Materials for organic electronic devices

Abstract

The present invention relates to compounds and organic electronic devices such as OLEDs (organic light emitting diodes) that contain these compounds, for example as hole transport materials and / or matrix materials, optionally combined with another matrix material. The present invention also relates to mixtures containing these compounds.

Description

[0001] Materials for organic electronic devices

[0002] Technical field

[0003] The present invention relates to compounds and organic electronic devices such as OLEDs (organic light-emitting diodes) which contain these compounds, for example as hole transport materials and / or matrix materials, optionally in combination with a further matrix material. The present invention further relates to mixtures containing these compounds.

[0004] State of the art

[0005] The design of organic electroluminescent devices (e.g., OLEDs or OLECs – organic light-emitting electrochemical cells), in which organic semiconductors are used as organic functional materials, is well established. In addition to fluorescent emitters, organometallic complexes exhibiting phosphorescence have become established as emitting materials. For quantum mechanical reasons, using organometallic compounds as phosphor emitters allows for up to four times the energy and power efficiency. Generally, there is still room for improvement in both singlet and triplet emission OLEDs, particularly with regard to efficiency, operating voltage, and lifetime.

[0006] The properties of organic electroluminescent devices are not solely determined by the emitters used. The other materials employed, such as host and matrix materials, hole-blocking materials, electron transport materials, and electron / exciton blocking materials, are also of particular importance. Improvements to these materials can lead to significant enhancements in electroluminescent devices. The term matrix material is commonly used to refer to a host material for phosphorescent emitters. This usage of the term "matrix material" is also applied to the present invention.

[0007] In the prior art, triarylamine compounds such as spirobifluorenamines and fluorenamines are known as hole transport and hole injection materials in electronic devices. Among others, carbazole derivatives, dibenzofuran derivatives, indenocarbazole derivatives, indolocarbazole derivatives, benzofurocarbazole derivatives, and benzothienocarbazole derivatives are used as matrix materials for phosphorescent emitters. Indolocarbazole derivatives, which can be used as matrix materials in OLEDs, are described, among others, in KR 10201800999539, US 2023 / 159550, US 2016 / 0293853, and WO 2011 / 128017.

[0008] However, there is still room for improvement in these compounds, for example for use as matrix materials, especially with regard to service life, but also with regard to the efficiency and operating voltage of the device.

[0009] The object of the present invention is therefore to provide compounds suitable for use in an organic electroluminescent device (synonymously used for use in an organic light-emitting device) and which, when used in this device, result in favorable properties, as well as to provide the corresponding organic light-emitting device. In particular, the object of the present invention is to provide compounds that lead to a long lifetime, good efficiency, and low operating voltage in a phosphorescent or fluorescent, especially phosphorescent, OLED. The properties of the matrix materials also have a significant influence on the lifetime and efficiency of the organic electroluminescent device.

[0010] It has now been found that organic light-emitting devices containing compounds according to the following formula (1) exhibit improvements over the prior art, particularly when the compounds are used as matrix material for phosphorescent emitters.

[0011] It was further found that the combination of at least one compound of formula (1) as the first host material and at least one electron-transporting compound, for example in combination with one or more compounds of formulas (A), (B), (C), (D) or (E), 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 (synonymous with organic light-emitting device), solves this problem and eliminates the disadvantages of the prior art.

[0012] Summary of the invention

[0013] A first object of the invention are compounds of formula (I), Formula (I), where:

[0014] Ar is an aromatic ring system with 6 to 40 ring atoms, separated by one or more R groups. 5 may be substituted or a heteroaromatic

[0015] Ring system selected from the group consisting of carbazole, dibenzofuran or dibenzothiophene, each of which is joined by one or more R groups 5 may be substituted;

[0016] R 1 , R 2 , R 3 , R 4are, in each occurrence, the same or different H, D, F, a straight-chain alkyl, alkoxy, or thioalkoxy group with 1 to 40 C atoms, a branched or cyclic alkyl, alkoxy, or thioalkoxy group with 3 to 40 C atoms, or an alkenyl group with 2 to 20 C atoms, wherein in each group one or more H atoms may be replaced by D, an aromatic ring system with 6 to 40 ring atoms, or a heteroaromatic ring system with 5 to 40 ring atoms, wherein the aromatic or heteroaromatic ring systems are each modified by one or more R groups 6 can be substituted; in this case, two or more adjacent residues R 1 , two or more adjacent residues R 2 , two or more adjacent residues R 3 , form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more Ds;

[0017] D is deuterium;

[0018] R 5 , R 6 are the same or different in each occurrence: D, F, OH, CN, a straight-chain alkyl group with 1 to 20 carbon atoms, a branched or cyclic alkyl group with 3 to 20 carbon atoms, in which one or more hydrogen atoms may be replaced by D or F, an aromatic ring system with 6 to 40 ring atoms, or a heteroaromatic ring system with 5 to 40 ring atoms, in which one or more hydrogen atoms may be replaced by D or an alkyl group with 1 to 4 carbon atoms; optionally, two or more adjacent R groups 5 , two or more adjacent residues R 6 , can form a mono- or polycyclic, aliphatic aromatic or heteroaromatic ring system which may be substituted with one or more D; wherein the compounds of formula (I) are partially or completely deuterated.

[0019] Another object of the invention is a mixture comprising at least one compound of formula (I) as previously described or more preferably described later, and at least one further compound selected from the group consisting of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0020] Another aspect of the invention is the use of at least one compound of formula (I) in an organic electronic device.

[0021] Another object of the invention is an organic electronic, preferably light-emitting, device comprising an anode, a cathode and at least one organic layer containing at least one compound of formula (I), as previously described or more preferably described later.

[0022] Description of the invention

[0023] In the present patent application, “D” or “D atom” denotes deuterium. The degree of deuteration, expressed in mol%, indicates the proportion of hydrogen atoms replaced by deuterium. Since deuterated compounds are often mixtures of compounds that differ in the precise position and proportion of D atoms, the degree of deuteration represents the average proportion of hydrogen atoms replaced by D. Thus, a degree of deuteration of 50 mol% means that, on average, 50 mol% of the hydrogen atoms in the compound are replaced by D, representing an average degree of deuteration.

[0024] An aryl group according to this invention contains 6 to 40 ring atoms, preferably carbon atoms. A heteroaryl group according to this invention contains 5 to 40 ring atoms, wherein the ring atoms comprise carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from nitrogen, oxygen, and / or sulfur. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e., phenyl, derived from benzene, or a simple heteroaromatic cycle, for example, derived from furan or thiophene, or a fused aryl or heteroaryl group, for example, derived from naphthalene, anthracene, phenanthrene, or benzopyrans.An aryl group with 6 to 30 carbon atoms is therefore preferably phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylenyl, fluoranthenyl, dibenzoanthracene, chrysenyl, or perylenyl, wherein the attachment of the aryl group as a substituent is not restricted. The aryl group according to this invention can bear one or more substituents, the suitable substituent being described below. Deuterium is preferred as the substituent.

[0025] In this context, a heteroaryl group is understood to be either a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine, or thiophene, or a condensed heteroaryl group, for example derived from quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, or carbazole. However, in the sense of this invention, the term heteroaryl group also includes a heteroaryl group that is bonded by a single bond to an aryl group or to another heteroaryl group, for example phenyl-bipyridyl or bipyridyl. The heteroaryl group in the sense of this invention may bear one or more substituents, the suitable substituent being described below. Deuterium is preferred as the substituent. If no such substituent is described, the heteroaryl group is unsubstituted.

[0026] An aromatic ring system according to this invention contains 6 to 40 carbon atoms in the ring system. The aromatic ring system comprises aryl groups, as previously described, and the term is used synonymously below.

[0027] An aromatic ring system with 6 to 18 carbon atoms is preferably selected from phenyl, biphenyl, naphthyl, phenanthryl, and triphenylenyl, which may bear one or more substituents, the suitable substituent being described below. Deuterium is preferred as the substituent. If no such substituent is described, the aromatic ring system is unsubstituted.

[0028] A heteroaromatic ring system according to this invention contains 5 to 40 ring atoms and at least one heteroatom. A preferred heteroaromatic ring system has 9 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system comprises heteroaryl groups as previously described, and the term is used synonymously hereafter.

[0029] An aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which can be linked via any position on the aromatic or heteroaromatic compound and which can bear one or more substituents, as described below, preferably includes the following groups, which are derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, triphenylene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, terphenyl, quaterphenyl, fluorene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, and spirotruxene. Spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, indole, isoindole, carbazole, indolocarbazole and indenocarbazole.

[0030] Furthermore, under a straight-chain alkyl group with 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 6 carbon atoms, a branched or cyclic alkyl group with 3 to 40 carbon atoms, more preferably with 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, even more preferably 3 to 8 carbon atoms, for example the residues 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 The term "cyclic alkyl group" here refers to 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 term "cyclic alkyl group" encompasses monocyclic, bicyclic, and polycyclic groups.

[0031] Under a straight-chain alkyl group with 1 to 20 carbon atoms, preferably with 1 to 10 carbon atoms, more preferably with 1 to 6 carbon atoms, or a branched alkyl group with 3 to 20 carbon atoms, preferably with 3 to 10 carbon atoms, more preferably with 3 to 8 carbon atoms, in which one or more non-adjacent CH2 groups may be replaced by O or S, and wherein at least one hydrogen atom may be replaced by D, F, or CN, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, thiomethyl, 1-thioethyl, 1-thio-i-propyl, 1-thio-n-propoyl, 1-thio-i-butyl, 1-Thio-n-butyl or 1-thio-t-butyl. Adjacent carbon atoms within the meaning of the present invention are carbon atoms that are directly linked to one another. Furthermore, "adjacent residues" in the definition of residues means that these residues are bonded to the same carbon atom or to neighboring carbon atoms.These definitions apply accordingly to, among other things, the terms “adjacent groups” and “adjacent substituents”.

[0032] The phrase "two or more residues can form a ring system" refers to the formation of an aliphatic, aromatic, or heteroaromatic ring system. Within the context of this description, it is understood, among other things, that the two residues are linked to each other by a chemical bond, formally involving the elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0033] Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring. This is illustrated by the following diagram:

[0034] The compounds of formula (I) and their preferred embodiments are described below. The preferred embodiments also apply to the mixture according to the invention and to the organic electronic or electroluminescent device according to the invention.

[0035] Within the scope of the invention, it is preferred that Ar represents an aromatic ring system with 6 to 25 ring atoms, preferably an aryl group with 6 to 18 carbon atoms, which is extended by one or more R groups. 5 may be substituted, or selected from the group consisting of carbazole, dibenzofuran or dibenzothiophene, each of which is modified by one or more R groups 5may be substituted. In compounds of formula (I), Ar is therefore preferably selected from the group consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl, in particular branched terphenyl, quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, in particular 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl, triphenylenyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, 1-, 2-, 3- or 4-carbazolyl, each of which is modified by one or more R groups. 5 may be substituted.

[0036] In compounds of formula (I), Ar is therefore particularly preferably selected from the group consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl, in particular branched terphenyl, triphenylenyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, 1-, 2-, 3- or 4-carbazolyl, each of which is modified by one or more R groups 5may be substituted.

[0037] The remains R 1 , R 2 , R 3 , R 4 are the same or different in each occurrence and are preferably selected from the group consisting of H, D, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 20 C atoms, preferably with 1 to 10 C atoms, particularly preferably with 1 to 6 C atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 20 C atoms, preferably with 3 to 10 C atoms, particularly preferably with 3 to 8 C atoms, wherein in each of the respective groups one or more H atoms may be replaced by D, or an alkenyl group with 2 to 4 C atoms, or an aryl group with 6 to 25 C atoms, preferably with 6 to 18 C atoms, or a heteroaryl group with 5 to 25 ring atoms, preferably with 5 to 13 ring atoms, wherein the aryl- or heteroaryl group each by one or more residues R 6can be substituted; in this case, two or more adjacent residues R 1 , two or more adjacent residues R 2 , two or more adjacent residues R 3 , form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more Ds.

[0038] In particular, the residues R 1 , R 2 , R 3 and R 4 The atoms are the same or different in each occurrence and are selected from the group consisting of H, D, an aryl group with 6 to 18 C atoms or a heteroaryl group with 5 to 13 ring atoms, each with one or more R groups. 6 They can be substituted. Suitable aryl groups as residue R 1 , R 2 , R 3 and R 4These are phenyl, ortho-, meta- or para-biphenyl, terphenyl, in particular branched terphenyl, quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, in particular 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl and / or triphenylenyl. Suitable heteroaryl groups as residue R 1 , R 2 , R 3 and R 4 These are 1-, 2-, 3- or 4-carbazolyl, N-carbazolyl, 1-, 2-, 3- or 4-dibenzofuranyl or 1-, 2-, 3- or

[0039] 4-Dibenzothiophenyl.

[0040] If Ar represents an aromatic ring system, then the residue R 5Preferably, in each occurrence, the group consisting of H, D, OH, a straight-chain alkyl group with 1 to 10 carbon atoms, preferably with 1 to 6 carbon atoms, a branched or cyclic alkyl group with 3 to 10 carbon atoms, preferably with 3 to 8 carbon atoms, wherein one or more hydrogen atoms in these alkyl groups may be replaced by D, or an aryl group with 6 to 18 carbon atoms or a heteroaryl group with 5 to 13 ring atoms, wherein in the aryl or heteroaryl group one or more hydrogen atoms may be replaced by D or an alkyl group with 1 to 4 carbon atoms, preferably by D. For example, a dibenzofuran, dibenzothiophene, or a carbazole may be selected as the heteroaryl group. In a particularly preferred embodiment, the R group is 5The group consisting of H, D, an aryl group with 6 to 18 C atoms, dibenzofuranyl or carbazolyl is selected in the same or different ways for each occurrence, with one or more H atoms being replaced by D.

[0041] If Ar represents an aromatic ring system, then the residue R 5 preferably selected from the group consisting of H or D, either the same or different for each occurrence.

[0042] If Ar represents a carbazole, dibenzofuran, or dibenzothiophene, then the residue R 5Preferably, in each occurrence, the group consisting of H, D, OH, a straight-chain alkyl group with 1 to 10 carbon atoms, preferably with 1 to 6 carbon atoms, a branched or cyclic alkyl group with 3 to 10 carbon atoms, preferably with 3 to 8 carbon atoms, wherein one or more hydrogen atoms in these alkyl groups may be replaced by D, or an aryl group with 6 to 18 carbon atoms or a heteroaryl group with 5 to 13 ring atoms, wherein in the aryl or heteroaryl group one or more hydrogen atoms may be replaced by D or an alkyl group with 1 to 4 carbon atoms, preferably by D. For example, a dibenzofuran, dibenzothiophene, or a carbazole may be selected as the heteroaryl group. In a particularly preferred embodiment, the R group is 5The group consisting of H, D, an aryl group with 6 to 18 C atoms, dibenzofuranyl or carbazolyl is selected in the same or different ways for each occurrence, with one or more H atoms being replaced by D.

[0043] If Ar represents a carbazole, dibenzofuran, or dibenzothiophene, then the residue R 5 Preferably selected from the group consisting of H or D, either the same or different for each occurrence. If Ar is a carbazolyl, then the residue R 5 preferably an aryl group with 6 to 18 C atoms or a heteroaryl group with 5 to 13 ring atoms at the N atom, wherein one or more H atoms in the aryl or heteroaryl group may be replaced by D.

[0044] According to further embodiments, in the compounds according to the invention at least one of the residues R 1 , R 2 , R 3 , R 4 or R 6 D and none of the remainders R 5represents D or, in the compounds of the invention, at least one of the residues is R. 5 D and none of the remainders R 1 , R 2 , R 3 , R 4 or R 6 represents D. It is further preferred within the scope of the present invention that at least one of the residues R 1 , R 2 , R 3 , R 4 or R 6 D is and at least one of the residues R 5 D is. Within the scope of the invention, it is further possible that all residues R 5 D are and none of the remainders R 1 , R 2 , R 3 , R 4 and R 6 D represents. It is also possible that all residues R 1 , R 2 , R 3 , R 4 and R 6 D represent and at least one of the residues R 5 D is.

[0045] Since the compounds of formula (I) are deuterated compounds, it is possible during their preparation, provided that the preparation is carried out by reacting a non-deuterated compound of formula (I) with a deuterating source, or provided that deuterated starting compounds are chosen for 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.

[0046] Such mixtures of deuterated compounds of the same basic chemical structure of formula (I) or of the basic structure of the preferred embodiments, which differ only in the degree of deuteration and / or the deuteration patterns, shall be understood under the term “at least one compound of formula (I)” within the meaning of the invention.

[0047] In a preferred embodiment of the compound of formula (I), as previously described or preferably described, the average degree of deuteration is 5 mol% to 100 mol%, preferably 30 mol% to 95 mol%, particularly preferably 50 mol% to 90 mol%, and most preferably 70 mol% to 95 mol%.

[0048] Suitable deuteration methods are known to those 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 hydrogen atoms for dium atoms is to treat the compound to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" means any compound that contains one or more dium atoms and can release them under suitable conditions.

[0049] The platinum catalyst is preferably dry platinum on carbon, preferably 5% dry platinum on carbon. The palladium catalyst is preferably dry palladium on carbon, preferably 5% dry palladium on carbon. A suitable deuterium source is D₂O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4, or toluene-d8. A preferred deuterium source is D₂O or a combination of D₂O and a fully deuterated organic solvent. A particularly preferred deuterium source is the combination of D₂O with a fully deuterated organic solvent, the fully deuterated solvent not being restricted here. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. A particularly preferred deuterium source is a combination of D₂O and toluene-d8.The reaction is preferably carried out under heating, more preferably under heating to temperatures between 100 °C and 200 °C. Furthermore, the reaction is preferably carried out under pressure.

[0050] Examples of suitable compounds of formula (I) according to the invention are listed below in Table 1.

[0051] Table 1:

[0052]

[0053]

[0054] In this context, an index such as D1-D29 means that in the corresponding compound, 1 to 29 H atoms can be replaced by D; that is, the first number indicates the minimum number of H substitutions by D, and the second number indicates the maximum number of H substitutions by D. For example, if Di is chosen, it means that one of the 29 H atoms can be replaced by a D atom.

[0055] Particularly suitable compounds of formula (I) are compounds H1 to H30 of Table 2.

[0056]

[0057] For the sake of simplicity, some of the compounds in Tables 1 and 2 are shown as fully deuterated compounds, which generally denote compounds with an average degree of deuteration of at least 50 mol%. The average degree of deuteration for these fully deuterated compounds in Tables 1 and 2 is preferably between 50 mol% and 100 mol%, or it is a preferably specified value as described above. Where partially deuterated compounds are described in Tables 1 and 2, a D atom indicates that the corresponding position in the molecule has a degree of deuteration of at least 40 mol%.

[0058] The compounds according to 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 preclude the presence of any further substituents in the processes. The methods shown for the synthesis of the compounds according to the invention are to be understood as examples. Those skilled in the art can develop alternative synthetic routes within the scope of their general technical knowledge.

[0059] Detailed reaction conditions for the processes shown in Scheme 1 below are known from the prior art or are described in the example section. These processes, optionally followed by purification such as recrystallization or sublimation, allow the compounds of formula (I) to be obtained in high purity, preferably more than 99% (determined by 1 H-NMR and / or HPLC).

[0060] Scheme 1: For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes, formulations of the compounds according to the invention or of mixtures of compounds according to the invention with further functional materials, such as matrix materials, fluorescent emitters, phosphorescent emitters and / or emitters exhibiting TADF, are required. These formulations can be, for example, solutions, dispersions or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents include, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-Dimethylanisol, 3,5-Dimethylanisol, Acetophenon, a- Terpineol, Benzothiazol, Butylbenzoat, Cumol, Cyclohexanol, Cyclohexanon, Cyclohexylbenzol, Decalin, Dodecylbenzol, Ethylbenzoat, Indan, NMP, p-Cymol, Phenetol, 1,4-Diisopropylbenzol, Dibenzylether, Diethylenglycolbutylmethylether, Tri- ethylenglycolbutylmethylether, Diethylenglycoldibutylether, Triethylenglycol- dimethylether, Diethylenglycolmonobutylether, Tripropyleneglycoldimethylether, Tetra- ethylenglycoldimethylether, 2-lsopropylnaphthalin, Pentylbenzol, Hexylbenzol, Heptylbenzol, Octylbenzol, 1,1-Bis(3,4-dimethylphenyl)ethan, 2-Methylbiphenyl, 3-Methylbi- phenyl, 1-Methylnaphthalin, 1-Ethylnaphthalin, Ethyloctanoat, Sebacinsäure- diethylester, Octyloctanoat, Heptylbenzol, Menthyl-isovalerat, Cyclohexylhexanoat oder Mischungen dieser Lösemittel.,

[0061] A suitable formulation is a formulation containing at least one compound according to the invention, as described above, or a mixture according to the invention, as described below, and at least one solvent. The solvent can be one of the solvents mentioned above or a mixture of these solvents.

[0062] The compounds of formula (I) according to the invention, as previously described or preferably described, are suitable for use in an organic electroluminescent device, in particular as a hole transport material, as a hole injection material, as an electron blocking material or as a matrix material.

[0063] When the compound according to the invention is used as a matrix material or, synonymously, host material in an emitting layer, it is preferably used in combination with another compound. A further object of the invention is therefore a mixture containing at least one compound of formula (I) or a compound from Table 1 or one of compounds H1 to H30 and at least one further compound selected from the group consisting of matrix materials, phosphorescent emitters, fluorescent emitters, and / or emitters exhibiting TADF (thermally activated delayed fluorescence). Suitable matrix materials and emitters that can be used in this mixture according to the invention are described below.

[0064] Another object of the present invention is an organic electronic device comprising an anode, a cathode and at least one organic layer, containing at least one compound of formula (I) or at least one preferred compound of formula (I), or a compound of Table 1 or one of the compounds H1 to H30.

[0065] The organic electronic device can be selected, for example, from organic integrated circuits (OlCs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors, and organic photoreceptors.

[0066] Preferably, the organic electronic device is an organic electroluminescent device (synonymously, an organic light-emitting device is used).

[0067] The organic electroluminescent device according to the invention (synonymous with organic electroluminescence device) is, for example, an organic light-emitting transistor (OLET), an organic field-quench device (OFQD), an organic light-emitting electrochemical cell (OLEC), an organic laser diode (O-Laser), or an organic light-emitting diode (OLED). The organic electroluminescent device according to the invention is, in particular, an organic light-emitting diode or an organic light-emitting electrochemical cell. An OLED is especially preferred.

[0068] The organic layer of the device according to the invention preferably comprises, in addition to a light-emitting layer (EML), a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), an exciton blocking layer, an electron blocking layer, and / or charge-generation layers. The device according to the invention may also contain several layers of this group, preferably selected from EML, HIL, HTL, ETL, EIL, and HBL. Likewise, interlayers, which, for example, have an exciton-blocking function, may be introduced between two emitting layers.

[0069] If multiple emission layers are present, these preferably exhibit several emission maxima between 380 nm and 750 nm, resulting in overall white emission. This means that different emitting compounds capable of fluorescence or phosphorescence are used in the emitting layers. Multiple fluorescent and / or phosphorescent compounds can also be contained within a single emitting layer. Systems with three emitting layers are particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission. Alternatively to the combination described above, an emitting layer can also exhibit yellow emission. Such combinations are known to those skilled in the art. The organic electroluminescent device according to the invention can also be a tandem electroluminescent device, particularly for white-emitting LEDs.The device may also contain inorganic materials or layers that are entirely composed of inorganic materials.

[0070] It presents no difficulty to draw upon a large number of materials known in the prior art to select suitable materials for use in the previously described layers of the organic electroluminescence device. In doing so, the person skilled in the art makes standard considerations regarding the chemical and physical properties of the materials, since they are aware that the materials in an organic electroluminescence device are interrelated. This includes, for example, the energy positions of the orbitals (HOMO, LUMO) or the positions of triplet and singlet energies, as well as other material properties.

[0071] The compound of formula (I) according to the invention, as previously described or preferably described, can be used in different layers, depending on the precise structure. A preferred application is an organic electroluminescent device containing a compound according to formula (I) or the preferred embodiments described above in an emitting layer as a matrix material for fluorescent emitters, phosphorescent emitters, or emitters exhibiting TADF (thermally activated delayed fluorescence), particularly for phosphorescent emitters. Furthermore, the compound according to the invention can also be used in a hole transport layer and / or in an exciton blocking layer and / or in an electron blocking layer. The compound according to the invention is particularly preferably used as a matrix material in an emitting layer or as a hole transport or electron blocking material in a hole transport or electron blocking layer.

[0072] Another object of the present invention is an organic electronic device as previously described, wherein the organic layer contains at least one light-emitting layer which contains at least one compound of formula (I) or a compound of Table 1 or one of the compounds H1 to H30.

[0073] In one embodiment of the invention, at least one further matrix material is selected for the light-emitting layer of the device according to the invention, which is used with compounds of formula (I) as previously described or preferably described, or with the compounds of Table 1 or the compounds H1 to H30.

[0074] Another object of the present invention is therefore an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer comprising at least one compound of formula (I) or a compound of Table 1 or one of compounds H1 to H30 and at least one further matrix material.

[0075] Another object of the present invention is therefore also an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer comprising at least one compound of formula (I) or a compound of Table 1 or one of compounds H1 to H30 and at least two further matrix materials.

[0076] Suitable matrix materials that can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, biscarbazoles, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, azaborols or boron esters, triazine derivatives, zinc complexes, diazasilol or tetraazasilol derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or dibenzofuran derivatives. Likewise, another phosphorescent emitter, which emits at a shorter wavelength than the actual emitter, can be present in the mixture as a co-host, or a compound that does not participate in charge transport, or does not participate to a significant extent, such as a wide band-gap compound.

[0077] Hereinafter, wide-band-gap-Mater\a\ is understood to be a material as defined in the revelation of US 7,294,849, characterized by a band gap of at least 3.5 eV, where band gap is understood to be the distance between the HOMO and LUMO energy of a material.

[0078] Particularly suitable matrix materials, which are advantageously combined with compounds of formula (I), as previously or preferably described, in a mixed matrix system, can be selected from the compounds of formulas (A), (B), (C), (D) or (E), as described below.

[0079] A further object of the invention is therefore an organic electronic, in particular organic electroluminescent, device comprising an anode, a cathode and at least one organic layer, containing at least one light-emitting layer, wherein the at least one light-emitting layer comprises at least one compound of formula (I) as matrix material 1, as previously described or preferably described, and at least one compound of formulas (A), (B), (C), (D) or (E) as matrix material 2 (further matrix material): Formula (B), el (E), where the following applies to the symbols and indices used:

[0080] X is the same or different in each occurrence N or CR X , preferably N;

[0081] L is, in each occurrence, either the same or different, a single bond or an aromatic or heteroaromatic ring system with 5 to 24 ring atoms, each with one or more R groups.11 may be substituted;

[0082] R## is the same or different in each occurrence D, F, CN, a straight-chain alkyl group with 1 to 10 C atoms, a branched or cyclic alkyl group with 3 to 10 C atoms, or an alkenyl group with 2 to 10 C atoms, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which is coupled with one or more R substituents. 8 can be substituted and two adjacent substituents R## can together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, which is joined with one or more R groups 8 may be substituted;

[0083] Y is the same or different in each occurrence N or CR 1 1 , excluding the possibility that two adjacent Ys simultaneously represent N; 2 is O or S;

[0084] R xis the same or different in each occurrence D, F, CN, a straight-chain alkyl group with 1 to 20 C atoms or an alkenyl or alkynyl group with 2 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each linked to one or more R groups 1 1 can be substituted and where one or more non-adjacent CHs groups are replaced by Si(R 11 )2, C=O, NR 11 , O, S or CONR 11 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which may be partially or completely deuterated;

[0085] Ar 1 In each instance, the term represents, in the same or different ways, an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which is coupled with one or more R groups. 1 1 may be substituted;

[0086] R 8is the same or different H, D, F or an aliphatic, aromatic or heteroaromatic organic residue, in particular a hydrocarbon residue, with 1 to 20 C atoms, in which one or more H atoms may also be replaced by F;

[0087] R 10 is the same or different in each occurrence H, D, F, CI, 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 with 1 to 20 carbon atoms, or an alkenyl or alkynyl group with 2 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group is each linked to one or more R groups 12 can be substituted, with one or more non-adjacent CH2 groups being replaced by Si(R 8 )2, C=O, NR 8, O, S or CONR 8 can be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is replaced by one or more R groups 12 It can be substituted; in this case, two or more residues R can be involved. 10 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;

[0088] R 11 is the same or different in each occurrence D, F, CI, 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 with 1 to 20 carbon atoms, or an alkenyl or alkynyl group with 2 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group is each linked to one or more R groups 12can be substituted, with one or more non-adjacent CH2 groups being replaced 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, which may be partially or completely deuterated; in which case two or more R groups may be present. 11 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;

[0089] R 12 is the same or different in each occurrence D, F, CN, a straight-chain alkyl group with 1 to 20 C atoms or an alkenyl or alkynyl group with 2 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each linked to one or more R groups 11 can be substituted, with one or more non-adjacent CH2 groups being replaced by Si(R 11 )2, C=O, NR 1 1 , O, S or CONR 11may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be partially or completely deuterated; b1 is 0, 1, 2, 3 or 4; and b2 is 0, 1, 2 or 3.

[0090] The substituent R 8 Each term independently preferentially represents H, D or phenyl, where the H atoms of the phenyl group can be replaced by D once or multiple times.

[0091] Another object of the invention is an organic electronic device, in particular an organic electroluminescent device comprising an anode, cathode and at least one organic layer, containing at least one light-emitting layer, wherein the at least one light-emitting layer comprises at least one compound of formula (I) as matrix material 1, as previously described or preferably described, and at least one compound of formulas (A), (B), (C), (D) and / or (E) as matrix material 2, as previously or preferably described.

[0092] Preferred compounds of formula (A) are the compounds of formulas (Aa), (Ab), (Ac), (Ad), (Ae) and (Af), Formula (Aa)

[0093] , where the symbols and indices for these formulas have the following meanings:

[0094] W, W 1 O, S, C(R) mean the same or different in each occurrence. W)2 or N-Ar 1 ;

[0095] R w In each occurrence, the compound may be a straight-chain alkyl group with 1 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein one or more hydrogen atoms may be replaced by D, F, or CN; or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group with 1 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein one or more hydrogen atoms of the alkyl group on the aromatic or heteroaromatic ring system may be replaced by D, F, or CN; the two R groups may be w , which bind to the same carbon atom, also form a ring system with each other;

[0096] A is the same or different in each occurrence CR 11or N, where a maximum of two groups A per cycle represent N and where A represents C if L is bound to that position; a3 is either the same or different from 0, 1, 2, 3 or 4 for each occurrence; b3 is either the same or different from 0, 1, 2 or 3 for each occurrence; BJ

[0097] Ring B^^ is derived from an aryl group with 6 to 20 ring atoms, which may be substituted with one or more substituents R##;

[0098] D R-ing

[0099] L 1 is an aromatic ring system with 6 to 40 ring atoms or a heteroaromatic ring system with 5 to 40 ring atoms, which are coupled with one or more R groups 1 1 can be substituted; where L, X, Ar 1 , R 11 and R## have the meanings given above.

[0100] In compounds of formulas (A) , (Aa) to (Af) or their preferred embodiments, X preferably represents N.

[0101] In compounds of formula (Aa) or their preferred embodiments, W preferably represents O or N-Ar. 1 .

[0102] In compounds of formula (Aa) or their preferred embodiments, A preferably represents CR in the same or different ways in each occurrence. 11 , where A represents a C atom when bonded to L.

[0103] In a preferred embodiment of the compounds of formula (Aa), W represents N-Ar 1 and the linker L, which is bonded to the structural unit containing W, preferably represents L-1 to L-13, which are linked with one or more substituents R 1 1 can be substituted,

[0104] L-1 L-2 L-3 L-4

[0105] where the dashed line indicates the connection to the rest of the formula (Aa) and where R 11 has a meaning as described above or below. In L-1 to L-13, R 11preferably for D or a non-deuterated, partially or fully deuterated aryl group with 6 to 18 carbon atoms. In L-1 to L-13, R 1 1 especially preferred for D.

[0106] Particularly preferred compounds of formulas (A) and (Aa) are the compounds of formulas (Aa-1) to (Aa-8), Formula (Aa-1),

[0107] , , where the following applies to the symbols and indices used:

[0108] Ar 2 is the same or different, an aromatic ring system with 6 to 40

[0109] Ring atoms that have one or more substituents R 11 may be substituted;

[0110] L 2 is a bond or an aromatic ring system with 6 to 40 ring atoms, which includes one or more substituents R 11 may be substituted,

[0111] (R 11 )x, (R 11 )y, (R 11 )xi , (R 1 1)yi represent a monosubstitution, a disubstitution, a trisubstitution, or the maximum permissible substitution with the substituent R. 1 1 dar, R 18 In each occurrence, the alkyl group is either the same or different, consisting of a straight chain.

[0112] 1 to 10 carbon atoms or an aryl group with 6 to 12 carbon atoms, wherein two substituents R 18 together they can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may contain one or more substituents R 11 can be substituted, where X, L, Ar 1 and R 11 have a previously mentioned meaning or a meaning that has been previously and subsequently preferred.

[0113] In combinations of the formulas (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7) and (Aa-8), all X preferably represent N.

[0114] In combinations of formulas (Aa-1), (Aa-2), (Aa-3), (Aa-4) and (Aa-8), the linkers are L and L. 2Preferably a single binding.

[0115] In compounds of formula (Aa-5), the linker L is preferentially a single bond in every occurrence.

[0116] In compounds of formulas (Aa-6) and (Aa-7), one of the linkers L preferably represents one of the groups L-1 to L-13, which are linked with one or more substituents R. 11 They can be substituted as described above. In compounds of formulas (Aa-6) and (Aa-7), one of the linkers L preferentially represents the group L-12, which is substituted with one or more substituents R. 11 It can be substituted, as previously described. This one linker L is preferentially bound to the diazadibenzofuran or diazadibenzothiophene unit. All other linkers L are preferably single bonds.

[0117] In compounds of formulas (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7) and (Aa-8), the substituents are R 1 1 in (R 11 )x, (R 11 )y, (R 11 )xi , (R11 )yi, if occurring, preferably as indicated below, especially preferred D.

[0118] In compounds of formula (Aa-5), the substituents are R 11 of the substituent Ar 2 preferably selected from D and / or CN. Particularly preferred is at least one R. 11 of the substituent Ar 2 CN.

[0119] In compounds of formulas (Aa-6) and (Aa-7), the substituents R 11 in (R 1 1 )x upon occurrence preferably as indicated, especially preferred D.

[0120] In compounds of formulas (Aa-6) and (Aa-7), the substituents R 11 in (R 1 1 )y preferably occur as indicated, but particularly preferably represent a non-deuterated, partially or completely deuterated aryl group with 6 to 18 C atoms.

[0121] Preferred compounds of formula (Ac) are compounds in which one of the linkers L is selected from the groups L-1 to L-13, wherein L-1 to L-13 are equipped with one or more substituents R 11 can be substituted, as described above. In compounds of the formula (Ac), one of the linkers L is particularly preferentially selected from the groups L-1, L-2, L-3, L-8, L-9, L-12 and L-13, which are equipped with one or more substituents R. 11 They can be substituted, as previously described. This single linker L is preferentially bound to the carbazole unit of the compounds of formula (Ac).

[0122] All other left-handed L ties are preferably single ties.

[0123] Preferred compounds of formula (Ad) are compounds in which one of the linkers L is selected from the groups L-1 to L-13, wherein L-1 to L-13 is equipped with one or more substituents R 11They can be substituted as described above. In compounds of formula (Ad), one of the linkers L is particularly preferentially selected from the groups L-1, L-2, L-3, L-8, L-9, L-12 and L-13, which are equipped with one or more substituents R. 11 They can be substituted, as described above. In compounds of formula (Ad), one of the linkers L is particularly favorably placed for the group L-12, which is accompanied by one or more substituents R. 1 1 It can be substituted, as described above. In compounds of formula (Ad), one of the linkers L is particularly favorably placed in group L-9, which is represented by one or more substituents R. 11 The linker L can be substituted as described above. This single linker L is preferably bonded to the 4 / 7-naphtho[1,2,3,4-de / ]carbazole unit of the compounds of formula (Ad). All other linkers L are preferably single bonds.

[0124] In an alternative embodiment of the compounds of formula (Ad), all linkers L represent a single bond.

[0125] Preferred compounds of formula (Ae) are compounds in which W 1 for O or C(R W )2 stands, especially preferably for C(R W )2 stands where R w has a meaning as described above. In this embodiment, it is preferred that R w stands for methyl, or that two substituents R w together with the carbon atom to which they bond, they form a ring system. In compounds of formula (Ae), preferred are those in which one of the linkers L is selected from groups L-1 to L-13, where L-1 to L-13 has one or more substituents R. 1 1 They can be substituted, as described above. In compounds of formula (Ae), one of the linkers L is particularly favorably selected from groups L-1, L-2, and L-3, which contain one or more substituents R. 11The linker L can be substituted as described above. This single linker L is preferably bonded to the carbazole-containing structural unit of the compounds of formula (Ae). All other linkers L are preferably single bonds. In an alternative embodiment of the compounds of formula (Ae), all linkers L represent single bonds.

[0126] Particularly preferred compounds of formulas (A) and (Af) are the compounds of formulas (Af-1) to (Af-3),

[0127]

[0128] 5 where the following applies to the symbols and indices used: (R 11 )x, (R 11 )y represent a monosubstitution, a disubstitution, a trisubstitution, or the maximum permissible substitution with the substituent R. 11 dar

[0129] R 18The group consists of a straight-chain alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 12 carbon atoms, either the same or different in each occurrence, with two substituents R. 18 together they can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may contain one or more substituents R 11 may be substituted;

[0130] L 3 is a bond or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which includes one or more substituents R 11 can be substituted, where X, L, Ar 1 and R 1 1 have a previously mentioned meaning or a meaning that has been previously and subsequently preferred.

[0131] In combinations of formulas (Af-1), (Af-2) and (Af-3), all X are preferentially N.

[0132] In combinations of the formulas (Af-1), (Af-2) and (Af-3), the left L 3preferably as a single bond or selected from the group L-1 to L-13, wherein L-1 to L-13 have one or more substituents R 1 1 They can be substituted, as described previously. In compounds of formulas (Af-1), (Af-2) and (Af-3), the linker L 3 particularly preferably selected from the group L-1 to L-7 and L-12, wherein L-1 to L-7 and L-12 have one or more substituents R 11 They can be substituted, as described above.

[0133] In combinations of the formulas (Af-1), (Af-2) and (Af-3), the left L 3 especially preferred from group L-12, which have one or more substituents R 11 It can be substituted, as described above.

[0134] In compounds of formulas (Af-1), (Af-2) and (Af-3), the linker L is preferably selected independently of each other as a single bond or from the group L-1 to L-13, wherein L-1 to L-13 are linked with one or more substituents R1 1 They can be substituted, as described previously. In compounds of formulas (Af-1), (Af-2) and (Af-3), all linkers L are preferably single bonds.

[0135] In compounds of the formulas (Af-1), (Af-2) and (Af-3), the substituents R 11 in (R 11 )x, (R 11 )y, when occurring, is preferably as indicated below, most especially preferred D.

[0136] In a preferred embodiment of the further matrix material, it is selected from a compound of formulas (Aa-1), (Aa-2), (Aa-4), (Ad), (Ae), and (Af-1). In compounds of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), and (Af-3), Ar is 1 at every

[0137] Occurrence independently, preferably from groups Ar 1 -1 to Ar 1 -12 selected where

[0138] Y 3 for O, S, NAr 4 or C(R# )2 stands, preferably for O or NAr 4 ;

[0139] R 13 for H or R 11 stands, preferably for H, D, F, CI, 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 with 1 to 20 carbon atoms, or an alkenyl or alkynyl group with 2 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group is each linked to one or more R groups 12 can be substituted, with one or more non-adjacent CH2 groups being replaced by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be partially or completely deuterated, the dashed bond represents the bond to the rest of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2) and (Af-3),

[0140] R# represents a methyl group or phenyl, which can be partially or completely deuterated, and where two substituents R# can represent a spirobifluorenyl group, which can be partially or completely deuterated, m represents 0 or 1 and

[0141] Ar* stands for phenyl, biphenyl or terphenyl, which may be partially or completely deuterated.

[0142] In Y 3 R# preferably stands for Methyl.

[0143] In Ar 1 -9 to Ar 1 -12 stands for Y 3 preferably for O or S, especially preferred for O.

[0144] In Ar 1 -9 to Ar 1 -12 is preferably m 0.

[0145] In Ar 1 -1 to Ar 1 -12 stands for R 13 Particularly preferred for H, D, or a non-deuterated, partially or fully deuterated aryl group with 6 to 18 carbon atoms. ln Ar 1 -1 to Ar 1 - 12 stands for R 13 especially preferred for H, D or non-deuterated, partially or fully deuterated phenyl. In Ar 1 -1 to Ar 1 -12 stands for R 13 especially preferred for H or D.

[0146] Within the groups Ar 1 -1 to Ar 1 -12 are the groups in Ar 1 -1, Ar 1 -2, Ar 1 -3, Ar 1 -9, Ar 1 -10, Ar 1 -11 and Ar 1 -12 is particularly preferred, with all symbols and indices having a meaning as previously described.

[0147] Preferred compounds of formula (B) are the compounds of formula (Ba), Formula (Ba), where Y, V 2 , L, R 10 , R 11 and a3 has a previously specified meaning, D corresponds to deuterium and a4 means 0, 1 or 2.

[0148] Particularly preferred compounds of formula (B) are the compounds of form ( c), where Y, V 2 , L, R 10 , R 11 and a3 have a previously specified meaning, D

[0149] Deuterium corresponds to and a4 means 0, 1 or 2. In compounds of formula (B),

[0150] (Ba), (Bb) and (Bc) L is preferably a single bond.

[0151] Preferred compounds of formula (C) are the compounds of formula (Ca), Formula (Ca) where the symbols and indices for this formula (Ca) have the following meaning: W 1 is the same or different in each occurrence O, S, C(R W )2 or N-Ar 1 ;

[0152] #X is CR or NAr 1 , preferably NAr 1 ;

[0153] R w is, in each occurrence, the same or different: a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein one or more H atoms may be replaced by D, F, or CN; or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group with 1 to 20 C atoms, or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein one or more H atoms of the alkyl group on the aromatic or heteroaromatic ring system may be replaced by D, F, or CN; a3 is, in each occurrence, the same or different: 0, 1, 2, 3, or 4;

[0154] Ring B is derived from an aryl group with 6 to 20 ring atoms, which may be substituted with one or more substituents R##; where L, Ar 1 and R## have the meanings given above.

[0155] In a preferred embodiment of the compounds of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D) or (E), which can be combined according to the invention with the aforementioned compounds as described above, R 11 same or different at each occurrence selected from the group consisting of D, F, CN, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may each be partially or completely deuterated.

[0156] In a particularly preferred embodiment of the compounds of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D) or (E), which can be combined according to the invention with the aforementioned compounds as described above, R 11 The ring atoms, whether identical or different at each occurrence, are selected from the group consisting of D or an aromatic or heteroaromatic ring system with 6 to 30 ring atoms, each of which may be partially or completely deuterated. The preparation of the compounds of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D), or (E) are generally known, and some of the compounds are commercially available.

[0157] If at least one of the other matrix materials is a deuterated compound, it is possible that this at least one matrix material is a mixture of deuterated compounds with the same basic chemical structure, differing only in the degree of deuteration and / or the deuteration pattern. The explanations regarding deuterated mixtures and the preparation of deuterated materials, as previously described for compounds of formula (I), apply accordingly.

[0158] In a preferred embodiment of the at least one further matrix material, this is a mixture of deuterated compounds of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D) or (E), as previously described, wherein the average degree of deuteration of these compounds is at least 10 mol% to 100 mol%, preferably 50 mol% to 95 mol%, and particularly preferably 70 mol% to 90 mol%.

[0159] Suitable compounds of formula (A) are known, for example, from the following publications: W02007 / 077810A1, W02008 / 056746A1, W02010 / 136109A1, WO2011 / 057706A2, WO2011 / 160757A1, WO2012 / 023947A1, WO2012 / 048781 A1, WO2013 / 077352A1, WO2013147205A1, WO2013 / 083216A1, WO2014 / 094963A1, WO2014 / 007564A1, W02014 / 015931A1, W02015 / 090504A2, W02015 / 105251A1, WO2015 / 169412A1, WO2016 / 015810A1, WO2016 / 013875A1, W02016 / 010402A1, WO2016 / 033167A1, WO2017 / 178311A1, WO2017 / 076485A1, WO2017 / 186760A1, W02018 / 004096A1, WO2018 / 016742A1, WO2018 / 123783A1, WO2018 / 159964A1, WO2018 / 174678A1, WO2018 / 174679A1, WO2018 / 174681 A1, WO2018 / 174682A1, WO2019 / 177407A1, WO2019 / 245164A1, WO2019 / 240473A1, W02019 / 017730A1, W02019 / 017731A1, WO2019 / 017734A1, WO2019 / 145316A1, WO2019 / 121458A1, W02020 / 130381 A1, W02020 / 130509A1, W02020 / 169241 A1, WO2020 / 141949A1, WO2021 / 066623A1, W02021 / 101220A1, W02021 / 037401A1, W02021 / 180614A1, WO2021 / 239772A1, W02022 / 015084A1, WO2022 / 025714A1, WO2022 / 055169A1, EP3575296A1,EP3591728A1 , US2014 / 0361254A1 , U S2014 / 0361268A1 , KR20210036304A, KR20210036857A, KR2021147993A, JP2011 / 160367A2 and JP2017 / 107992A2. Particularly suitable compounds of formula (A) are compounds from WO2015 / 169412A1, described on pages 28 to 63, 93 and 110 to 114, compounds from W02019 / 007866A1, described in Tables 1 to 8 on pages 37 to 100, compounds from WO2019 / 096717A2, described in Table 1 on pages 27 to 33 and the compounds described on pages 96 to 102, compounds from W02019 / 229011A1, described in Tables 1 and 2 on pages 31 to 117 and compounds described on pages 251 to 254, compounds from W02021 / 037401A1, described on pages 31 to 64 and compounds P1 to P110 on pages 132 to 144, compounds from W02020 / 169241 A1,described in Table 1 on pages 30 to 73 and compounds 1 to 36 and 67 to 81 on pages 74 to 78, as well as compounds described on pages 223 to 231, compounds from WO2023247662A1, described in Tables 1 and 2 on pages 18 to 23 and compounds described on pages 100 to 102, compounds from WO2023247663A1, described in Tables 1 and 2 on pages 43 to 58 and compounds described on pages 151 to 173, compounds from US2023172065 A, described on pages 6 to 413 and 435 to 498, compounds from W02016 / 015810A1, described on pages 27 to 34, 51 to 56 and 61 to 64, compounds from WO18174678 A1, described on pages 20 to 32 and 38 to 50, compounds from WO18174681 A1, described on pages 20 to 32 and 42 to 61, compounds from WO2021 / 052921A1, described in Table 1 on pages 20 to 27,Connections 1 to 11 and 29 to 44 on pages 27 to 31 and connections described on pages 122 to 125, connections from WO2017 / 178311A1, described on pages 37 to 44 and the connections described on pages 97 to 105, connections from W02010 / 136109A1, described on pages 32 to 54 and the connections of examples 1 to 54 described on pages 74 to 139, connections from W02011 / 000455A1, described on pages 19 to 32 and the connections of examples 1 to 7a described on pages 51 to 59, connections from WO2021 / 239772A1, described in Table 1 on pages 27 to 120 and connections E55 to E60 on pages 223 to 224 and E61 on page 227.

[0160] Suitable compounds of formula (B) are known, for example, from the following publications: WO2015 / 182872A1, W02015 / 105316A1, WO2017 / 109637A1, W02018 / 060307A1, WO2018 / 151479A2, WO2018 / 088665A2, WO2018 / 060218A1, WO2018 / 234932A1, W02019 / 058200A1, W02019 / 017730A1, W02019 / 017731A1, WO2019 / 066282A1, WO2019 / 059577A1, WO2020 / 141949A1 W02020 / 067657A1, WO2022063744A1, W02022 / 090108A1, WO2022 / 207678A1, WO2023061998A1, KR20170139443A, KR20190036867A, KR2019035308A, KR2021147993A, CN110294753A, CN110437241A, US2016 / 072078A1, US2019 / 148646A1.

[0161] Suitable compounds of formula (C) are known, for example, from the following publications: W02017 / 160089A1, W02019 / 017730A1, WO2019 / 017731 A1, W02020 / 032424A1. Suitable compounds of formula (E) are known, for example, from the following publications: WO2015 / 093878A1, WO2016 / 033167A1, WO2017 / 183859A1, WO2017 / 188655A1, WO2018 / 159964A1.

[0162] For combination with the compounds according to the invention, as described above or preferably, compounds of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb) and / or (Bc) are particularly suitable, as described above or preferably, or corresponding compounds from the following tables that fall under these formulas. Compounds of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2) and / or (Af-3) are particularly preferred.

[0163] Further examples of suitable host materials of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (C), (Ca), (D) or (E) which can be combined according to the invention with the above-mentioned compounds as described above are the structures listed below in Tables 3 and 4.

[0164] Table 3:

[0165]

[0166]

[0167] Particularly suitable compounds of formulas (A), (Aa), (Ab), (Ac), (Ad), (Ae), (Af) and / or (B), which can be combined according to the invention with the above-mentioned compounds as described above and used in the electroluminescent device or mixture according to the invention, are compounds E1 to E56 of Table 4.

[0168] Table 4:

[0169]

[0170] For the sake of simplicity, some of the compounds in Tables 3 and 4 are shown as fully deuterated compounds, which generally denote compounds with an average degree of deuteration of at least 50 mol%. The average degree of deuteration for these fully deuterated compounds in Tables 3 and 4 is preferably between 50 mol% and 100 mol%, or it is a preferably specified value as described above. Where partially deuterated compounds are described in Tables 3 and 4, a D atom indicates that the corresponding position in the molecule has a degree of deuteration of at least 40 mol%.

[0171] The host materials mentioned above according to the invention, as well as their preferably described embodiments, can be combined in the device according to the invention as desired with the aforementioned matrix materials / host materials, the matrix materials / host materials of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D) or (E), as well as their preferably described embodiments of Table 3 or the compounds E1 to E56 of Table 4. Particularly preferred mixtures of the compounds of formula (1) with the host materials of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D) or (E) for the device according to the invention are obtained by combining the compounds H1 to H30 with the compounds E1 to E56.Table 5 below shows highly preferred mixtures. The first mixture, M1, for example, is a combination of compound E1 with H1.

[0172] Table 5:

[0173] The concentration of the host material of formula (I), as previously described or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is typically in the range of 10 wt.% to 95 wt.%, preferably in the range of 15 wt.% to 90 wt.%, more preferably in the range of 15 wt.% to 80 wt.%, even more preferably in the range of 20 wt.% to 70 wt.%, most preferably in the range of 40 wt.% to 80 wt.% and most preferably in the range of 50 wt.% to 70 wt.%, based on the entire mixture or based on the entire composition of the light-emitting layer.

[0174] The concentration of the sum of all host materials of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D) or (E), as previously or preferably described, in the inventive mixture or in the light-emitting layer of the inventive device is typically in the range of 5 wt.% to 90 wt.%, preferably in the range of 10 wt.% to 85 wt.%, more preferably in the range of 20 wt.% to 85 wt.%, even more preferably in the range of 30 wt.% to 80 wt.%, most preferably in the range of 20 wt.% to 60 wt.% and most preferably in the range of 30 % by weight to 50% by weight, based on the total mixture or based on the total composition of the light-emitting layer.

[0175] The present invention also relates to a mixture which, in addition to the host materials of formula (I) mentioned above, hereinafter referred to as host material 1, and the host material of at least one of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D) or (E), as previously described or preferably described, contains at least one phosphorescent emitter.

[0176] The present invention also relates to a mixture selected from a combination of compounds H1 to H30 with compounds E1 to E56 or mixtures M1 to M630, which contains at least one phosphorescent emitter.

[0177] The present invention also relates to an organic electroluminescent device as previously described or preferably described, wherein the light-emitting layer, in addition to the aforementioned host materials of formula (1) and at least one of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D) and (E), as previously described or preferably described, in particular the material combinations M1 to M630, contains at least one phosphorescent emitter.

[0178] The term phosphorescent emitters typically encompasses compounds in which light emission occurs through a spin-forbidden transition from an excited state with a higher spin multiplicity, i.e., a spin state > 1, for example, through a transition from a triplet state or a state with an even higher spin quantum number, such as a quintet state. A transition from a triplet state is preferred.

[0179] Suitable phosphorescent emitters (= triplet emitters) are compounds that, upon suitable excitation, emit light, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, and particularly preferably greater than 56 and less than 80, especially a metal with this atomic number. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are preferred as phosphorescent emitters, especially compounds containing iridium or platinum. For the purposes of the present invention, all luminescent compounds containing the aforementioned metals are considered phosphorescent emitters.

[0180] In general, all phosphorescent complexes are suitable, such as those used in phosphorescent OLEDs according to the prior art and as are known to those skilled in the art in the field of organic electroluminescence devices.

[0181] Preferred phosphorescent emitters according to the present invention correspond to formulas (1), (2), (3), (4) or (5), where the symbols and indices for these formulas (1), (2), (3), (4) and (5) are

[0182] Have meaning:

[0183] Ri is H or D, R2 is H, D, F, CN or a branched or linear alkyl group with 1 to 10 C atoms or a partially or completely deuterated branched or linear alkyl group with 1 to 10 C atoms or a cycloalkyl group with 4 to 10 C atoms, which may be partially or completely substituted with deuterium.

[0184] Preferred phosphorescent emitters according to the present invention Formula (6), where the symbols and indices for this formula (6) have the following meanings: n+m is 3, n is 1 or 2, m is 2 or 1 ,

[0185] X is the same or different N or CR in each occurrence,

[0186] R is the same or different in each occurrence H, D, F, CN or a branched or linear alkyl group with 1 to 10 C atoms or a partially or completely deuterated branched or linear alkyl group with 1 to 10 C atoms or a cycloalkyl group with 4 to 7 C atoms, which may be partially or completely substituted with deuterium or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, which may be partially or completely substituted with deuterium. In emitters of formula (6) n is preferably 1 and m is preferably 2.

[0187] In emitters of formula (6), preferably one X is selected from N and the other X represent CR, or all X represent CR, either the same or different, in each occurrence. In emitters of formula (6), at least one R is preferably different from H. In emitters of formula (6), preferably two R are different from H and have one of the meanings previously given for the emitters of formula (6).

[0188] Another object of the invention is therefore an organic electroluminescent device, as previously described or preferably described, characterized in that the light-emitting layer contains, in addition to the host materials 1 and 2, at least one phosphorescent emitter corresponding to one of formulas (1) to (6), as previously described, preferably to formula (6).

[0189] Preferred examples of phosphorescent emitters are described in WO2019 / 007867 on pages 120 to 126 in Table 5 and on pages 127 to 129 in Table 6. These emitters are included in the description by reference.

[0190] Particularly favored examples of phosphorescent emitters are listed in Table 6 below.

[0191] Table 6:

[0192] In the mixtures according to the invention or in the light-emitting layer of the device according to the invention, each mixture is preferably selected from the sum of the mixtures M1 to M630 and combined with a compound of formulas (1) to (6) or a compound from Table 6.

[0193] The light-emitting layer in the organic electroluminescent device according to the invention, comprising at least one phosphorescent emitter, is preferably an infrared-emitting, yellow, orange, red, green, blue or ultraviolet-emitting layer, particularly preferably a yellow or green-emitting layer, and most preferably a green-emitting layer.

[0194] A yellow emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 540 to 570 nm. An orange emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 570 to 600 nm. A red emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 600 to 750 nm. A green emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 490 to 540 nm. A blue emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 440 to 490 nm.The photoluminescence maximum of the layer is determined by measuring the photoluminescence spectrum of the layer with a layer thickness of 50 nm at room temperature, wherein the layer contains the inventive combination of the host material 1 of formula (I) and the host material 2, consisting of at least one of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D) and (E), and the corresponding emitter.

[0195] The photoluminescence spectrum of the layer is recorded, for example, using a commercially available photoluminescence spectrometer.

[0196] The photoluminescence spectrum of the chosen emitter is usually measured in oxygen-free solution, 10' 5The triplet energy T1 in eV is measured at room temperature, using any solvent in which the chosen emitter dissolves at the specified concentration. Particularly suitable solvents are typically toluene or 2-methyl-THF, but also dichloromethane. The measurement is performed 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).

[0197] Preferred phosphorescent emitters are therefore yellow emitters, preferably of formulas (1) to (6) or from Table 6, whose triplet energy T1 is preferably at ~2.3 eV to ~2.1 eV.

[0198] Preferred phosphorescent emitters are therefore green emitters, preferably of formulas (1) to (6) or from Table 6, whose triplet energy T1 is preferably at ~2.5 eV to ~2.3 eV.

[0199] Particularly preferred phosphorescent emitters are therefore green emitters, preferably of formulas (1) to (6) or from Table 6, as previously described, whose triplet energy T1 is preferably at ~2.5 eV to ~2.3 eV.

[0200] Particularly preferred are green emitters, preferably of formulas (1) to (6) or from Table 6, as previously described, selected for the mixture or emitting layer according to the invention.

[0201] The light-emitting layer of the device or mixture according to the invention may also contain fluorescent emitters. Preferred fluorescent emitting compounds are selected from the class of arylamines, wherein preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a condensed ring system, particularly preferably with at least 14 ring atoms. Preferred examples are aromatic anthracene amines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrenediamines, aromatic chrysene amines, or aromatic chrysenediamines. An aromatic anthracene amine is understood to be a compound in which a diarylamine group is directly bonded to an anthracene group, preferably at position 9. An aromatic anthracene diamine is understood to be a compound in which two diarylamine groups are directly bonded to an anthracene group, preferably at positions 9 and 10.Aromatic pyrenamines, pyrendiamines, chrysenamines, and chrysendiamines are defined analogously, wherein the diarylamine groups are preferably bonded to the pyrene at the 1-position or the 1,6-position. Further preferred emitting compounds are indenofluorenamines or diamines, benzoindenofluorenamines or diamines, and dibenzoindenofluorenamines or diamines, as well as indenofluorene derivatives with fused aryl groups. Pyrene arylamines are also preferred. Benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives linked to furan or thiophene units are also preferred. Furthermore, the light-emitting device or the mixture according to the invention can also contain materials exhibiting TADF (thermally activated delayed fluorescence).

[0202] In a further preferred embodiment of the 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 include, for example, wide-band-gap materials, bipolar host materials, electron transport materials (ETMs), or hole transport materials (HTMs) as a third or fourth matrix material, in addition to host material 1 or host material 2. Preferably, the mixed-matrix system is optimized for an emitter of formulas (1) to (6) or for an emitter from Table 6.

[0203] According to one embodiment of the present invention, the mixture contains, in addition to the components of the host material of formula (I) and host material 2 as previously or preferably described, no further components, i.e., functional materials. These are material mixtures used as such for the production of the light-emitting layer. These mixtures are also referred to as premix systems, which are used as the sole material source during the deposition of the host materials for the light-emitting layer and which have a constant mixing ratio during deposition. This allows for the simple and rapid deposition of a layer with a uniform distribution of components without the need for precise control of a multitude of material sources.

[0204] According to an alternative embodiment of the present invention, the mixture contains, in addition to the components of the host material of formula (I) and the host material 2, as previously or preferably described, a phosphorescent emitter, as previously described. With a suitable mixing ratio during evaporation, this mixture can also be used as the sole material source. Premix systems consisting of two matrix materials are preferred, namely a compound of formula (1) and a compound of one of the following formulas: (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D), or (E).

[0205] Preferred are premix systems consisting of three matrix materials, namely a compound of formula (1) and two compounds of one of the formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D) or (E).

[0206] The components of the light-emitting layer of the device according to the invention can thus be processed by vapor deposition or from solution. The material combination of the host materials 1 and 2, as previously or preferably described, optionally with the phosphorescent emitter, as previously or preferably described, is provided for this purpose in a formulation containing at least one solvent. Suitable formulations have been previously described.

[0207] The light-emitting layer in the device according to the invention, according to the preferred embodiments, and the emitting compound preferably contains between 99.9 and 1 vol.%, more preferably between 99 and 10 vol.%, particularly preferably between 98 and 60 vol.%, and most preferably between 97 and 80 vol.% of matrix material consisting of at least one compound of formula (1) and at least one compound of one of formulas (A), (Aa), (Aa-1), (Aa-2), (Aa-3), (Aa-4), (Aa-5), (Aa-6), (Aa-7), (Aa-8), (Ab), (Ac), (Ad), (Ae), (Af), (Af-1), (Af-2), (Af-3), (B), (Ba), (Bb), (Be), (C), (Ca), (D) or (E) 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.%, and particularly preferably between 2 and 40 vol.%.-%, most preferably between 3 and 20 vol% of the emitter based on the total composition of the light-emitting layer consisting of emitter and matrix material. If the compounds are processed from solution, the corresponding amounts in wt% are preferably used instead of the amounts in vol% specified above.

[0208] The present invention also relates to an organic electroluminescent

[0209] Device as previously described or preferably described, wherein the organic layer comprises 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.

[0210] The sequence of layers in the organic electroluminescence device according to the invention is preferably the following:

[0211] Anode / Hole injection layer / Hole transport layer / Emitting layer / Hole blocking layer / Electron transport layer / Electron injection layer / Cathode.

[0212] This sequence of layers is a preferred sequence.

[0213] It should be noted again that not all of the mentioned layers need to be present and / or that additional layers may be present.

[0214] In addition to the compounds of formula (I) according to the invention, all materials used as electron transport materials in the electron transport layer according to the prior art can be used as materials for the electron transport layer. In particular, aluminum complexes, for example Alqa, 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 are suitable.

[0215] The present invention also relates to an organic electroluminescent device as previously or preferably described, wherein the organic layer comprises a hole injection layer (HIL) and / or a hole transport layer (HTL) and / or an electron blocking layer, the hole-injecting material and hole-transporting material of which is selected from the compounds of formula (1) as previously or preferably described.

[0216] Suitable cathodes for the device according to the invention include metals with low work function, metal alloys, or multilayer structures made of different metals, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys of an alkali or alkaline earth metal and silver are also suitable, for example, a magnesium-silver alloy. In multilayer structures, additional metals with relatively high work functions, such as Ag or Al, can be used, typically in combinations of these metals, such as Ca / Ag, Mg / Ag, or Ba / Ag. It may also be advantageous to insert a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor.Suitable materials for this purpose include alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Ü₂O, BaFz, MgO, NaF, CsF, CS₂CO₃). Lithium quinolinate (LiQ) can also be used. The thickness of this layer is preferably between 0.5 and 5 nm.

[0217] Materials with a high work function are preferred as anodes. Preferably, the anode has a work function greater than 4.5 eV vs. vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Alternatively, metal / metal oxide electrodes (e.g., Al / Ni / NiOx, Al / PtOx) may also be preferred. For some applications, at least one of the electrodes must be transparent or semi-transparent to allow either the irradiation of the organic material (organic solar cell) or the extraction of light (OLED, O-LASER). Conductive mixed metal oxides are preferred anode materials in this case. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Conductive doped organic materials, especially conductive doped polymers, are also preferred.Furthermore, the anode can also consist of several layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0218] The organic electroluminescent device according to the invention is structured, contacted and finally sealed accordingly during its manufacture (depending on the application), since the lifetime of the devices according to the invention is shortened in the presence of water and / or air.

[0219] The manufacture of the device according to the invention is not limited in this respect. It is possible to coat one or more organic layers, including the light-emitting layer, using a sublimation process. In this process, the materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10⁻⁶. 5 mbar, preferably less than 10 6mbar vapor deposition. However, it is also possible that the initial pressure is even lower, for example less than 10⁻⁵ mbar. 7 mbar.

[0220] The organic electroluminescence device according to the invention is preferably characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or with the aid of carrier gas sublimation. The materials are coated at a pressure between 10 -5 Pressures of mbar and 1 bar are applied. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured.

[0221] A further preferred feature of the organic electroluminescent device according to the invention is that one or more organic layers containing the composition according to the invention are produced from solution, e.g., by spin coating, or by any printing process, e.g., screen printing, flexographic printing, nozzle printing, or offset printing, but particularly preferably LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. Soluble host materials 1 and 2 and phosphorescent emitters are required for this purpose. Processing from solution has the advantage that, for example, the light-emitting layer can be applied very easily and cost-effectively. This technique is particularly suitable for the mass production of organic electroluminescent devices.

[0222] Hybrid processes are also possible, in which, for example, one or more layers of solution are applied and one or more further layers are vapor-deposited.

[0223] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices.

[0224] A further object of the description is therefore a method for producing the organic electroluminescent device according to the invention, as previously described or preferably described, characterized in that the organic layer, preferably the light-emitting layer, the hole injection layer and / or hole transport layer, is applied by vapor phase deposition, in particular with a sublimation process and / or with an OVPD (Organic Vapor Phase Deposition) process and / or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing process.

[0225] In the production process using vapor deposition, there are fundamentally two ways in which the organic layer according to the invention, preferably the light-emitting layer, can be applied or evaporated onto any substrate or the previous layer. Firstly, the materials used can each be placed in a separate material source and then evaporated from the various material sources ("co-evaporation"). Secondly, the various materials can be premixed ("premix systems") and the mixture placed in a single material source from which it is then evaporated ("premix evaporation"). This allows for the simple and rapid deposition of the light-emitting layer with a uniform distribution of the components, without the need for precise control of numerous material sources.

[0226] The following procedures are possible:

[0227] A method for producing the organic electroluminescent device according to the invention, as previously described or preferably described, characterized in that the organic layer, preferably the light-emitting layer, the electron transport layer and / or hole-blocking layer, is applied by vapor deposition, in particular by a sublimation process and / or by an OVPD (Organic Vapor Phase Deposition) process and / or by means of carrier gas sublimation, or from solution, in particular by spin coating or by a printing process.

[0228] A method for producing the organic electroluminescent device according to the invention, as previously described 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 formula (I) together with the other materials forming the light-emitting layer are deposited successively or simultaneously from at least two material sources from the gas phase.

[0229] A method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of formula (I) together with at least one further matrix material as a premix, is deposited from the gas phase successively or simultaneously with the light-emitting materials selected from the group of phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0230] The electronic devices according to the invention, in particular organic electroluminescence devices, are characterized by one or more of the following surprising advantages over the prior art:

[0231] 1. Electronic devices, in particular organic electroluminescent devices containing compounds according to formula (I) or the preferred embodiments described above and below, especially as matrix material or as hole-conducting materials, exhibit a very good lifetime. These compounds, in particular, result in a low roll-off, i.e., a low decrease in the power efficiency of the device at high luminance levels.

[0232] 2. The compounds according to the invention according to formula (I) or the preferred embodiments described above and below exhibit very high stability and service life.

[0233] 3. With compounds according to formula (I) or the preferred embodiments described above and below, the formation of optical loss channels can be avoided in electronic devices, in particular organic electroluminescent devices. This results in these devices exhibiting high PL and thus high EL efficiency of emitters, or excellent energy transfer from the matrices to dopants.

[0234] 4. The compounds according to formula (I) or the preferred embodiments described above and below have a triplet level T1, which may, for example, be in the range of 2.40 eV to 2.90 eV.

[0235] These aforementioned advantages do not come at the cost of an excessively high deterioration of other electronic properties.

[0236] A further object of the present invention is the use of a compound according to formula (I) or a mixture according to the invention in an organic electroluminescent device.

[0237] It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Unless explicitly excluded, each feature disclosed in the present invention may be replaced by alternative features serving the same, an equivalent, or a similar purpose. Thus, unless otherwise stated, each feature disclosed in the present invention is to be considered as an example of a generic series or as an equivalent or similar feature.

[0238] All features of the present invention can be combined with one another in any way, unless certain features and / or steps are mutually exclusive. This applies in particular to preferred features of the present invention. Likewise, features of non-essential combinations can be used separately (and not in combination).

[0239] The teaching on technical action disclosed in the present invention can be abstracted and combined with other examples. The invention is further explained by the following examples, without being intended to limit it.

[0240] Examples

[0241] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be obtained, for example, from Sigma-ALDRICH or ABCR. The corresponding CAS numbers are given for the compounds known from the literature. a) 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)indolo[3,2,1-jk]carbazole

[0242] 4-Bromoindolo[3,2,1-jk]carbazole (89 g, 280 mmol) and 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane (76.20 g, 300 mmol) are placed in 1,4-dioxane (2000 mL) under an inert atmosphere and treated with potassium acetate (82.33 g, 1.40 mol) and trans-dichlorobis(tricyclohexylphosphine)palladium(II) (6.21 g, 83.9 mmol) and stirred under reflux for 32 h. After cooling, the solvent is removed by rotary evaporation, the residue is worked up extractively with toluene / water, and the organic phase is dried over sodium sulfate. The crude product is stirred under reflux with ethanol (1100 mL), the solid is filtered off after cooling and washed with ethanol.

[0243] Yield: 74.5 g (203 mmol, 73%), 94% according to 1 H-NMR. Analogously, the following compounds are produced: b) 4-(2-nitrophenyl)indolo[3,2,1-jk]carbazole

[0244] A well-stirred, degassed suspension of 41 g (114 mmol) 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indolo[3,2,1-jk]carbazole, 13.4 g (47 mmol) 2,5-dibromonitrobenzene, and 29.6 g (140 mmol) potassium carbonate in a mixture of 150 mL water and 150 mL THF is treated with 0.5 g (0.4 mmol) Pd(PPhs)₄ and heated under reflux for 20 h. After cooling, the organic phase is separated, washed three times with 200 mL water and once with 200 mL saturated aqueous saline, dried over magnesium sulfate, and rotated to dryness under vacuum. The gray residue is recrystallized from T0IU0I / CH₂CI₂. The precipitated crystals are vacuum-sealed, washed with a little MeOH, and dried under vacuum;

[0245] Yield: 34 g (94 mmol), 85% of theory; Purity: 98.0% n. HPLC.

[0246] The following compounds can be prepared analogously. Here, Pd₂(dba)₃ with SPhos [657408-07-6] or tetrakis(triphenylphosphine)palladium(0) or bis(triphenylphosphine)palladium(II) chloride [13965-03-2] can also be used as a catalyst system (palladium source and ligand). Column chromatography can also be used for purification, or other common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or for recrystallization, Hocir boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacet- | amide, N-methylpyrrolidone, etc. are used.

[0247] c) 11-phenyl-5H-pyrrolo[2,3-c:4,5,1-j'k']dicarbazole A mixture of 52 g (120 mmol) of 4-(2-nitrophenyl)-11-phenylindolo[3,2,1-jk]carbazole and 290.3 ml (1670 mmol) of triethyl phosphite is heated under reflux for 12 h. The remaining triethyl phosphite is then distilled off (72–76 °C / 9 mm Hg). The residue is treated with water / MeOH (1:1), the solid is filtered off, and recrystallized.

[0248] Yield: 43 g (106 mmol), 89% of theory; Purity: 98.2% by HPLC

[0249] The following connections can be represented analogously. d) 5-(Phenyl-d5)-5H-Diindolo[2,3-c:3',2',T-jk]carbazole

[0250] 7 g (44 mmol) of bromobenzene-ds, 13.5 g (41 mmol) of 5H-pyrrolo[2,3-c:4,5,1-j'k']dicarbazole and 7.82 g (81.4 mmol; 2.00 eq.) of sodium tert-butoxide [CAS 865-47-4] are suspended in 500 mL of ort / 70-xylene [CAS 95-47-6]. To this suspension, 1.50 g (3.66 mmol; 9 mol%) of dicyclohexyl-(2',6'-dimethoxy-biphenyl-2-yl)phosphane (SPhos) [CAS 657408-07-6] and 1.12 g (1.22 mmol, 3 mol%) of tris(dibenzylideneacetone)dipalladium [CAS 51364-51-3] are added, and the reaction mixture is heated under reflux for 16 h. The reaction mixture is cooled to room temperature, and the solvent is removed under reduced pressure. The resulting solid is washed with 300 mL of ethanol and recrystallized several times from a mixture of heptane and xylene. After hot filtration through Alox and final sublimation under high vacuum, the purified product is obtained as a colorless solid: 12.3 g (30 mmol; 73%).

[0251] Similarly, the following connections are made: e) 5H-pyrrolo[2,3-c:4,5,1-j'k']dicarbazole-di3

[0252] 5.1 g (15.5 mmol; 1.00 eq) of 5H-pyrrolo[2,3-c:4,5,1-j'k']dicarbazole and 20.0 g of 5% potassium phosphate on activated carbon are suspended in 400 g (502 mmol; 1.00 eq) of deuterium oxide [CAS 7789-20-0] and 200 g (778 mmol; 1.55 eq) of toluene-d8 [CAS 2037-26-5]. The reaction mixture is stirred for 5 days at 165°C and elevated pressure. After cooling, the mixture is extracted twice with tetrahydrofuran, and the combined organic phases are washed with saline solution and dried over sodium sulfate. After filtration, the solvent is removed under reduced pressure. The product shown above, in mixture with portions of H / D isotopomers and H / D isotopologues, is obtained after further purification by extraction, recrystallization, and sublimation. The yield is 3.1 g (9.3 mmol), corresponding to 60% of the theoretical yield.

[0253] Similarly, the following connections are made: Manufacturing of OLEDs

[0254] In the following examples V1 to V3 and Ex1 to Ex8 (see Tables 7 and 8), data for various OLEDs are presented. Examples Ex1 to Ex8 show data for OLEDs according to the invention, while examples V1 to V3 show corresponding comparative examples according to the prior art.

[0255] The OLEDs listed in Table 7 are substrates made of glass platelets coated with 50 nm thick, structured ITO (indium tin oxide). The exact structure of the OLEDs is shown in Table 7. The materials required for fabricating the OLEDs are listed in Table 9, unless otherwise described earlier.

[0256] 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 (emitter), which is added to the matrix material(s) by cover vapor deposition in a specific volume fraction. A specification such as E3:H2:TEG2 (48%:40%:12%) 40nm means that material E3 is present in a volume fraction of 48% as host material 1, compound H2 as host material 2 in a fraction of 40%, and TEG2 in a fraction of 12% in a 40nm thick layer. Similarly, the hole injection layer (HIL) and the electron transport layer (ETL) can also consist of a mixture of two materials.

[0257] The OLEDs are characterized according to standard procedures. For this, the electroluminescence spectra and current-voltage-luminance (IUL) characteristics are measured, and the EQE is calculated from these measurements. The calculation assumes a Lambertian emission characteristic. EQE10 denotes the external quantum efficiency at a current density of 10 mA / cm². 2 .

[0258] For each example, the relative EQE is calculated in comparison to the respective comparison example: rel. EQE (Ex) = 100 * (EQE10(Ex) / EQE10(V)).

[0259] The lifetime LT90 is defined as the time after which the luminance decreases when operating at a constant current density jo in mA / cm². 2 from a starting luminance L0 (in cd / m²) 2 ) drops to 90% of this initial luminance. In the examples shown here, the current density used is 80 mA / cm². 2For each example, the relative LT is calculated in comparison to the respective reference example: rel. LT (Ex) = 100 * (LT90(Ex) / LT90(V)). Use of mixtures according to the invention in OLEDs

[0260] The compounds or material combinations according to the invention can be used in the emission layer in phosphorescent green OLEDs.

[0261] The data for the various OLEDs are summarized in Table 8. Example V1 is a comparative example according to the prior art, while examples Ex1 to Ex10 show data for OLEDs according to the invention. The examples according to the invention demonstrate, in particular, an advantage in the lifetime of the device.

[0262] Table 7: Structure of OLEDs

[0263] Table 8:

[0264] Table 9: Materials used, unless otherwise described

Claims

Patent claims 1. Compounds of formula (I), Formula (I), where: Ar is an aromatic ring system with 6 to 40 ring atoms, separated by one or more R groups. 5 may be substituted or a heteroaromatic Ring system selected from the group consisting of carbazole, dibenzofuran or dibenzothiophene, each of which is joined by one or more R groups 5 may be substituted; R 1 , R 2 , R 3 , R 4are, in each occurrence, the same or different H, D, F, a straight-chain alkyl, alkoxy, or thioalkoxy group with 1 to 40 C atoms, a branched or cyclic alkyl, alkoxy, or thioalkoxy group with 3 to 40 C atoms, or an alkenyl group with 2 to 20 C atoms, wherein in each group one or more H atoms may be replaced by D, an aromatic ring system with 6 to 40 ring atoms, or a heteroaromatic ring system with 5 to 40 ring atoms, wherein the aromatic or heteroaromatic ring systems are each modified by one or more R groups 6 can be substituted; in this case, two or more adjacent residues R 1 , two or more adjacent residues R 2 , two or more adjacent residues R 3 , form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more Ds; D is deuterium; R5 , R 6 are the same or different in each occurrence D, F, OH, CN, a straight-chain alkyl group with 1 to 20 C atoms, a branched or cyclic alkyl group with 3 to 20 C atoms, wherein in these alkyl groups one or more H atoms may be replaced by D or F, an aromatic ring system with 6 to 40 ring atoms or a heteroaromatic ring system with 5 to 40 ring atoms, in each of which one or more H atoms may be replaced by D or an alkyl group with 1 to 4 carbon atoms; wherein optionally two or more adjacent residues R 5 , two or more adjacent residues R 6 , can form a mono- or polycyclic, aliphatic aromatic or heteroaromatic ring system which may be substituted with one or more D; wherein the compounds of formula (I) are partially or completely deuterated.

2. Compounds according to claim 1, wherein Ar represents an aromatic ring system with 6 to 25 ring atoms, which is separated by one or more R groups. 5 may be substituted, or signifies a heteroaromatic ring system selected from the group consisting of carbazole, dibenzofuran or dibenzothiophene, each of which is modified by one or more R groups. 5 may be substituted.

3. Compound according to claim 1 or 2, wherein at least one of the residues R 1 , R 2 , R 3 , R 4 or R 6 D is and none of the remainders R 5 D is.

4. Compound according to claim 1 or 2, wherein at least one of the residues R 5 D is and none of the remainders R 1 , R 2 , R 3 , R 4 or R 6 D is.

5. Compound according to claim 1 or 2, wherein at least one of the residues R 1 , R 2 , R 3 , R 4 or R 6D is and at least one of the residues R 5 D is.

6. Compound according to at least one of claims 1 to 5, wherein the The connection is selected from the group consisting of H1 to H30:

7. Mixture comprising at least one of the compounds according to one of claims 1 to 6 and at least one further compound selected from the group consisting of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

8. Use of at least one compound of formula (I) according to one or more of claims 1 to 6 or of a mixture according to claim 7 in an organic electronic device.

9. Organic electronic device comprising an anode, a cathode and at least one organic layer, containing at least one compound of formula (I) according to one or more of claims 1 to 6.

10. Organic electronic device according to claim 9, wherein the electronic device is an organic integrated circuit (OlCs), an organic field-effect transistor (OFET), an organic thin-film transistor (OTFT), an organic electroluminescent device, an organic solar cell (OSC), an organic optical detector or an organic photoreceptor.

11. Organic electronic device according to claim 9 or 10, wherein the organic layer comprises at least one light-emitting layer, one hole-transporting layer, one hole-injecting layer or one electron-blocking layer comprising at least one compound according to any one of claims 1 to 6.

12. Organic electronic device according to claim 11, wherein the light-emitting layer contains at least one further matrix material in addition to the compound of formula (I) according to any one of claims 1 to 6.

13. Organic electroluminescent device according to claim 12, characterized in that the further matrix material corresponds to one or more of the compounds of formulas (A), (B), (C), (D) and / or (E), Formula (A), mel (E), where the following applies to the symbols and indices used: X is the same or different in each occurrence N or CR X , preferably N; L is, in each occurrence, either the same or different, a single bond or an aromatic or heteroaromatic ring system with 5 to 24 ring atoms, each with one or more R groups. 11 may be substituted; R## is the same or different in each occurrence D, F, CN, a straight-chain alkyl group with 1 to 10 C atoms, a branched or cyclic alkyl group with 3 to 10 C atoms, or an alkenyl group with 2 to 10 C atoms, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, coupled with one or more R groups 8 can be substituted and two adjacent substituents R## can together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, which is joined with one or more R groups 8 may be substituted; Y is the same or different in each occurrence N or CR 11 , excluding the possibility that two adjacent Ys simultaneously represent N; V 2 is O or S; R xis the same or different in each occurrence D, F, CN, a straight-chain alkyl group with 1 to 20 C atoms or an alkenyl or alkynyl group with 2 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each linked to one or more R groups 11 can be substituted and where one or more non-adjacent CH2 groups are replaced by Si(R 1 1 )2, C=O, NR 11 , O, S or CONR 11 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which may be partially or completely deuterated; Ar 1 In each instance, the term represents, in the same or different ways, an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which is coupled with one or more R groups. 11 may be substituted; R 8The substance is, in each occurrence, the same or different: H, D, F or an aliphatic, aromatic or heteroaromatic organic residue, in particular a hydrocarbon residue, with 1 to 20 C atoms, in which one or more H atoms may also be replaced by F R 10 is the same or different in each occurrence H, D, F, CI, 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 with 1 to 20 carbon atoms, or an alkenyl or alkynyl group with 2 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group is each linked to one or more R groups 12 can be substituted, with one or more non-adjacent CH2 groups being replaced by Si(R 8 )2, C=O, NR 8 , O, S or CONR8 can be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is replaced by one or more R groups 12 It can be substituted; in this case, two or more residues R can be involved. 10 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R 11 is the same or different in each occurrence D, F, CI, 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 with 1 to 20 carbon atoms, or an alkenyl or alkynyl group with 2 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group is each linked to one or more R groups 12can be substituted, with one or more non-adjacent CH2 groups being replaced 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, which may be partially or completely deuterated; in which case two or more Leftovers R 11 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R 12 The group is the same or different in each occurrence: D, F, CN, a straight-chain alkyl group with 1 to 20 carbon atoms, or an alkenyl or alkynyl group with 2 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms. C atoms, wherein the alkyl, alkenyl or alkynyl group is each associated with one or more R groups 11 can be substituted, with one or more non-adjacent CH2 groups being replaced by Si(R 1 1 )2, C=O, NR 11 , O, S or CONR11 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be partially or completely deuterated; b1 is 0, 1, 2, 3 or 4 and b2 is 0, 1, 2 or 3.

14. Organic electronic device according to one or more of the claims 9 to 13, characterized in that the light-emitting layer contains a phosphorescent emitter.

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