) or formula (1A) or preferred compounds of formula (1) or formula (1A), as previously described or preferably described, are the compounds described in KR 2023 / 0034896 A, on pages 42 to 47, compounds [2-1] to [2-110], or on pages 49 to 51, compounds [3-1] to [3-26]. For a combination with compounds of formulas (5), (6), (7), (8), (9), (10), (11) and (12), as described above or preferably described, compounds of formula (HH-1) and / or formula (HH-5) are particularly suitable, as described above or preferably described.For a combination with compounds of the formulas (5), (6), (7), (8), (9), (10), (11) and (11), as described above or preferably described, compounds of the formula (HH-1) are particularly suitable in which at least one group Ar5 represents a heteroaromatic ring system having 5 to 40 ring atoms which is reacted with one or more radicals R. 7may be substituted and / or compounds of the formula (HH-5). For a combination with a compound of the formulas (5), (6), (7), (8), (9), (10), (11) and (12), as described above or preferably described, compounds of the formula (HH-5) are very particularly preferably suitable.] Further examples of preferred host materials of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6) for a combination with compounds of the formula (1) or the formula (1A) or preferred compounds of the formula (1) or the formula (1A), as described above or particularly preferably described, are the structures listed below in Table 3 and Table 4. Table 3:

[0009]

[0010] n in Table 3 above means the number of D atoms in the respective compound and is 0 or D1 to D max , preferably D1 to D max . If n = 0, this means that the compound is non-deuterated. n = D1 means that in the respective compound, one H atom is replaced by a D atom. D max means the maximum number of D atoms possible in the respective compound. The maximum number of D max can vary from connection to connection. D maxcan assume the following values ​​depending on the compound: 20, 24, 26, 28, 30, 31, 32, 34, 35, 36, 37, 38 and 40. Particularly preferred compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), which are selected according to the invention and are preferably used in combination with at least one compound of the formula (1) or the formula (1A) in the electroluminescent device according to the invention, are the compounds of the following Table 4.

[0011] The aforementioned host materials of formula (1) or formula (1A) and their preferred embodiments, or the compounds of Table 1 and compounds E1 to E36, can be combined in any desired manner in the device according to the invention with the aforementioned matrix materials / host materials, the matrix materials / host materials of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), or (HH-6), as well as their preferred embodiments in Table 3, or compounds H1 to H48. Very particularly preferred mixtures of the compounds of formula (1) or formula (1A) with the host materials of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), or (HH-6) for the device according to the invention are obtained by combining compounds E1 to E36 with compounds H1 to H48, as shown below in Table 5. The first mixture M1, for example, is a combination of compound E1 with H1. Table 5:

[0012] The concentration of the host material of formula (1) or formula (1A), as described above or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 5 wt.% to 90 wt.%, preferably in the range from 10 wt.% to 85 wt.%, more preferably in the range from 20 wt.% to 85 wt.%, even more preferably in the range from 30 wt.% to 80 wt.%, very particularly preferably in the range from 20 wt.% to 60 wt.% and most preferably in the range from 30 wt.% to 50 wt.%, based on the total mixture or based on the total composition of the light-emitting layer.The concentration of the sum of all host materials of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), as described above or described as preferred, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 10 wt.% to 95 wt.%, preferably in the range from 15 wt.% to 90 wt.%, more preferably in the range from 15 wt.% to 80 wt.%, even more preferably in the range from 20 wt.% to 70 wt.%, very particularly preferably in the range from 40 wt.% to 80 wt.% and most preferably in the range from 50 wt.% to 70 wt.%, based on the total mixture or based on the total composition of the light-emitting layer. The present invention also relates to a mixture which, in addition to the aforementioned host materials of the formula (1) orof formula (1A), hereinafter referred to as host material 1, and the host material of at least one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), hereinafter referred to as host material 2, as previously described or preferably described, contains at least one phosphorescent emitter. The present invention also relates to a mixture selected from M1 to M1728, which contains at least one phosphorescent emitter. It is furthermore preferred to use a mixture of two or more triplet emitters together with a matrix of host material 1 and host material 2. The triplet emitter with the shorter-wave emission spectrum serves as a co-matrix for the triplet emitter with the longer-wave emission spectrum. 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 the formulas (1) orof formula (1A) and at least one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), as previously described or preferably described, in particular the material combinations M1 to M1728, contains at least one phosphorescent emitter. The term phosphorescent emitters typically includes compounds in which the light emission occurs through a spin-forbidden transition from an excited state with 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, for example a quintet state. A transition from a triplet state is preferably understood here.Particularly suitable phosphorescent emitters (= triplet emitters) are compounds that emit light upon suitable excitation, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are used as phosphorescent emitters, in particular compounds containing iridium or platinum. For the purposes of the present invention, all luminescent compounds containing the above-mentioned metals are considered phosphorescent emitters.In general, all phosphorescent complexes as used in the prior art for phosphorescent OLEDs and as known to those skilled in the art in the field of organic electroluminescent devices are suitable. Preferred phosphorescent emitters according to the present invention correspond to the formulas (I), (II), (III), (IV) or (V):.

[0013] where the symbols and indices for these formulas (I), (II), (III), (IV) and (V) have the following meaning: R1 is H or D, R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium. Preferred phosphorescent emitters according to the present invention correspond to the formulas (VI), (VII) or (VIII):

[0014] where the symbols and indices for these formulas (VI), (VII) and (VIII) have the following meaning: R1 is H or D, R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium. Preferred phosphorescent emitters according to the present invention correspond to formula (IX), where the symbols and indices for this formula (IX) have the meaning: n + m is 3, n is 1 or 2, m is 2 or 1, X is, identically or differently on each occurrence, N or CR, R is, identically or differently on each occurrence, H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 7 C atoms which may be partially or fully substituted with deuterium or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms which may be partially or fully substituted with deuterium.The invention accordingly further provides an organic electroluminescent device as described above or preferably described, characterized in that the light-emitting layer, in addition to the host materials 1 and 2, contains at least one phosphorescent emitter which corresponds to the formula (IX), as described above. In emitters of the formula (IX), n is preferably 1 and m is preferably 2. In emitters of the formula (IX), one X is preferably selected from N and the other Xs are CR or all Xs, identical or different on each occurrence, are CR. In emitters of the formula (IX), at least one R is preferably different from H. In emitters of the formula (IX), two Rs are preferably different from H and have one of the meanings otherwise given above for the emitters of the formula (IX).Preferred examples of phosphorescent emitters are described in WO 2019 / 007867 A1 on pages 120 to 126 in Table 5 and on pages 127 to 129 in Table 6. The emitters are incorporated into the description by this reference. Particularly preferred examples of phosphorescent emitters are listed in Table 6 below. Table 6:.

[0015] In the mixtures according to the invention or in the light-emitting layer of the device according to the invention, each mixture selected from the sum of the mixtures M1 to M1728 is preferably combined with a compound of the formulas (I) to (IX) or a compound from Table 6. 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 very particularly preferably a green-emitting layer. A yellow-emitting layer is understood to mean a layer whose photoluminescence maximum is in the range from 540 to 570 nm. An orange-emitting layer is understood to mean a layer whose photoluminescence maximum is in the range from 570 to 600 nm.A red-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 600 to 750 nm. A green-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 490 to 540 nm. A blue-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 440 to 490 nm. The photoluminescence maximum of the layer is determined by measuring the photoluminescence spectrum of the layer with a layer thickness of 50 nm at room temperature, wherein the layer contains the inventive combination of host material 1 of formulas (5), (6), (7), (8), (9), (10), (11) or (12) and host material 2, consisting of at least one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), and the corresponding emitter. The photoluminescence spectrum of the layer is recorded, for example, using a commercially available photoluminescence spectrometer.The photoluminescence spectrum of the selected emitter is usually measured in oxygen-free solution, 10. -5molar, measured at room temperature, and any solvent in which the selected emitter dissolves at the specified concentration is suitable. Particularly suitable solvents are usually toluene or 2-methyl-THF, but also dichloromethane. The measurement is carried out using a commercially available photoluminescence spectrometer. The triplet energy T1 in eV is determined from the photoluminescence spectra of the emitters. First, the peak maximum Plmax. (in nm) of the photoluminescence spectrum is determined. The peak maximum Plmax. (in nm) is then converted to eV according to: E(T1 in eV) = 1240 / E(T1 in nm) = 1240 / PLmax. (in nm). Preferred phosphorescent emitters are therefore yellow emitters, preferably of formulas (I) to (IX) or from Table 6, whose triplet energy T1 is preferably between ~2.3 eV and ~2.1 eV. Preferred phosphorescent emitters are therefore green emitters, preferably of formulas (I) to (IX) or from Table 6, whose triplet energy T1 is preferably between ~2.5 eV to ~2.3 eV. Accordingly, particularly preferred phosphorescent emitters are green emitters, preferably of the formulas (I) to (IX) or from Table 6, as described above, whose triplet energy T1 is preferably ~2.5 eV to ~2.3 eV. Very particular preference is given to selecting green emitters, preferably of the formulas (I) to (IX) or from Table 6, as described above, for the mixture according to the invention or emitting layer according to the invention. Fluorescent emitters can also be present in the light-emitting layer of the device according to the invention or in the mixture according to the invention. 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 having at least 14 ring atoms.Preferred examples are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysenamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to be a compound in which one diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. An aromatic anthracenediamine is understood to be a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10-position. Aromatic pyreneamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, with the diarylamino groups on the pyrene preferably being bonded in the 1-position or 1,6-position. Further preferred emitting compounds are indenofluorenamines or diamines, benzoindenofluorenamines or diamines, and dibenzoindenofluorenamines or diamines, as well as indenofluorene derivatives with condensed aryl groups.Pyrene-arylamines are also preferred. Also preferred are benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives linked to furan units or to thiophene units. Furthermore, the light-emitting device or the mixture according to the invention can also contain materials that exhibit TADF (thermally activated delayed fluorescence). In a further preferred embodiment of the present invention, the at least one light-emitting layer of the organic electroluminescent device can have three or four different matrix materials, preferably three different matrix materials.These corresponding mixed-matrix systems can consist of the matrix materials described for host material 1 and host material 2, but they can also contain, as a third or fourth matrix material, for example, in addition to host material 1 or host material 2, wide-band-gap materials, bipolar host materials, electron-transport materials (ETM), or hole-transport materials (HTM). The mixed-matrix system is preferably optimized for an emitter of one of the formulas (I) to (IX) or for an emitter from Table 6. According to one embodiment of the present invention, the mixture contains no further constituents, i.e., functional materials, in addition to the constituents of the host material of formula (1) or formula (1A) and host material 2, as described above or preferably described. These are material mixtures that are used as such to produce the light-emitting layer.These mixtures are also referred to as premix systems, which are used as the sole material source during the vapor deposition of the host materials for the light-emitting layer and which have a constant mixing ratio during vapor deposition. This allows the vapor deposition of a layer with a uniform distribution of the components to be achieved in a simple and rapid manner, without the need for precise control of a large number of material sources. According to an alternative embodiment of the present invention, the mixture contains, in addition to the constituents of the host material of formula (1) or formula (1A) and the host material 2, as described above or preferably described, a phosphorescent emitter as described above. With a suitable mixing ratio during vapor deposition, this mixture can also be used as the sole material source.Premix systems consisting of two matrix materials are preferred, namely a compound of the formulas (5), (6), (7), (8), (9), (10), (11) or (12) and a compound of one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6). Premix systems consisting of three matrix materials are preferred, namely a compound of (5), (6), (7), (8), (9), (10), (11) or (12) and two compounds of one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6). The components or constituents 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 host materials 1 and 2, as described above or preferably described, optionally with the phosphorescent emitter, as described above or preferably described, is provided in a formulation containing at least one solvent. Suitable formulations have been described previously.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.%, very particularly preferably between 97 and 80 vol.% of matrix material made of at least one compound of the formulas (5), (6), (7), (8), (9), (10), (11) or (12) and at least one compound of one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) according to the preferred embodiments, based on the total composition of emitter and matrix material. Accordingly, 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.%, very particularly 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 above-mentioned amounts in vol.%. The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the organic layer contains a hole-injection layer (HIL) and / or a hole-transport layer (HTL), whose hole-injecting material and hole-transporting material belong to the class of arylamines. Preferred hole-injecting materials and / or hole-transporting materials are shown in the following table. The materials in this table can also be partially or fully deuterated. Table: the following compounds can also be partially or fully deuterated.

[0016]

[0017]

[0018] The sequence of layers in the organic electroluminescent device according to the invention is preferably as follows: anode / hole-injection layer / hole-transport layer / emitting layer / hole-blocking layer / electron-transport layer / electron-injection layer / cathode. This sequence of layers is a preferred sequence. It should be noted again that not all of the layers mentioned need to be present and / or that additional layers may be present. All materials used in the prior art as electron-transport materials in the electron-transport layer can be used as materials for the electron-transport layer.Particularly suitable are aluminum complexes, for example Alq3, zirconium complexes, for example Zrq4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives. The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the organic layer contains an electron injection layer (EIL) and / or an electron transport layer (ETL) and / or a hole blocking layer, the electron-injecting material and electron-transporting material of which is selected from the compounds of formulas (5), (6), (7), (8), (9), (10), (11), or (12), as described above or preferably described.Furthermore, an electronic device, preferably an organic electroluminescent device, is preferred, which comprises one or more compounds according to the invention in one or more electron-transport layers in combination with a material having a high dielectric constant. Materials having a high dielectric constant include, for example, alkali metal or alkaline earth metal fluorides, alkali metal or alkaline earth metal oxides, alkali metal or alkaline earth metal carbonates, lanthanide compounds, or organic alkali metal complexes, with a combination of organic alkali metal complexes, preferably with lithium quinolate = LiQ, with a compound according to the invention being particularly preferred. Suitable materials having a high dielectric constant include, for example, LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, Yb2O3, or lithium quinolate.The two different materials of the electron-transport layer can be present in a ratio of 1:50 to 50:1, preferably 1:10 to 10:1, particularly preferably 1:4 to 4:1, and most preferably 1:2 to 2:1. It is also possible to introduce an electron-injection layer between the electron-transport layer according to the invention and the cathode. Suitable materials for the electron-injection layer are, for example, LiF, lithium quinolinate, CsF, Cs2CO3, Li2O, LiBO2, K2SiO3, Cs2O, or Al2O3. Metals with a 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, Yb, Sm), are suitable as the cathode of the device according to the invention. Alloys made from an alkali or alkaline earth metal and silver are also suitable, for example an alloy made from magnesium and silver.In multilayer structures, in addition to the metals mentioned, other metals with a relatively high work function can be used, such as Ag or Al, in which case combinations of the metals, such as Ca / Ag, Mg / Ag, or Ba / Ag, are generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor. Examples of suitable materials for this include alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3). Lithium quinolinate (LiQ) can also be used. The thickness of this layer is preferably between 0.5 and 5 nm. Materials with a high work function are preferred as the anode. The anode preferably has a work function greater than 4.5 eV vs. vacuum.On the one hand, metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. On the other hand, metal / metal oxide electrodes (e.g., Al / Ni / NiO) can also be used. x , Al / PtO x) may be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to enable either the irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive, doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of several layers, for example an inner layer made of ITO and an outer layer made of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.The organic electroluminescent device according to the invention is structured, contacted, and finally sealed during production (depending on the application), since the lifetime of the devices according to the invention is shortened in the presence of water and / or air. The production of the device according to the invention is not restricted by this. It is possible to coat one or more organic layers, including the light-emitting layer, using a sublimation process. The materials are heated 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 that the initial pressure is even lower, for example less than 10 -7mbar. The organic electroluminescent device according to the invention is preferably characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) method or by means of carrier gas sublimation. The materials are then sublimated at a pressure between 10 -5 -5mbar and 1 bar. A special case of this process is the OVJP (Organic Vapour Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (e.g. MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301). Furthermore, the organic electroluminescent device according to the invention is preferably characterized in that one or more organic layers comprising the composition according to the invention are produced from solution, for example by spin coating, or using any printing process, such as screen printing, flexographic printing, nozzle printing or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or inkjet printing. This requires soluble host materials 1 and 2 and phosphorescent emitters. 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. Hybrid processes are also possible, in which, for example, one or more layers are applied from solution and one or more additional layers are deposited by vapor deposition. These processes are generally known to those skilled in the art and can be applied to organic electroluminescent devices.The present invention therefore further provides a process for producing the organic electroluminescent device according to the invention, as described above 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 deposition, in particular using a sublimation process and / or 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 using a printing process. When produced by vapor deposition, there are basically two ways in which the organic layer according to the invention, preferably the light-emitting layer, can be applied or vapor-deposited onto any desired substrate or the previous layer.On the one hand, the materials used can each be placed in a single material source and then evaporated from the different material sources ("co-evaporation"). On the other hand, the different materials can be premixed ("premixed 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 a large number of material sources.The following methods are possible: A method for producing the organic electroluminescent device according to the invention, as described above or preferably described, characterized in that the organic layer, preferably the light-emitting layer, the electron transport layer and / or the hole blocking layer, is applied by vapor phase deposition, in particular with a sublimation method and / or with an OVPD (Organic Vapor Phase Deposition) method and / or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing method.A method for producing the organic electroluminescent device according to the invention, as described above or preferably described, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of the formulas (5), (6), (7), (8), (9), (10), (11) or (12) together with the further materials which form the light-emitting layer are deposited successively or simultaneously from at least two material sources from the gas phase.A method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein the at least one compound of formulas (5), (6), (7), (8), (9), (10), (11), or (12) is deposited from the vapor phase together with at least one further matrix material as a premix, sequentially 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). The electronic devices according to the invention, in particular organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art: 1.Electronic devices, in particular organic electroluminescent devices comprising compounds of the formula (1) or the formula (1A) and the preferred embodiments set out above and below, in particular as matrix material or as electron-conducting materials, have a very good lifetime. In this case, these compounds bring about a low roll-off, i.e. a low drop in the power efficiency of the device at high luminance levels. 2. Electronic devices, in particular organic electroluminescent devices comprising compounds of the formula (1) or the formula (1A) and the preferred embodiments set out above and below as electron-conducting materials and / or matrix materials, have an excellent efficiency. In this case, compounds according to the formula (1) orof formula (1A) and the preferred embodiments set out above and below, a low operating voltage when used in electronic devices. 3. The compounds according to the invention according to formula (1) or formula (1A) and the preferred embodiments set out above and below display very high stability and lifetime. 4. Using compounds according to formula (1) or formula (1A) and the preferred embodiments set out above and below, the formation of optical loss channels can be avoided in electronic devices, in particular organic electroluminescent devices. As a result, these devices are characterized by high PL and thus high EL efficiency of emitters and excellent energy transfer from the matrices to dopants. 5. The use of compounds according to formula (1) orof formula (1A) and the preferred embodiments outlined above and below in layers of electronic devices, in particular organic electroluminescent devices, leads to a high mobility of the electron conductor structures. 6. Compounds according to formula (1) or formula (1A) and the preferred embodiments outlined above and below exhibit excellent glass film formation. 7. Compounds according to formula (1) or formula (1A) and the preferred embodiments outlined above and below form very good films from solutions. 8. The compounds according to formula (1) or formula (1A) and the preferred embodiments outlined above and below have a triplet level T1, which can be, for example, in the range of 2.50 eV - 2.90 eV. These advantages mentioned above are not accompanied by an excessively high deterioration of the other electronic properties.It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Any feature disclosed in the present invention may, unless explicitly excluded, be replaced by alternative features serving the same, equivalent, or similar purpose. Thus, unless otherwise stated, any feature disclosed in the present invention is to be considered as an example of a generic series or as an equivalent or similar feature. All features of the present invention may be combined with each other in any way, unless certain features and / or steps are mutually exclusive. This applies in particular to preferred features of the present invention. Likewise, features of non-essential combinations may be used separately (and not in combination).The teaching of technical practice disclosed by the present invention can be abstracted and combined with other examples. The invention is explained in more detail by the following examples, without intending to limit it. Examples: Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be obtained from ALDRICH or ABCR. The numbers given for the non-commercially available starting materials are the corresponding CAS numbers. Synthesis examples Example 1a: 12'-(4,6-bis(phenyl-d5)-1,3,5-triazin-2-yl-12'H-spiro[fluorene-9,7'-indeno[1,2-a]carbazole] 1a. 4.2 g of 60% NaH in mineral oil (0.11 mol) are dissolved in 300 mL of dimethylformamide under a protective atmosphere. 43 g (0.106 mol) of spiro[9H-fluorene-9,7'(1'H)-indeno[1,2- a]carbazole] are dissolved in 250 mL of DMF and added dropwise to the reaction mixture. After 1 hour at room temperature, a solution of 2-chloro-4,6-bis(phenyl-d5)-[1,3,5]triazine (34.5 g, 0.12 mol) in 200 mL of THF is added dropwise. The reaction mixture is then stirred at room temperature for 12 hours. After this time, the reaction mixture is poured onto ice. The precipitated solid is warmed to room temperature, filtered, and washed with ethanol and heptane. The residue is extracted with hot toluene, recrystallized from toluene / n-heptane, and finally sublimed under high vacuum; the purity is 99.9%. The yield is 28.4 g (44.5 mmol; 42%). The following compounds are prepared analogously: Example 2a: 12'-(4-([1,1'-biphenyl]-4-yl-d9)-6-(phenyl-d5)-1,3,5-triazin-2-yl-12'H-spiro[fluorene- 9,7'-indeno[1,2-a]carbazole]-1,1',2,2',3,3',4,4',5,5',6,6',7,8,8',9',10',11'-d18 2a 16 g of 12'-(4-([1,1'-biphenyl]-4-yl)-6-(phenyl)-1,3,5-triazin-2-yl-12'H-spiro[fluorene-9,7'-indeno[1,2-a]carbazole]- (22.4 mmol; 1.00 eq) is suspended in 190 mL (80 eq) of toluene-d8. 20 mL (10.00 eq) of trifluoromethanesulfonic acid is added to this mixture while cooling. The reaction mixture is stirred at ambient temperature for 6 hours. Subsequently, 40 mL (130 eq) of deuterium oxide is added dropwise at 0°C. After neutralization with a NaOH solution (38 mL; 20%), the reaction mixture is treated with 150 mL of heptane, the precipitated solid is filtered, and ethanol. The solvent is removed under reduced pressure. The product shown above, in a mixture with portions of H / D isotopomers and H / D isotopologues, is precipitated under high vacuum (p = 5 x 10 -7mbar) (12 g, 75% of theory) purity 99.9%). The following compounds are prepared analogously: Production of the OLEDs The following comparative examples C1 to C7 and inventive examples E1 to E6 (see Tables 7 and 8) present the data for various OLEDs. Examples E1 to E6 show data for OLEDs according to the invention. The substrate for the OLEDs in Table 7 is glass flakes coated with structured ITO (indium tin oxide) with a thickness of 50 nm. The exact structure of the OLEDs can be found in Table 7. The materials required to produce the OLEDs are shown in Table 9, unless previously described. All materials are thermally vapor-deposited in a vacuum chamber. The emission layer always consists of at least one matrix material (also called host material) and an emitting dopant (dopant, emitter), which is admixed with the matrix material(s) in a specific volume fraction by co-evaporation.A specification such as eV2:hV1:TEG2 (32%:60%:8%) 40 nm means that the material eV2 is present in a volume fraction of 32% as host material 1, the compound hV1 as host material 2 in a fraction of 60%, and TEG2 in a fraction of 8% in a 40 nm thick layer. Analogously, the hole injection layer (HIL) and the electron transport layer (ETL), for example, can also consist of a mixture of two materials. OLEDs are characterized as standard. For this purpose, the electroluminescence spectra and current-voltage-luminance characteristics (IUL characteristics) are measured, from which the EQE is calculated. The calculation is performed assuming a Lambertian radiation characteristic. The electroluminescence spectra are determined at a luminance of 1000 cd / m². The value U10 in Table 8 refers to the voltage required for a current density of 10 mA / cm². EQE10 refers to the external quantum efficiency at a current density of 10 mA / cm².The lifetime LT is defined as the time after which the luminance drops from an initial luminance L0 (in cd / m²) to a certain proportion L1 (in cd / m²) when operated at a constant current density j0 in mA / cm². A value of L1 / L0 = 90% in Table 8 means that the lifetime specified in column LT corresponds to the time (in hours) after which the luminance drops to 90% of its initial value (L0). Use of mixtures according to the invention in OLEDs The compounds or material combinations according to the invention can be used in the emission layer in phosphorescent green OLEDs. 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 E1 to E6 show data for OLEDs according to the invention. The examples according to the invention show, in particular, a clear advantage in the lifetime of the device. Table 7: Structure of the OLEDs.

[0019] Table 8: OLED data Table 9: Structural formulas of the materials used for the OLEDs, unless previously described

Claims

Claims 1. Compound according to formula (1) or formula (1A), where the following applies to the symbols and indices used: Y is the same or different for each occurrence CR 1 or N, with the proviso that at least one group Y is N; X is the same or different at each occurrence CR 1 or N; or two adjacent Xs represent S, O or NR 1 , so that a five-membered ring is formed; or two adjacent X represent a group of the following formula (2), (3) or (4), where ^ denotes the corresponding adjacent groups X in formula (1) or formula (1A); V is at each occurrence, the same or different from C(R 1 )2, NR 1 , O, S, BR 1 , Si(R 1 )2or C=O; Z is the same or different at each occurrence CR 1or N; Ar is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is substituted by one or more radicals R 1 may be substituted; R is at each occurrence, identically or differently, selected from the group consisting of H, D, F, Cl, Br, I, CN, N(Ar 1 )2, a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, with one or more non-adjacent CH2 groups being substituted by R 2 C=CR 2 , C≡C or O and where one or more H atoms can be replaced by D or F, or an aromatic ring system with 6 to 60 aromatic ring atoms, which is substituted with one or more radicals R 2may be substituted; two adjacent substituents R may form a monocyclic or polycyclic, aliphatic or aromatic ring system which may be substituted with one or more radicals R 2 may be substituted; R 1 is selected at each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO2, N(Ar 1 )2, N(R 2 )2, C(=O)Ar 1 , C(=O)R 2 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, Si(Ar 1 )3, Si(R 2 )3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, with one or more non-adjacent CH2 groups being substituted by R 2 C=CR 2 , C≡C, Si(R 2)2, C=O, C=S, C=NR 2 , P(=O)(R 2 ), SO, SO2, NR 2 , O, S or CONR 2 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 with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted with one or more radicals R 2 may be substituted; optionally two adjacent substituents R 1 form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which, with one or more radicals R 2 can be substituted; Ar 1is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is substituted by one or more non-aromatic radicals R 2 can be substituted; two residues Ar 1 which bind to the same N-atom or P-atom, also by a single bond or a bridge, selected from N(R 2 ), C(R 2 )2, O or S, may be bridged together; R 2 is selected, identically or differently at each occurrence, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN, where two or more adjacent substituents R 2can form a mono- or polycyclic, aliphatic ring system with each other; m, n is the same or different on each occurrence and is 0 or 1, with the proviso that m + n ≥ 1; p is the same or different on each occurrence and is 0, 1, 2, 3 or 4; q is 0, 1 or 2, characterized in that the compound according to formula (1) or according to formula (1A) contains at least one deuterium atom as a substituent.

2. A compound according to claim 1, characterized in that at least one of the radicals R of the spirobifluorene group and / or one of the radicals R 1 of the 6-membered ring formed from the X groups is a D atom.

3. A compound according to claim 1 or 2, characterized in that at least one of the radicals R 1of the aromatic or heteroaromatic ring system Ar and / or the 6-membered ring formed from the Y groups is a D atom.

4. A compound according to one or more of claims 1 to 3, characterized in that the degree of deuteration of the compounds of formula (1) or formula (1A) is in the range from 1 to 100 mol%, preferably in the range from 10 to 100 mol%.

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

6. A mixture comprising at least one compound according to formula (1) or formula (1A) according to one or more of claims 1 to 4 and at least one further compound selected from the group of electron transport materials, electron injection materials, hole blocking materials, materials which have a high dielectric constant and / or a solvent.

7. An organic electronic device comprising an anode, a cathode and at least one organic layer comprising at least one compound according to formula (1) orFormula (1A) according to one or more of claims 1 to 4.

8. Organic electronic device according to claim 7, wherein the electronic device is an electroluminescent device.

9. Organic electronic device according to claim 7 or 8, wherein the organic layer contains at least one light-emitting layer which contains at least one compound of formula (1) or formula (1A) according to one of claims 1 to 4.

10. Organic electronic device according to one or more of claims 7 to 9, characterized in that the light-emitting layer contains a further matrix material.

11. Organic electroluminescent device according to claim 10, characterized in that the further matrix material corresponds to a compound of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6). , - , where the symbols and indices used are: A 1is C(R 7 )2, NR 7 , O or S; L is a bond, O, S, C(R 7 )2or NR 7 ; A is at each occurrence independently a group of the formula (HH-4-1) or (HH-4-2), Formula (HH41) Formula (HH42); X2is the same or different at each occurrence CH, CR 6 or N, where a maximum of 2 symbols can represent X2N; * indicates the binding site to the formula (HH-4); U 1 , U 2 are a bond, O, S, C(R 7 )2or NR 7 ; R 6 is, identically or differently at each occurrence, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; two radicals R 6 also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar5, identically or differently at each occurrence, independently represents an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is reacted with one or more radicals R 7 may be substituted; R 7 is the same or different at each occurrence D, F, Cl, Br, I, N(R 8 )2, CN, NO2, 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)2R 8 , OSO2R8 , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 8 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted; two or more radicals R 7 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R 7 no such ring system; R 8is, identically or differently at each occurrence, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may also be replaced by F; c, c1, c2 each independently at each occurrence is 0 or 1, where the sum of the indices at each occurrence is c+c1+c2 = 1; d, d1, d2 each independently at each occurrence is 0 or 1, where the sum of the indices at each occurrence is d+d1+d2 = 1; q, q1, q2 each independently denote 0, 1, 2, 3 or 4 on each occurrence; s is the same or different on each occurrence and is 0, 1, 2, 3 or 4; t is the same or different on each occurrence and is 0, 1, 2 or 3; u is the same or different on each occurrence and is 0, 1 or 2; u1, u2 each independently denote 0 or 1 on each occurrence, where the sum u1 + u2 = 1; and v is 0, 1, 2 or 3.

12. Organic electronic device according to one or more of claims 7 to 11, characterized in that the light-emitting layer contains a phosphorescent emitter.

13. The organic electronic device according to claim 7 or 8, wherein the organic layer contains at least one electron-transport layer or an electron-injection layer or a hole-blocking layer containing the compounds according to formula (1) or formula (1A) according to any one of claims 1 to 4. 14.The organic electronic device according to one or more of claims 7 to 13, characterized in that it is an electroluminescent device selected from the group consisting of 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).

15. The method for producing an organic electronic device according to one or more of claims 7 to 14, characterized in that the organic layer is applied by vapor deposition or from solution.

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