WO2025045842A1 - Materials for organic light-emitting devices - Google Patents

Abstract

The present invention relates to OLED materials for use in electronic devices, in particular in organic light-emitting devices, and to electronic devices, in particular organic light-emitting devices, which contain these OLED materials.

Description

Materials for organic light-emitting devices

The present invention relates to OLED materials for use in electronic devices, in particular in organic light-emitting devices, as well as electronic devices, in particular organic light-emitting devices, containing these OLED materials.

Electronic devices containing organic and/or organometallic semiconductors will be used in many commercial products, for example in organic light-emitting diodes (OLEDs). There is a great need to improve the performance data, especially lifetime, efficiency and operating voltage. This applies in particular to blue phosphorescent OLEDs or hyperphosphorescent OLEDs.

The object of the present invention is to provide compounds which are suitable for use in an electronic device, in particular an OLED, in particular as electron blocking materials and/or as host materials, and which lead to good properties there. WO 2010/054729 discloses diaza- and tetraazasilane derivatives which are used as electron blocking material and/or as matrix material for green or blue phosphorescent compounds. Even if good results have already been achieved with these compounds, further improvements are desirable, in particular with regard to efficiency, voltage and/or service life.

Surprisingly, it has been found that certain asymmetric tetraazasilane derivatives described in more detail below solve this problem and are well suited for use in electronic devices, in particular OLEDs. The OLEDs in particular have an improved service life, higher efficiency and/or lower operating voltage compared to OLEDs that contain symmetric tetraazasilane derivatives. These compounds and electronic devices, in particular organic electroluminescent devices that contain these compounds, are therefore the subject matter of the present invention. The present invention relates to a compound according to formula (1),

Formula (1 ) where the symbols used are:

X is the same or different at each occurrence and is CR or N, with the proviso that not more than two Xs per cycle represent N;

Ar ¹ , Ar ² , Ar ³ , Ar ⁴ is, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms which may be substituted by one or more radicals R;

SO oder SO2 ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 60 aromatischen Ringatomen, bevorzugt mit 5 bis 40 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R¹ substituiert sein kann; dabei können zwei oder mehrere Reste R miteinander ein Ringsystem bilden; R¹ ist bei jedem Auftreten gleich oder verschieden H, D, F, CI, Br, I, B(OR²)2, CHO, C(=O)R², CR²=C(R²)2, CN, C(=O)OR², Si(R²)₃, Ge(R²)₃, NO₂, P(=O)(R²)₂, OSO2R², SR², S(=O)R², S(=O)₂R², eine geradkettige Alkylgruppe mit 1 bis 20 C-Atomen oder eine Alkenyl- oder Alkinylgruppe mit 2 bis 20 C-Atomen oder eine verzweigte oder cyclische Alkylgruppe mit 3 bis 20 C-Atomen, wobei die Alkyl-, Alkenyl- oder Alkinylgruppe jeweils mit einem oder mehreren Resten R² substituiert sein kann und wobei eine oder mehrere CH2-Gruppen in den oben genannten Gruppen durch -R²C=CR²-, -C=C-, Si(R²)2, C=O, C=S, -C(=O)O-, CONR², P(=O)(R²), -S-, SO oder SO2 ersetzt sein können und wobei ein oder mehrere H-Atome in den oben genannten Gruppen durch D, F, CI, Br, I, CN oder NO2 ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 30 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R² substituiert sein kann, wobei zwei oder mehr Reste R¹ miteinander ein Ringsystem bilden können; R is, identically or differently on each occurrence, H, D, F, CI, Br, I, OR ¹ , SR ¹ , B(OR ¹ ) ₂ , CHO, C(=O)R ¹ , CR ¹ =C(R ¹ ) ₂ , CN, C(=O)OR ¹ , C(=O)NR ¹ , Si(R ¹ ) ₃ , Ge(R ¹ ) ₃ , NO2, P(=O)(R ¹ ) ₂ , OSO2R ¹ , OR ¹ , N(R ¹ ) ₂ , S(=O)R ¹ , S(=O)2R ¹ , SR ¹ , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group can each be substituted by one or more radicals R ¹ , where one or more non-adjacent CH2 groups are substituted by -R ¹ C=CR ¹ -

SO or SO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ ; two or more radicals R can form a ring system with one another; R ¹ is, identically or differently on each occurrence, H, D, F, CI, Br, I, B(OR ² )2, CHO, C(=O)R ² , CR ² =C(R ² )2, CN, C(=O)OR ² , Si(R ² ) ₃ , Ge(R ² ) ₃ , NO ₂ , P(=O)(R ² ) ₂ , OSO2R ² , SR ² , S(=O)R ² , S(=O) ₂ R ² , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted with one or more radicals R ² can be substituted and wherein one or more CH2 groups in the abovementioned groups can be replaced by -R ² C=CR ² -, -C=C-, Si(R ² )2, C=O, C=S, -C(=O)O-, CONR ² , P(=O)(R ² ), -S-, SO or SO2 and wherein one or more H atoms in the abovementioned groups can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ² , where two or more radicals R ¹ can form a ring system with one another;

R ² is, on each occurrence, identically or differently, H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms can also be replaced by D or F; two or more substituents R ² can be linked to one another and form a ring; characterized in that not all of the groups Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are identical and/or that the two cycles containing X are different and/or the two cycles containing X are differently substituted; the following compound is excluded from the invention:

The condition that not all of the groups Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are identical can also mean that Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same aromatic or heteroaromatic ring system, but are differently substituted.

An aryl group in the sense of this invention contains 6 to 40 C atoms; a heteroaryl group in the sense of this invention contains 5 to 40 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e. benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc., or a condensed (fused) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatics linked to one another by a single bond, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

An aromatic ring system in the sense of this invention contains 6 to 60 C atoms, preferably 6 to 40 C atoms in the ring system. A heteroaromatic ring system in the sense of this invention contains 1 to 60 C atoms, preferably 1 to 40 C atoms and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the sense of this invention is to be understood as a system which does not necessarily only contain aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be connected by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as a C, N or O atom or carbonyl group. This also includes systems in which two or more aryl or heteroaryl groups are directly linked to one another, such as biphenyl, terphenyl, bipyridine or phenylpyridine. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are also to be understood as aromatic ring systems in the sense of this invention, as are systems in which two or more aryl groups are connected, for example, by a linear or cyclic alkyl group or by a silyl group. Preferred aromatic or heteroaromatic ring systems are simple aryl or heteroaryl groups as well as groups in which two or more aryl or heteroaryl groups are directly linked to one another, for example biphenyl, terphenyl, quaterphenyl or bipyridine, as well as fluorene or spirobifluorene.

An electron-rich heteroaromatic ring system is characterized by the fact that it is a heteroaromatic ring system that does not contain any electron-poor heteroaryl groups. An electron-poor heteroaryl group is a six-membered ring heteroaryl group with at least one nitrogen atom or a five-membered ring heteroaryl group with at least two heteroatoms, one of which is a nitrogen atom and the other is oxygen, sulfur or a substituted nitrogen atom, where further aryl or heteroaryl groups can be fused to each of these groups. In contrast, electron-rich heteroaryl groups are five-membered ring heteroaryl groups with exactly one heteroatom selected from oxygen, sulfur or substituted nitrogen, to which further aryl groups and/or further electron-rich five-membered ring heteroaryl groups can be fused. Examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene or indenocarbazole. An electron-rich heteroaryl group is also called an electron-rich heteroaromatic residue. An electron-poor heteroaromatic ring system is characterized in that it contains at least one electron-poor heteroaryl group, and particularly preferably no electron-rich heteroaryl groups.

In the context of the present invention, the term alkyl group is used as a generic term for both linear or branched alkyl groups and for cyclic alkyl groups. Analogously, the terms alkenyl group and alkynyl group are used as generic terms for both linear or branched alkenyl or alkynyl groups, as well as for cyclic alkenyl or alkynyl groups. A cyclic alkyl, alkoxy or thioalkoxy group in the sense of this invention is understood to mean a monocyclic, bicyclic or polycyclic group.

In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which can contain 1 to 40 C atoms and in which individual H atoms or CH2 groups can also be substituted by the abovementioned groups, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 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-methylcyclo-hexyl, n-octyl, cyclooctyl, 2-ethylhexyl, 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 -Diethyl-n-hexadec-1 -yl,

1, 1 -Diethyl-n-octadec-1 -yl, 1 -(n-Propyl)-cyclohex-l -yl, 1 -(n-Butyl)-cyclohex-1 -yl, 1 -(n-Hexyl)-cyclohex-1 -yl, 1 -(n-Octyl)-cyclohex-l -yl and l -(n-Decyl)-cyclohex-1 -yl, Ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, cyclooctadienyl, ethynyl, propynyl, butynyl, pentinyl, hexynyl, heptynyl or Octynyl is understood. An alkoxy group OR ¹ with 1 to 40 C atoms is preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. A thioalkyl group SR ¹ with 1 to 40 C atoms is particularly understood to mean methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio,

1-Butylthio, s-Butylthio, t-Butylthio, n-Pentylthio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclooctylthio,

2-Ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. In general, alkyl, alkoxy or thioalkyl groups according to the present invention can be straight-chain, branched or cyclic, where one or more non-adjacent CH2 groups can be replaced by the abovementioned groups; furthermore, one or more H atoms can also be replaced by D, F, CI, Br, I, CN or NO2, preferably D, F, CI or CN, particularly preferably D, F or CN.

An aromatic or heteroaromatic ring system with 5 - 60 aromatic ring atoms, preferably 5 - 40 aromatic ring atoms, which can be substituted by the above-mentioned radicals or a hydrocarbon radical and which can be linked to the aromatic or heteroaromatic via any position, is understood to mean in particular groups which are derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, Truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, iso- quinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazine-imidazole, quinoxalinimidazole, oxazole, benzoxazole, Naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1 ,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1 ,2,3-triazole, 1 ,2,4-triazole, benzotriazole, 1 ,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1 ,2,4-Triazine, 1 ,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole or groups derived from combinations of these systems. These groups can also be deuterated.

The phrase that two or more residues can form a ring system with one another is to be understood in the context of the present description to mean, among other things, that the two residues are linked to one another by a chemical bond with formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

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

In a preferred embodiment of the invention, all X groups are CR, or two X groups in each of the two cycles are N, so that a pyrazine is formed, or two X groups in one of the two cycles are N, so that a pyrazine is formed, and all X in the other cycle are CR. Preference is therefore given to the compounds of the following formula (2), (3) and (4), with the compounds of the formula (2) being particularly preferred,

Formula (4) where the symbols used have the meanings given above.

According to the invention, these are asymmetric structures. These are characterized by the fact that not all four groups Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are identical and/or by the fact that the two cycles containing the groups X are different, as is the case, for example, in the compounds of formula (4). Compounds in which the two cycles containing the groups X are different also exist when, for example, as in formula (2), all X are CR, but the R residues on the two cycles are chosen differently and/or are bound in different positions.

When substituents are attached to the two phenylene rings in structures of formula (2), preferred structures are the compounds of the following formulas (2a) to (2f),

Formula (2c) Formula (2d)

Formula (2e) Formula (2f) where the structure can also be partially or completely deuterated, and Ar ¹ to Ar ⁴ and R have the meanings given above. The structures of the formulas (2a), (2b) and (2d) are preferred.

When Ar ¹ to Ar ⁴ are identical, the substituents R on the two phenylene rings are different and/or are bonded in different positions. Examples of such compounds are compounds of formula (2d) or (2e) in which one R is H or D and the other R is phenyl, ortho-, meta- or para-biphenyl, N-carbazolyl, 1-, 2-, 3- or 4-dibenzofuranyl or N-benzimidazobenzimidazole. In a preferred embodiment of the invention, not all four groups Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are identical. Various embodiments are suitable for this:

(1 ) Ar ¹ = Ar ² and Ar ³ = Ar ⁴ , but Ar ¹ + Ar ³

(2) Ar ¹ = Ar ³ and Ar ² = Ar ⁴ , but Ar ¹ + Ar ²

(3) Ar ¹ = Ar ² = Ar ³ and Ar ⁴ + Ar ¹

(4) Ar ¹ = Ar ² and Ar ³ + Ar ⁴ + Ar ¹

(5) Ar ¹ = Ar ³ and Ar ² + Ar ⁴ + Ar ¹

(6) Ar ¹ + Ar ² + Ar ³ + Ar ⁴ .

Embodiments (1), (2) and (6) are particularly preferred. Different groups Ar ¹ to Ar ⁴ can be different aromatic or heteroaromatic ring systems, and/or they are the same aromatic or heteroaromatic ring systems but are differently substituted.

Preferred embodiments for Ar ¹ to Ar ⁴ are described below. In a preferred embodiment of the invention, Ar ¹ to Ar ⁴ are the same or different on each occurrence and are selected from an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, particularly preferably having 6 to 24 aromatic ring atoms and very particularly preferably having 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.

In a preferred embodiment of the invention, at least one of the groups Ar ¹ to Ar ⁴ contains at least 12 aromatic ring atoms. Particularly preferably, at least two of the groups Ar ¹ to Ar ⁴ each contain at least 12 aromatic ring atoms.

If all groups Ar ¹ to Ar ⁴ each contain only 6 aromatic ring atoms, it is preferred if the compound has at least one aromatic or heteroaromatic substituent R which contains at least 12 aromatic ring atoms, and/or if the compound bond has at least two aromatic or heteroaromatic substituents R.

Suitable aromatic or heteroaromatic ring systems Ar ¹ to Ar ⁴ are selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which can be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which can be linked via the 1-, 2-, 3- or 4-position, naphthalene, which can be linked via the 1- or 2-position, indole, benzofuran, benzothiophene, which can be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which can be linked via the 1-, 2-, 3- or 4-position, carbazole, which can be linked via the 1-, 2-, 3- or 4-position. can be dibenzothiophene, which can be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, benzimidazole, benzimidazobenzimidazole, phenanthrene, triphenylene or a combination of two or three of these groups, each of which can be substituted by one or more radicals R, preferably non-aromatic radicals R. If Ar ¹ bis is a heteroaryl group, in particular triazine, pyrimidine, quinazoline or carbazole, aromatic or heteroaromatic radicals R on this heteroaryl group can also be preferred.

Preferred groups Ar ¹ to Ar ⁴ are selected, identically or differently at each occurrence, from the groups of the following formulas (Ar-1) to (Ar-144),

Ar-29 Ar-30

wobei R die oben genannten Bedeutungen aufweist, die gestrichelte Bindung die Bindung an ein Stickstoffatom in Formel (1 ) darstellt und weiterhin gilt:

where R has the meanings given above, the dashed bond represents the bond to a nitrogen atom in formula (1 ) and furthermore:

Ar# is, identically or differently at each occurrence, a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, each of which may be substituted by one or more radicals R;

A ¹ is, identically or differently at each occurrence, BR, C(R) 2, C=O, NR, 0 or S; p is 0 or 1, where p = 0 means that the group Ar# is not present and that the corresponding aromatic or heteroaromatic group is directly bonded to the nitrogen atom; r is 0 or 1, where r = 0 means that no group A ¹ is bonded at this position and R radicals are bonded to the corresponding carbon atoms instead.

In a preferred embodiment, Ar ¹ to Ar ⁴ do not contain any fused aryl groups. In contrast, fused heteroaryl groups in which no six-membered rings are directly fused to one another may be suitable, for example carbazole, dibenzofuran or dibenzothiophene.

wobei die gestrichelte Bindung die Bindung an das Stickstoffatom darstellt und diese Strukturen auch teilweise oder vollständig deuteriert sein können. Particularly preferred groups Ar ¹ to Ar ⁴ are the same or different at each occurrence and are selected from the group consisting of the following structures Ar-a to Ar-I,

where the dashed bond represents the bond to the nitrogen atom and these structures can also be partially or completely deuterated.

Examples of particularly preferred combinations of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are the combinations listed in the following table:

Preferred substituents R, R ¹ and R ² are described below. In a particularly preferred embodiment of the invention, the preferences for R, R ¹ and R ² mentioned below occur simultaneously and apply to the structures of the formula (1) as well as to all preferred embodiments.

Preferred substituents R which are bonded to Ar ¹ to Ar ⁴ are selected, identically or differently at each occurrence, from the group consisting of H, D, F, CN, Si(R ¹ ) s, Ge(R ¹ ) s, a straight-chain alkyl group having 1 to 10 C atoms or cyclic alkyl group having 3 to 10 C atoms, where the alkyl group can be substituted in each case by one or more radicals R ¹ , but is preferably unsubstituted, and where one or more non-adjacent CH2 groups can be replaced by 0; two adjacent radicals R can form a ring system with one another. Particularly preferably, R, which is bonded to Ar ¹ to Ar ⁴ , is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, Si(R ¹ ) s, a straight-chain alkyl group having 1 to 6 C atoms, in particular having 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group having 3 to 6 C atoms, where the alkyl group can in each case be substituted by one or more radicals R ¹ , but is preferably unsubstituted; two adjacent Rs can form a ring system with one another. Very particularly preferably, R, which is bonded to Ar ¹ to Ar ⁴ , is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, Si(C6Hs) 3, where the phenyl group can optionally be deuterated and/or can be substituted by one or more optionally deuterated methyl groups, or optionally deuterated methyl. Preferred substituents R which bind to the carbon atom for X = CR are selected, identically or differently at each occurrence, from the group consisting of H, D, F, CN, OR ¹ , N(R ¹ ) 2, Si(R ¹ ) s, Ge(R ¹ ) s, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl group can in each case be substituted by one or more radicals R ¹ , but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which can in each case be substituted by one or more radicals R ¹ . Particularly preferably, R, which binds to the carbon atom for X = CR, is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, Si(R ¹ ) s, a straight-chain alkyl group having 1 to 6 C atoms, in particular having 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group having 3 to 6 C atoms, where the alkyl group can be substituted in each case by one or more radicals R ¹ , but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which can optionally be deuterated and in each case can be substituted by one or more radicals R ¹ , preferably non-aromatic radicals R ¹ . R, which binds to the carbon atom for X = CR, is very particularly preferably selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, Si(C6Hs)3, where the phenyl group can optionally be deuterated and/or can be substituted by one or more optionally deuterated methyl groups, or an optionally deuterated aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, particularly preferably having 6 to 18 aromatic ring atoms, which can each be substituted by one or more radicals R ¹ , preferably non-aromatic radicals R ¹ .

Suitable aromatic or heteroaromatic ring systems R are selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which can be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which can be linked via the 1-, 2-, 3- or 4-position, naphthalene, which can be linked via the 1- or 2- position, indole, benzofuran, benzothiophene, which can be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which can be linked via the 1-, 2-, 3- or 4-position, carbazole, which can be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, which can be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, benzimidazole, phenanthrene, triphenylene or a combination of two or three of these groups, each of which can be substituted by one or more radicals R ¹ . If R represents a heteroaryl group, in particular triazine, pyrimidine or quinazoline, aromatic or heteroaromatic radicals R ¹ on this heteroaryl group may also be preferred.

The groups R, when they represent an aromatic or heteroaromatic ring system, are preferably selected from the groups of the following formulas R-1 to R-144,





35

wobei R¹ die oben genannten Bedeutungen aufweist, die gestrichelte Bindung die Bindung der Gruppe darstellt und weiterhin gilt:

where R ¹ has the meanings given above, the dashed bond represents the bond of the group and furthermore:

Ar* is at each occurrence, identically or differently, a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ ;

A ¹ is, identical or different at each occurrence, BR ¹ , C(R ¹ ) 2, C=O, NR ¹ , 0 or S; p is 0 or 1, where p = 0 means that the group Ar* is not present and that the corresponding aromatic or heteroaromatic group is directly attached to the associated carbon atom; r is 0 or 1 , where r = 0 means that no group A ¹ is bonded at this position and residues R ¹ are bonded to the corresponding carbon atoms instead.

If the abovementioned groups Ar-1 to Ar-144 for Ar or R-1 to R-144 for R have several groups A ¹ , all combinations from the definition of A ¹ are possible. Preferred embodiments are then those in which one group A ¹ stands for C(R) 2, NR, 0 or S and the other group A ¹ stands for C(R) 2, NR, 0 or S if it is a group Ar, or in which one group A ¹ stands for C(R ¹ ) 2, NR ¹ , 0 or S and the other group A ¹ stands for C(R ¹ ) 2, NR ¹ , 0 or S if it is a group R.

If A ¹ stands for NR or NR ¹ , the substituent R or R ¹ which is bonded to the nitrogen atom preferably stands for an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R ¹ or R ² . In a particularly preferred embodiment, this substituent R or R ¹ is the same or different on each occurrence and stands for an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, and which can also be substituted by one or more radicals R ¹ or R ² . Particularly preferred are phenyl, biphenyl, terphenyl and quaterphenyl with linkage patterns as listed above for Ar-1 to Ar-35 or R-1 to R-35, where these structures can be substituted by one or more radicals R or R ¹ , but are preferably unsubstituted.

If A ¹ is C(R)2 or C(R ¹ )2, the substituents R or R ¹ which are bonded to this carbon atom are preferably identical or different on each occurrence and represent a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more radicals R ¹ or R ^2. Particularly preferred Preferably R or R ¹ is a methyl group or a phenyl group. The radicals R or R ¹ can also form a ring system with each other, resulting in a spiro system.

In one embodiment, the compound according to the invention contains at least one substituent Ar ¹ to Ar ⁴ and/or R which stands for an electron-rich heteroaryl group or benzimidazobenzimidazole, which can be substituted by R or R ¹ , respectively, and/or two radicals R which bind to X for adjacent X = CR form with each other and the carbon atoms to which they bind an electron-rich heteroaryl group which can be substituted by R ^1. In a further embodiment of the compound according to the invention, none of the substituents Ar ¹ to Ar ⁴ or R stands for an electron-rich heteroaryl group or benzimidazobenzimidazole, and two radicals R which bind to X for adjacent X = CR do not form an electron-rich heteroaryl group with each other and the carbon atoms to which they bind.

In a further preferred embodiment of the invention, R ¹ is the same or different on each occurrence and is selected from the group consisting of H, D, F, CN, Si(R ² ) s, Ge(R ² ) s, a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl or alkenyl group may in each case be substituted by one or more radicals R ² , or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R ² ; two or more radicals R ¹ may form an aliphatic ring system with one another. In a particularly preferred embodiment of the invention, R ¹ is the same or different on each occurrence and is selected from the group consisting of H, D, Si(C6Hs)3, where the phenyl group can be substituted in each case by one or more methyl groups, a straight-chain alkyl group having 1 to 6 C atoms, in particular with 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group having 3 to 6 C atoms, where the alkyl group can be substituted by one or more radicals R ² , but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R ² .

In a further preferred embodiment of the invention, R ² is the same or different on each occurrence and is H, D, CN, F, an alkyl group having 1 to 4 C atoms or an aryl group having 6 to 10 C atoms, which may be substituted by an alkyl group having 1 to 4 C atoms, but is preferably unsubstituted.

In a further preferred embodiment of the invention, all radicals R ¹ , insofar as they represent an aromatic or heteroaromatic ring system, are selected from the groups R-1 to R-144, which, however, are then each substituted accordingly with R ² instead of R ¹ .

In a preferred embodiment, the compounds are at least 30%, in particular at least 50%, particularly preferably at least 70%, very particularly preferably at least 90%, particularly preferably at least 98% deuterated. This means that in such a compound the corresponding proportion of the hydrogen atoms contained in the undeuterated compound have been exchanged for D. The undeuterated compound is the corresponding compound which contains hydrogen in the natural isotope distribution. In a fully deuterated compound, all H are exchanged for D.

In a further embodiment of the invention, the compounds according to the invention are undeuterated, i.e. they contain hydrogen in the natural isotope distribution.

The alkyl groups in compounds according to the invention which are processed by vacuum evaporation preferably have no more than five C atoms, particularly preferably no more than 4 C atoms, very particularly preferably no more than 1 C atom.

The compounds according to the invention can be present as racemates or as pure enantiomers when used. The formation of enantiomers mers is possible, for example, if the groups Ar ¹ , Ar ² , Ar ³ and Ar ⁴ in the compounds according to the invention are all chosen differently.

The above-mentioned preferred embodiments can be combined with one another as desired within the limitations defined in claim 1. In a particularly preferred embodiment of the invention, the above-mentioned advantages occur simultaneously.

Examples of preferred compounds according to the embodiments listed above are the compounds listed in the following table. The compounds shown as deuterated can be fully deuterated compounds or partially deuterated compounds, or they can also be a mixture of compounds that are deuterated at different positions and/or have a different degree of deuteration.

The synthesis of the compounds (5) according to the invention can be carried out, inter alia, according to Scheme 1. Starting from 1,2-diamino-substituted aromatics or heteroaromatics (1), two consecutive mono-N-arylations lead to the 1,2-bis(aryl-/heteroarylamino)aromatics or Heteroaromatics (2). The couplings can be carried out by methods known to those skilled in the art, e.g. B. the Buchwald-Hartwig or Ullmann coupling starting from Ar-Hal with Hal = CI, Br, I in the presence of a base (e.g. alkyllithium, such as n-BuLi or n-Hex-Li, an alkali metal alkoxide, such as NaO- t-Bu or KO-t-Bu, an inorganic base, such as alkali phosphates or carbonates), a palladium source (e.g. Pd2dba3, Pd(OAc)2, etc.) in combination with a preferably electron-rich phosphine (e.g. DPPF, BiNap, P(t-Bu) ₃ , S-Phos, X-Phos, AmPhos, etc.) or a copper source (e.g. Cu, CuCI, Cul, CuOTf, etc.) in combination with an amine (e.g. pyridine, bipyridine, phenanthroline, glycine, DACH, etc.) in anhydrous solvents (e.g. toluene, xylene, THF, dioxane, DMF, DMAc, NMP, DMSO, etc.). In addition, the coupling can be carried out via an SN2Ar reaction with Ar-Hal with Hal = F, CI in the presence of a base (e.g. alkyllithium, such as n-BuLi or n-Hex-Li, an alkali metal alkoxide such as NaO-t-Bu or KO-t-Bu, an inorganic base such as alkali phosphates or carbonates) in a dipolar aprotic solvent (DMF, DMAc, NMP, DMSO, sulfolane, etc.). If the radicals Ar ¹ and Ar ² to be introduced are identical, the coupling can be carried out in one step using the above methods. In a second step, the secondary diamine (2) is bis-lithiated using a base (alkyllithium or aryllithium compounds such as n-BuLi, t-BuLi, PhLi etc., or lithium amides such as lithium diisopropylamide (LDA), lithium 2,2',6,6'-tetramethylpiperidide (LiHMP), lithium hexamethyldisilazide (LiHMDS), etc.) in a solvent (e.g. diethyl ether, di-n-butyl ether, methyl t-butyl ether, tetrahydrofuran (THF), dioxane, toluene, etc.) and then reacted with a silicon halide, preferably silicon tetrachloride SiCU, to give intermediate (3). With a reactant stoichiometry of (2) to SiCU of 1:1, the reaction proceeds selectively to give intermediate (3), since this has a greatly reduced reactivity compared to a further reaction to give (5). In a third step, the intermediate (3) is reacted with the bis-lithiated diamine (4) to give the product (5) according to the invention. If the diamines (2) to be introduced are identical, ie radicals Ar ¹ = Ar ³ and Ar ² = Ar ⁴ , the coupling can be carried out in one step using the above-mentioned method at a reactant stoichiometry of (2) to SiCU of 2:1.

SN₂Ar

Scheme 1 :

SN ₂ Ar

A further object of the present invention is therefore a process for preparing the compounds according to the invention, characterized by the following steps:

(A) providing a benzene derivative or corresponding heteroaromatic derivative which is substituted in the ortho position to each other with a group -NHAr ¹ and -NHAr ² and optionally providing a benzene derivative or corresponding heteroaromatic derivative which is substituted in the ortho position to each other with a group -NHAr ³ and -NHAr ⁴ ; and

(B) reaction of SiHak, in particular SiCk, with the benzene derivative or corresponding heteroaromatic derivative which is substituted in ortho-position to each other with a group -NHAr ¹ and a group -NHAr ² , optionally followed by reaction with the benzene derivative or corresponding heteroaromatic derivative which is substituted in ortho-position to each other with a group -NHAr ³ and a group -NHAr ⁴ .

Another object of the present invention is an oligomer, polymer or dendrimer comprising one or more compounds according to formula (1 ), in which instead of one or more radicals R there is a bond to the polymer chain.

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 are required. These formulations can be, for example, solutions, dispersions or emulsions. It may be preferable to use mixtures of two or more solvents for this purpose. Suitable solvents are known to the person skilled in the art. The preparation of such solutions is known to the person skilled in the art and is described, for example, in WO 2002/072714, WO 2003/019694 and the literature cited therein.

A further subject matter of the present invention is therefore a formulation, in particular a solution, dispersion or emulsion, comprising at least one compound according to the invention and at least one further compound. The further compound can be, for example, a solvent and/or a further organic or inorganic compound which is also used in the electronic device, for example an emitting compound and/or a matrix material.

The compounds according to the invention are suitable for use in an electronic device, in particular in an organic electroluminescent device (OLED). Depending on the substitution, the compounds can be used in different functions and layers. A further subject matter of the present invention is therefore the use of a compound according to the invention in an electronic device.

Yet another object of the present invention is an electronic device comprising at least one compound according to the invention.

An electronic device in the sense of the present invention is a device which contains at least one layer containing at least one organic compound. The component can also contain inorganic materials or layers that are made entirely of inorganic materials.

The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), dye-sensitized organic solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic photodiodes (OPD), organic field quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic plasmon emitting devices.

The device is particularly preferably an organic electroluminescent device (OLED) comprising a cathode, anode and at least one emitting layer, wherein at least one layer comprises at least one compound according to the invention. In addition to these layers, the organic electroluminescent device can contain further layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers and/or organic or inorganic p/n junctions. Interlayers can also be introduced between two emitting layers, which have an exciton-blocking function, for example. It should be noted, however, that not all of these layers necessarily have to be present. The organic electroluminescent device can contain one emitting layer or several emitting layers. If several emission layers are present, these preferably have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, ie different emitting compounds are used in the emitting layers, which can fluoresce or phosphoresce. Systems with three emitting layers are particularly preferred, with the three layers emitting blue, green and orange or red. The organic electroluminescent device according to the invention can also be a tandem OLED, in particular for white-emitting OLEDs.

Preferably, the compound according to formula (1) is used in an organic electroluminescent device which comprises one or more phosphorescent emitters, wherein the compound according to the invention can be used in different layers depending on the exact structure.

In a preferred embodiment of the invention, the compounds of formula (1) are used as hole-transporting material. In this case, the compound according to the invention is preferably contained in a hole-transport layer or an exciton blocking layer or a hole-conducting host material.

A hole transport layer in the sense of the present application is a layer with a hole transporting function between the anode and the emitting layer. An exciton blocking layer in the sense of the present application is a layer that directly adjoins an emitting layer on the anode side. This is a specific embodiment of a hole transport layer.

If the compound of formula (1) is used as a hole transport material in a hole transport layer or an exciton blocking layer, the compound can be used as a pure material, i.e. in a proportion of 100% in the layer, or it can be used in combination with one or more other compounds.

In a further preferred embodiment of the invention, the compound according to the invention is used as a matrix material in an emitting layer, wherein the emitting layer can be phosphorescent, hyperphosphorescent or fluorescent.

A hyperphosphorescent emission layer is a layer which usually contains one or more matrix materials as well as one or more phosphorescent compounds which are used as sensitizers and whose luminescence is not or not significantly observed, and one or more fluorescent emitters which are responsible for the emission of the OLED.

The term "phosphorescent compound" or "phosphorescent compound" (= triplet emitter) typically refers to compounds in which the emission of light occurs through a spin-forbidden transition, e.g. a transition from an excited triplet state or a state with a higher spin quantum number, e.g. a quintet state. Preferably, luminescent complexes with transition metals or lanthanides are considered to be phosphorescent compounds, especially if they contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds that contain iridium, platinum or copper. In the context of the present invention, all luminescent iridium, platinum or copper complexes are considered to be phosphorescent emitting compounds. Iridium or platinum complexes are particularly preferred.

Examples of phosphorescent emitters can be found in the applications WO 00/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373, US 2005/0258742, WO 2009/146770, WO 2010/015307, WO 2010/031485, WO 2010/054731, WO 2010/054728, WO 2010/086089, WO 2010/099852, WO 2010/102709, WO 2011/032626, WO 2011/066898, WO 2011/157339, WO 2012/007086, WO 2014/008982, WO 2014/023377, WO 2014/094961, WO 2014/094960, WO 2015/036074, WO 2015/104045, WO 2015/117718, WO 2016/015815, WO 2016/124304, WO 2017/032439, WO 2018/011186, WO 2018/041769, WO 2019/020538, WO 2018/178001, WO 2019/115423 and WO 2019/158453. In general, all phosphorescent complexes as used in accordance with the prior art for phosphorescent OLEDs and as known to the person skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art can use further phosphorescent complexes without inventive step. For the person skilled in the art, it is also possible without inventive step Activity, it is possible to use further phosphorescent complexes in combination with the compounds of formula (1) in organic electroluminescent devices. Since the compounds according to the invention can also have a high triplet energy depending on the substitution, it is also possible in particular to use them as matrix material for blue phosphorescent emitters.

Suitable phosphorescent metal complexes that can be used in phosphorescent OLEDs or as sensitizers in hyperphosphorescent OLEDs are further disclosed, inter alia, in Sungho Nam et al., Adv. Sci. 2021, 2100586, Eungdo Kin et al., Sci. Adv. 2022, 8, 1641. Further compounds suitable as sensitizers are disclosed in EP 3435438 A2, in particular compounds 2 and 3 on page 21, in CN 109111487, in particular the compounds on pages 76 and 77, in US 2020/0140471, in particular the compounds on pages 166 to 175; in KR 2020108705, in particular the compounds on pages 8 to 14, in US 2019/0119312, in particular the compounds on pages 114 to 121, and in US 2020/0411775, in particular the compounds on pages 123 to 128. Further suitable phosphorescent metal complexes are disclosed in US 2022/0115607, US 2022/0298193, US 2016/0072082 and US 2022/0271236.

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

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

An emitting layer can also comprise systems that contain a plurality of matrix materials (mixed matrix systems) and/or a plurality of emitting compounds. In this case too, the emitting compounds are usually those that have the smaller proportion in the system and the matrix materials those that have the larger proportion in the system. In individual cases, however, the proportion of a single matrix material in the system may be lower than the proportion of a single emitting compound.

The compounds of formula (1) are preferably used as a component of mixed matrix systems. The mixed matrix systems preferably consist of two or three different matrix materials, particularly preferably of two different matrix materials. Preferably, one of the two materials is a material with hole-transporting properties and the other material is a material with electron-transporting properties. The compound of formula (1) is preferably the matrix material with hole-transporting properties. The other mixed matrix components can also fulfill other functions. The two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, even more preferably 1:10 to 1:1 and most preferably 1:4 to 1:1. Mixed matrix systems are preferably used in phosphorescent or hyperphosphorescent organic electroluminescent devices. Particularly suitable matrix materials that can be used in combination with the compounds according to the invention as matrix components of a mixed matrix system are explained in more detail below.

Examples of phosphorescent compounds are listed below.

In a preferred embodiment of the invention, the organic electroluminescent device according to the invention contains at least one blue phosphorescent metal complex, in particular at least one blue phosphorescent platinum complex. Preferably, the at least one blue phosphorescent metal complex has a LUMO of -1.8 eV to -2.2 eV, and a HOMO of -5.0 eV to -5.6 eV, as defined by quantum mechanical calculations. Preferably, the energy of the lowest triplet state Ti of the at least one blue phosphorescent metal complex is >2.55 eV, particularly preferably >2.65 eV, very particularly preferably >2.75 eV, as defined by quantum mechanical calculations.

The energy levels of molecular orbitals (highest occupied molecular orbital HOMO, lowest unoccupied molecular orbital LUMO, lowest triplet state Ti , lowest excited singlet state Si) are determined by quantum mechanical calculations. The Gaussian16 program package (Rev. B.01 ) is used in all quantum chemical calculations. The neutral singlet ground state is optimized at the B3LYP/6-31 G(d) level. HOMO and LUMO values are determined at the B3LYP/6-31 G(d) level for the ground state energy optimized with B3LYP/6-31 G(d). Then, TD-DFT singlet and triplet excitations (vertical excitations) are calculated using the same method (B3LYP/6-31 G(d)) and the optimized ground state geometry. The standard settings for SCF and gradient convergence are used. The HOMO and LUMO values in eV derived from the quantum chemical calculation are additionally scaled by the following factors:

HOMO_corr = 0.90603 * HOMO (in eV) - 0.84836 LUMO_corr = 0.99687 * LUMO (in eV) - 0.72445 For the purposes of this application, these values are to be regarded as HOMO or LUMO energy levels of the materials.

The lowest triplet state Ti is defined as the energy of the triplet state with the lowest energy resulting from the quantum chemical calculation described. The lowest excited singlet state Si is defined as the energy of the excited singlet state with the lowest energy resulting from the quantum chemical calculation described.

Suitable platinum complexes that are suitable as blue phosphorescent emitters or as sensitizers for hyperphosphorescent OLEDs are disclosed in US 2020/0140471, US 2020/0216481, US 2021/0284672, US 2022/0271236, US 2022/0399517, US 2023/0157041, US 2023/0147748 and US 2023/0065887.

The compounds of the formula (Pt-1 ) according to the following definition are very suitable as blue phosphorescent metal complexes:

Formula (Pt-1 ) where:

Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ on each occurrence, identically or differently, represent a group CR ^Y or N; or Y ¹ -Y ² and/or Y ³ -Y ⁴ or Y ⁴ -Y ⁵ can form a condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms, which in each case can also be substituted by one or more radicals R; E ⁵⁰ stands for C(R ^C0 ) ₂ , NR ^N0 , 0 or S, identically or differently at each occurrence;

Ar ⁵⁰ is, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may each also be substituted by one or more radicals R;

Ar ⁵¹ , Ar ⁵² , Ar ⁵³ are the same or different and represent a condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms, which may each also be substituted by one or more radicals R;

R ^Y on each occurrence, identically or differently, represents a radical selected from H, D, F, CI, Br, I, CHO, CN, C(=O)R, P(=O)(R) ₂ , S(=O)R, S(=O) ₂ Ar, N(R) ₂ , NO ₂ , Si(R)s, B(OR) ₂ , OSO ₂ R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH ₂ groups are substituted by RC=CR, C=C, Si(R) ₂ , Ge(R) ₂ , Sn(R) ₂ , C=O, C=S, C=Se, P(=O)(R), SO, SO ₂ , O, S or CONR and where one or more H atoms can be replaced by D, F, CI, Br, I, CN or NO ₂ , an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which can be substituted by one or more radicals R, and an aryloxy group having 5 to 40 aromatic ring atoms, which can be substituted by one or more radicals R, where two radicals R ^Y together can form an aliphatic, aromatic or heteroaromatic ring system, which can be substituted by one or more radicals R';

R ^co on each occurrence, identically or differently, represents a radical selected from H, D, a straight-chain alkyl group having 1 to 40 C atoms, which may be substituted by one or more radicals R, an aryl or heteroaryl group having 6 to 18 aromatic ring atoms, each of which may be substituted by one or more radicals R, where two radicals R ^c together can form an aliphatic, aromatic or heteroaromatic ring system which is substituted by one or more radicals R;

R ^N0 on each occurrence, identically or differently, represents a radical selected from H, D, F, a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, each of which is substituted by one or more radicals R and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R; and R has the same meaning as above.

Preferably, Ar ⁵⁰ is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 5 to 30, particularly preferably 6 to 24 and very particularly preferably 6 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R.

Preferably, Ar ⁵¹ , Ar ⁵² , Ar ⁵³ are the same or different and represent a condensed aryl or heteroaryl ring having 6 aromatic ring atoms, which may each also be substituted by one or more radicals R.

Preferably, R ^Y is identical or different on each occurrence and represents H, D, F, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40, preferably 1 to 20 and more preferably 1 to 10 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40, preferably 3 to 20 and more preferably 3 to 10 C atoms, each of which may be substituted by one or more radicals R, where one or more non-adjacent CH2 groups may be replaced by RC=CR, C=C, O or S and where one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 30, particularly preferably 5 to 18 aromatic ring atoms, each of which may be substituted by one or more R radicals.

Preferably, R ^co represents, identically or differently on each occurrence, a radical selected from H, D, a straight-chain alkyl group having 1 to 10, preferably 1 to 6 and more preferably 1 to 3 C atoms, which may be substituted by one or more radicals R, an aryl or heteroaryl group having 6 to 18 and preferably 6 to 12 aromatic ring atoms, each of which may be substituted by one or more radicals R, where two radicals R ^co together may form an aliphatic, aromatic or heteroaromatic ring system which is substituted by one or more radicals R.

Preferably, R ^N0 on each occurrence, identically or differently, represents a radical selected from an aromatic or heteroaromatic ring system having 5 to 40, particularly preferably 5 to 30 and even more preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.

Examples of particularly suitable blue phosphorescent metal complexes are shown below:

Other suitable blue phosphorescent compounds that can be used as sensitizers are those listed in the following table:

Preferred matrix materials for phosphorescent compounds, which can also be used in combination with the compounds according to the invention, are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g. according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives, e.g. CBP (N,N-biscarbazolylbiphenyl) or WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527, WO 2008/086851 or WO 2013/041176, indolocarbazole derivatives, e.g. B. according to WO 2007/063754 or WO 2008/056746, indenocarbazole derivatives, e.g. according to WO 2010/136109, WO 2011/000455, WO 2013/041176 or WO 2013/056776, azacarbazole derivatives, e.g. according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar matrix materials, e.g. according to WO 2007/137725, silanes, e.g. according to WO 2005/111172, azaboroles or boronic esters, e.g. according to WO 2006/117052, triazine derivatives, e.g. B. according to WO 2007/063754, WO 2008/056746, WO 2010/015306, WO 2011/057706, WO 2011/060859 or WO 2011/060877, zinc complexes, e.g. according to EP 652273 or WO 2009/062578, diazasilole or tetraazasilole derivatives, e.g. according to WO 2010/054729, diazaphosphole derivatives, e.g. according to WO 2010/054730, bridged carbazole derivatives, e.g. B. according to WO 2011/042107, WO 2011/060867, WO 2011/088877 and WO 2012/143080, triphenylene derivatives, e.g. according to WO 2012/048781, lactams, e.g. according to WO 2011/116865 or WO 2011/137951, or dibenzofuran derivatives, e.g. according to WO 2015/169412, WO 2016/015810, WO 2016/023608, WO 2017/148564 or WO 2017/148565. Likewise, another phosphorescent emitter, which emits at a shorter wavelength than the actual emitter, can be present in the mixture as a co-host, or a compound that does not participate, or does not participate to a significant extent, in charge transport, as described, for example, in WO 2010/108579.

Since the compound of formula (1) or the preferred embodiments has hole-transporting properties, this compound is preferably combined with a compound which has electron-transporting properties when used in a mixed matrix system.

Therefore, it is further preferred that the composition of the present invention contains at least one electron-transporting matrix material in addition to the hole-transporting matrix material of formula (1).

Particularly suitable matrix materials which are advantageously combined with the compounds according to the invention in a mixed matrix system can be selected from the compounds of the formulas (eTMM1), (eTMM2), (eTMM3), (eTMM4) or (eTMM5), as described below

orme (e ),

wobei für die verwendeten Symbole und Indizes gilt: A further subject matter of the invention is therefore a mixture comprising at least one compound according to the invention and at least one compound of the formula (eTMM1), (eTMM2), (eTMM3), (eTMM4) and/or (eTMM5),

orme (e ),

where the symbols and indices used are:

L ² is, identically or differently at each occurrence, a single bond or an aromatic or heteroaromatic ring system having 5 to 24 ring atoms, each of which may be substituted by one or more radicals R ⁷ ;

R# is, identically or differently at each occurrence, D, F, CN or an aromatic ring system having 6 to 24 ring atoms which may be substituted by one or more radicals R ⁶ ;

Y is the same or different at each occurrence and is N or CR ⁷ , whereby it is excluded that two adjacent Ys simultaneously represent N;

V ² is 0 or S;

R ⁶ is, identically or differently at each occurrence, H, D, F, CN, Si(R ⁷ )s, Ge(R ⁷ )s, a straight-chain alkyl group having 1 to 20 C atoms or a Alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group can each be substituted by one or more radicals R ⁷ and where one or more non-adjacent CH2 groups can be replaced by Si(R ⁷ ) 2, C=O, NR ⁷ , O, S or CONR ⁷ , or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which can each be substituted by one or more radicals R ⁷ ; two radicals R ⁶ can also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another;

Ar ⁵ represents, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by one or more radicals R ⁷ ;

R ⁷ is, identically or differently on each occurrence, H, D, F, CI, Br, I, N(R ⁸ ) ₂ , CN, NO _2I OR ⁸ , SR ⁸ , Si(R ⁸ ) ₃ , Ge(R ⁸ ) ₃ , B(OR ⁸ ) ₂ , C(=O)R ⁸ , P(=O)(R ⁸ ) ₂ , S(=O)R ⁸ , S(=O) ₂ R ⁸ , OSO ₂ R ⁸ , a straight-chain alkyl group having 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, where the alkyl, alkenyl or alkynyl group can each be substituted by one or more radicals R ⁸ , where one or more non-adjacent CH 2 groups can be replaced by Si(R ⁸ ) ₂ , C=O, NR ⁸ , O, S or CONR ⁸ , or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which can each be substituted by one or more radicals R ⁸ ; two or more radicals R ⁷ can form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another;

R ⁸ is, identically or differently at each occurrence, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may be replaced by F; b1 is 0, 1, 2, 3 or 4; b2 is 0, 1 , 2 or 3.

The invention further relates to an organic electronic device, in particular an organic electroluminescent device comprising anode, cathode and at least one organic layer containing at least one light-emitting layer, wherein at least one light-emitting layer contains the above-mentioned mixture of at least one compound according to the invention and at least one compound of the formulas (eTMM1), (eTMM2), (eTMM3), (eTMM4) and/or (eTMM5).

b)

MIe), wobei die Symbole und Indizes für diese Formeln die folgende Bedeutung haben: Preferred compounds of the formula (eTMM1 ) are the compounds of the formulas (eTMMIa), (eTMMI b), (eTMMIc), (eTMMId) and (eTMMIe),

b)

MIe), where the symbols and indices for these formulas have the following meaning:

W, W ¹ mean, identically or differently, O, S, C(R ^W ) 2 or N-Ar ⁵ at each occurrence; R ^w is, identically or differently on each occurrence, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more H atoms of the alkyl group on the aromatic or heteroaromatic ring system may be replaced by D, F or CN; the two radicals R ^w which are bonded to the same carbon atom can also form a ring system with one another;

ist abgeleitet von einer Arylgruppe mit 6 bis 20 Ringatomen, die mit einem oder mehreren Substituenten R# substituiert sein kann;

l_3 ist ein aromatisches Ringsystem mit 6 bis 40 Ringatomen oder ein heteroaromatisches Ringsystem mit 5 bis 40 Ringatomen, die mit einem oder mehreren Resten R⁷ substituiert sein können; A is the same or different at each occurrence and is CR ⁷ or N, where a maximum of two A groups per cycle stand for N and where A stands for C if L ² is attached to this position; a3 is the same or different at each occurrence and is 0, 1, 2, 3 or 4; b3 is the same or different at each occurrence and is 0, 1, 2 or 3;

is derived from an aryl group having 6 to 20 ring atoms, which may be substituted with one or more substituents R#;

l_3 is an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by one or more radicals R ⁷ ;

Formel (eTMMIc*) wobei die verwendeten Symbole und Indizes die oben genannten Bedeutungen aufweisen und die Verbindung auch teilweise oder vollständig deuteriert sein kann. Dabei sind besonders bevorzugte Gruppen Ar⁵ gleich oder verschieden bei jedem Auftreten ausgewählt aus Phenyl, meta- Biphenyl oder N-Carbazolyl, welches jeweils auch durch einen oder mehrere Reste R⁷ substituiert sein kann. Weiterhin bevorzugt ist mindestens einer und besonders bevorzugt genau einer der Substituenten, die an die N-Carbazolylgruppe oder an Ar⁵ gebunden sind, eine Triphenylsilyl- gruppe. Besonders bevorzugt weist die Verbindung der Formel (eTMMIc*) eine Gruppe Ar⁵ auf, welche für eine Phenylgruppe steht, die in meta- Position mit einer Triphenylsilylgruppe substituiert ist. L ² , X, Ars, R ⁷ and R# have the meanings given above. Particularly preferred matrix materials for blue phosphorescent OLEDs or hyperphosphorescent OLEDs are the compounds of the following formula (eTMMIc*),

Formula (eTMMIc*) where the symbols and indices used have the meanings given above and the compound can also be partially or fully deuterated. Particularly preferred groups Ar ⁵ are selected, identically or differently on each occurrence, from phenyl, meta-biphenyl or N-carbazolyl, each of which can also be substituted by one or more radicals R ^7. Furthermore, at least one and particularly preferably exactly one of the substituents which are bonded to the N-carbazolyl group or to Ar ⁵ is preferably a triphenylsilyl group. The compound of the formula (eTMMIc*) particularly preferably has a group Ar ⁵ which is a phenyl group which is substituted in the meta position with a triphenylsilyl group.

Formel (eTMM3a) wobei die Symbole und Indizes für diese Formel (eTMM3a) die folgende Bedeutung haben: W¹ ist bei jedem Auftreten gleich oder verschieden O, S, C(R^W)2 oder N-Ar⁵; Preferred compounds of the formula (eTMM3) are the compounds of the formula (eTMM3a),

Formula (eTMM3a) where the symbols and indices for this formula (eTMM3a) have the following meaning: W ¹ is, at each occurrence, the same or different, O, S, C(R ^W ) 2 or N-Ar ⁵ ;

#X is CR or NAr ⁵ , preferably NAr ⁵ ;

ist abgeleitet von einer Arylgruppe mit 6 bis 20 Ringatomen, die mit einem oder mehreren Substituenten R## substituiert sein kann;

wobei L², Ar⁵ und R# die zuvor angegebenen Bedeutungen haben. R ^w is, identically or differently on each occurrence, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where 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, identically or differently on each occurrence, 0, 1, 2, 3 or 4;

is derived from an aryl group having 6 to 20 ring atoms, which may be substituted by one or more substituents R##;

where L ² , Ar ⁵ and R# have the meanings given above.

In compounds of the formula (eTMMIa), W is preferably O or N-Ar ⁵ .

In compounds of the formula (eTMMIa), A is preferably the same or different at each occurrence and is CR ⁷ , where A stands for C when L ² is bonded to this position. In compounds of the formulas (eTMMI d) or (eTMM3a), W ¹ is preferably 0, C(R ^W ) ₂ or N-Ar ⁵ , particularly preferably N-Ar ⁵ .

In compounds of the formula (eTMMI e), L ³ is preferably a heteroaromatic ring system having 9 to 30 ring atoms, which may be substituted by one or more radicals R ⁷ .

In a preferred embodiment of the compounds of the formulas (eTMM1), (eTMMI a), (eTMMI b), (eTMMI e), (eTMMI d), (eTMMIe), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), R ⁷ is the same or different on each occurrence and is selected from the group consisting of H, D, F, CN, Si(R ⁸ )s, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl group may in each case be substituted by one or more radicals R ⁸ , or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, preferably having 5 to 40 ring atoms, which may in each case be substituted by one or more radicals R ⁸ .

In a particularly preferred embodiment of the compounds of the formulas (eTMM1), (eTMMI a), (eTMMI b), (eTMMI e), (eTMMI d), (eTMMI e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), R ⁷ is the same or different on each occurrence and is selected from the group consisting of H, D or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may be substituted by one or more radicals R ⁸ .

The preparation of the compounds of formulas (eTMM1 ), (eTMMI a), (eTMMI b), (eTMMI e), (eTMMI d), (eTMMI e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5) are generally known and some of the compounds are commercially available.

Suitable compounds of the formula (eTMM1 ) are known, for example, from the following publications: W02007/077810A1 , W02008/056746A1 , W02010/136109A1 , WO2011/057706A2, WO2011/160757A1 , WO201 2/023947A1 , WO2012/048781 A1 , WO2013/077352A1 , WO2013147205A1, WO2013/083216A1, WO2014/094963A1, W02014/007564A1, WO2014/015931 A1, W02015/090504A2, WO201 5/105251 A1 , WO2015/169412A1, WO2016/015810A1, WO201 6/013875A1, WO2016/010402A1, WO2016/033167A1, WO201 7/178311 A1, WO2017/076485A1, WO2017/186760A1, WO201 8/004096A1, WO2018/016742A1, WO2018/123783A1, WO201 8/159964A1, WO2018/174678A1, WO2018/174679A1, WO201 8/174681 A1, WO2018/174682A1, WO2019/177407A1, WO201 9/245164A1, WO2019/240473A1, WO2019/017730A1, WO201 9/017731 A1, WO2019/017734A1, WO2019/145316A1, WO201 9/121458A1, W02020/130381 A1, W02020/130509A1, W02020/169241 A1, WO2020/141949A1, WO2021/066623A1, W02021/101220A1, W02021/037401 A1, W02021/180614A1, WO2021/239772A1, W02022/015084A1, WO2022/025714A1, WO2022/055169A1 , EP3575296A1 , EP3591728A1 , US2014/0361254A1, US2014/0361268A1, KR20210036304A, KR20210036857A, KR2021147993A, JP2011/160367 A2 and JP2017/107992A2.

Suitable compounds of the formula (eTMM2) are known, for example, from the following publications: WO2015/182872A1, WO2015/105316A1, WO2017/109637A1, W02018/060307A1, WO2018/151479A2, WO201 8/088665A2, WO2018/060218A1, WO2018/234932A1, W02019/058200A1, WO2019/017730A1, WO2019/017731 A1, WO201 9/066282A1, WO2019/059577A1, W02020/141949A1 , W02020/067657A1, WO2022063744A1, W02022/090108A1, WO2022/207678A1, KR2019035308A, KR2021147993A, CN110437241A, US2016/072078A1.

Suitable compounds of the formula (eTMM3) are known, for example, from the following publications: WO2017/160089A1, WO2019/017730A1, WO201 9/017731 A1, W02020/032424A1.

Suitable compounds of the formula (eTMM5) are known, for example, from the following publications: WO2015/093878A1, WO2016/033167A1, WO2017/183859A1, WO2017/188655A1, WO2018/159964A1. For a combination with the compounds according to the invention, as described above or preferably described, compounds of the formulas (eTMM1), (eTMMIa), (eTMMI b), (eTMMIc), (eTMMId), (eTMMIe) and/or (eTMM2) are particularly suitable, as described above or preferably described, or corresponding compounds of the tables below which fall under these formulas. The compounds of the formulas (eTMM1), (eTMMIa), (eTMMI b), (eTMMIc), (eTMMId) and/or (eTMMIe) are particularly preferred.

Further examples of suitable host materials of the formulas (eTMM1), (eTMMIa), (eTMMIb), (eTMMIc), (eTMMId), (eTMMIe), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), which can be combined according to the invention with the above-listed compounds of the invention, as described above, are the structures listed below in Tables A and B below.

Table A:

Particularly suitable compounds of the formulas (eTMM1), (eTMMIa), (eTMMI b), (eTMMIc), (eTMMId), (eTMMIe), (eTMMIf) and/or (eTMM2), which can be combined according to the invention with the above-mentioned compounds according to the invention, as described above, and in the electroluminescent device according to the invention or The compounds E1 to E40 of Table B are used in the mixture.

Die vorstehend genannten erfindungsgemäßen Hostmaterialien sowie deren bevorzugt beschriebene Ausführungsformen können in der erfindungsgemäßen Vorrichtung beliebig mit den zuvor genannten Matrixmaterialien/Hostmaterialien, den Matrixmaterialien/Hostmaterialien der Formeln (eTMM1 ), (eTMMIa), (eTMMI b), (eTMMIc), (eTMMId), (eTMMIe), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) oder (eTMM5), sowie deren bevorzugt beschriebenen Ausführungsformen der Tabelle 1 oder den Verbindungen E1 bis E45 der Tabelle 2 kombiniert werden. Table B:

The above-mentioned host materials according to the invention and their preferred embodiments described can be combined as desired in the device according to the invention with the previously mentioned matrix materials/host materials, the matrix materials/host materials of the formulas (eTMM1), (eTMMIa), (eTMMI b), (eTMMIc), (eTMMId), (eTMMIe), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), and their preferred embodiments described in Table 1 or the compounds E1 to E45 in Table 2.

If the matrix material is a deuterated compound, it is possible that the matrix material is a mixture of deuterated compounds with the same basic chemical structure, which differ only in the degree of deuteration.

In a preferred embodiment of the matrix material, this is a mixture of deuterated compounds according to the invention or of the formula (eTMM1), (eTMMIa), (eTMMI b), (eTMMIc), (eTMMId), (eTMMIe), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), as described above, wherein the degree of deuteration of these compounds is at least 50% to 90%, preferably 70% to 100%.

The concentration of the sum of all host materials according to the invention, as described above or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 5 vol.% to 90 vol.%, preferably in the range from 10 vol.% to 85 vol.%, more preferably in the range from 20 vol.% to 85 vol.%, even more preferably in the range from 30 vol.% to 80 vol.%, very particularly preferably in the range from 20 vol.% to 60 vol.% and most preferably in the range from 30 vol.% to 50 vol.%, based on the entire mixture or based on the entire composition of the light-emitting layer.

The concentration of the sum of all host materials of formulas (eTMM1 ), (eTMMIa), (eTMMI b), (eTMMIc), (eTMMId), (eTMMIe), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), 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 usually in the range from 5 vol.% to 90 vol.%, preferably in the range from 10 vol.% to 85 vol.%, more preferably in the range from 20 vol.% to 85 vol.%, even more preferably in the range from 30 vol.% to 80 vol.%, very particularly preferably in the range from 20 vol.% to 60 vol.% and most preferably in the range from 30 vol.% to 50 vol.%, based on the entire mixture or based on the entire composition of the light-emitting layer.

The present invention also relates to a mixture which, in addition to the abovementioned host materials according to the invention and the host material of at least one of the formulas (eTMM1), (eTMMIa), (eTMMI b), (eTMMIc), (eTMMId), (eTMMIe), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), as described above or preferably described, contains at least one phosphorescent emitter.

Examples of particularly suitable matrix materials for blue phosphorescent metal complexes are shown below:

Preferably, the at least one fluorescent emitter in the composition has a peak emission wavelength between 420-550 nm, preferably between 420-470 nm.

Preferred fluorescent emitting compounds for hyperphosphorescent OLEDs are selected from the class of arylamines. In the context of the present invention, an arylamine or an aromatic amine is understood to mean a compound which contains three substituted or unsubstituted aromatic or heteroaromatic ring systems which are bonded directly to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a condensed ring system, particularly preferably with at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. An aromatic anthraceneamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. An aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9- and 10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously, in which the diarylamino groups are preferably bonded to the pyrene in the 1-position or 1,6-position. Further preferred emitting compounds are indenofluorenamines or fluorenediamines, for example according to WO 2006/108497 or WO 2006/122630, benzoindenofluorenamines or fluorenediamines, for example according to WO 2008/006449, and dibenzoindenofluorenamines or diamines, for example according to WO 2007/140847, and the indenofluorene derivatives with condensed aryl groups disclosed in WO 2010/012328. The pyrenarylamines disclosed in WO 2012/048780 and in WO 2013/185871 are also preferred. Also preferred are the benzoindenofluorenamines disclosed in WO 2014/037077, the benzofluorenamines disclosed in WO 2014/106522, the extended benzoindenofluorenes disclosed in WO 2014/111269 and in WO 2017/036574, the phenoxazines disclosed in WO 2017/028940 and in WO 2017/028941 and the fluorine derivatives bound to furan units or to thiophene units disclosed in WO 2016/150544. Furthermore, boron compounds according to WO 2020/208051, WO 2015/102118, WO 2016/152418, WO 2018/095397, WO 2019/004248, WO 2019/132040, US 2020/0161552 and WO 2021/089450, WO 2015/102118, KR 2018046851, WO 2019/009052, WO 2020/101001, US 2020/0207787, WO 2020/138874, KR 2020081978, JP 2020-147563, US 2020/0335705 or KR 2022041028 may be used.

Preferably, the at least one fluorescent emitter has a full width at half peak height (FWHM) < 50 nm, preferably FWHM < 40 nm, more preferably FWHM < 30 nm.

Preferably, the at least one fluorescent emitter has a LUMO of -2.1 eV to -2.5 eV, preferably from -2.2 eV to -2.4 eV, as defined by quantum chemical calculations. Preferably, the at least one fluorescent emitter has a HOMO of -4.8 eV to -5.2 eV, preferably from -4.9 eV to -5.1 eV, as defined by quantum chemical calculations.

Preferably, the energy of the lowest singlet state Si of the fluorescent emitter is 2.65 eV to 2.9 eV, preferably 2.7 to 2.8 eV, more preferably 2.7 to 2.75 eV, as defined by quantum mechanical calculations.

Formel (F-1) wobei R die oben genannten Bedeutungen aufweist und für die weiteren verwendeten Symbole und Indizes gilt: In a preferred embodiment of the invention, the fluorescent emitter is selected from structures of the following formula (F-1 ),

Formula (F-1) where R has the meanings given above and the other symbols and indices used are:

Ar ³⁰ , Ar ³¹ , Ar ³² is the same or different on each occurrence and is a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms; Y ³⁰ is B or N;

Y ³¹ Y ³² , Y ³³ is the same or different on each occurrence and represents O, S, C(R°)2, C=O, C=S, C=NR°, C=C(R°)2, Si(R°) ₂ , BR°, NR°, PR°, SO2, SeO2 or a chemical bond, with the proviso that when Y ³⁰ represents B, at least one of the groups Y ³¹ , Y ³² , Y ³³ represents NR°, and when Y ³⁰ represents N, at least one of the groups Y ³¹ , Y ³² , Y ³³ represents BR°;

R° is the same or different on each occurrence and is H, D, F, a straight-chain alkyl group having 1 to 20, preferably 1 to 10, C atoms or a branched or cyclic alkyl group having 3 to 20, preferably 3 to 10, C atoms, each of which may be substituted by one or more substituents R, where one or more non-adjacent CH2 groups may be replaced by O or S and where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, particularly preferably 6 to 18 aromatic ring atoms, each of which may be substituted by one or more substituents R; two adjacent substituents R° may form an aliphatic or aromatic ring system with one another, which may be substituted by one or more substituents R; q is 0 or 1 .

Particularly preferred are compounds where:

- q = 0; Y ³⁰ = B; and Y ³¹ , Y ³² = NR°; or

- q = 0; Y ³⁰ = B; and Y ³¹ , Y ³² = NR°; or

- q = 1 ; Y ³⁰ = N; and Y ³¹ , Y ³² = BR°; Y ³³ = chemical bond.

Examples of suitable fluorescent emitters are shown in the table below:

Suitable charge transport materials, as can be used in the hole injection or hole transport layer or in the electron-Zexciton blocking layer or in the electron transport layer of the electronic component according to the invention, are, in addition to the compounds of formula (1), for example those in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials as used in these layers according to the prior art.

All materials that are used according to the state of the art as hole transport materials in the hole transport layer can be used as materials for the hole transport layer. Aromatic amine compounds can be used. Further compounds which are preferably used in hole-transporting layers of the OLEDs according to the invention are in particular indenofluorenamine derivatives (for example according to WO 2006/122630 or WO 2006/100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (for example according to WO 01/049806), amine derivatives with fused aromatics (for example according to US 5,061,569), the amine derivatives disclosed in WO 95/09147, monobenzoindenofluorenamines (for example according to WO 08/006449), dibenzoindenofluorenamines (for example according to WO 07/140847), spirobifluorenamines (for example according to WO 2012/034627 or WO 2013/120577), fluorenamines (for example according to WO 2014/015937, WO 2014/015938, WO 2014/015935 and WO 2015/082056), spirodibenzopyranamines (for example according to WO 2013/083216), dihydroacridine derivatives (for example according to WO 2012/150001), spirodibenzofurans and spirodibenzothiophenes (for example according to WO 2015/022051, WO 2016/102048 and WO 2016/131521), phenanthrenedarylamines (for example according to WO 2015/131976), spirotribenzotropolones (for example according to WO 2016/087017), spirobifluorenes with meta-phenyldiamine groups (for example according to WO 2016/078738), spirobisacridines (for example according to WO 2015/158411), xanthenediarylamines (for example according to WO 2014/072017), and 9,10-dihydroanthracene spiro compounds with diarylamino groups according to WO 2015/086108.

Very particular preference is given to the use of spirobifluorenes substituted by diarylamino groups in the 4-position as hole-transporting compounds, in particular the use of those compounds disclosed in WO 2013/120577, and the use of spirobifluorenes substituted by diarylamino groups in the 2-position as hole-transporting compounds, in particular the use of those compounds disclosed in WO 2012/034627.

The OLED according to the invention preferably comprises two or more different electron-transporting layers. Compounds that can be used in these layers are all materials that are used according to the prior art as electron-transport materials in the electron-transport layer. Particularly suitable are aluminum complexes, e.g. Alqs, zirconium complexes, e.g. Zrq4, lithium complexes, e.g. Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives and phosphine oxide derivatives. Other suitable materials are derivatives of the aforementioned compounds as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300.

The device is structured accordingly (depending on the application), contacted and finally sealed to exclude harmful influences from water and air.

In the further layers of the organic electroluminescent device according to the invention, all materials can be used as they are usually used according to the prior art. Therefore, without inventive step, all materials known for organic electroluminescent devices can be used in combination with the compounds according to the invention according to formula (1) or the preferred embodiments described above.

Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using a sublimation process. The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10' ⁵ mbar, preferably less than 10' ⁶ mbar. However, it is also possible for the initial pressure to be even lower, for example less than 10' ⁷ mbar.

Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using the OVPD (Organic Vapour Phase Deposition) method or with the aid of carrier gas sublimation. The materials are applied at a pressure between 10' ⁵ mbar and 1 bar. A special case of this method is the OVJP (Organic Vapour Jet Printing) method, in which the materials are applied directly through a nozzle and thus structured.

Also preferred is an organic electroluminescent device, characterized in that one or more layers are produced from solution, such as by spin coating, or using any printing method, such as screen printing, flexographic printing, offset printing, LITI (light induced thermal imaging, thermal transfer printing), ink-jet printing or nozzle printing. Soluble compounds are required for this, which are obtained, for example, by suitable substitution.

Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are vapor deposited.

These processes are generally known to the person skilled in the art and can be applied by him without inventive step to organic electroluminescent devices containing the compounds according to the invention. The compounds according to the invention and the organic electroluminescent devices according to the invention are characterized by one or more of the following properties:

1. The connections according to the invention lead to an improvement in the service life compared to symmetrically constructed connections according to the prior art.

2. The compounds according to the invention lead to an improvement in power efficiency compared to symmetrically constructed compounds according to the prior art.

3. The connections according to the invention lead to a reduction in the operating voltage compared to symmetrically constructed connections according to the prior art.

The invention is explained in more detail by the following examples, without intending to restrict it thereby. From the descriptions, the person skilled in the art can carry out the invention in the entire disclosed area and, without inventive step, produce further compounds according to the invention and use them in electronic devices or apply the method according to the invention.

Examples:

Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be obtained from ALDRICH or ABCR.

1) Synthesis of the compounds according to the invention:

Example B1:

A well-stirred mixture of 67.3 g (200 mmol) of N ¹ - [1 ,1 '-biphenyl]-3-yl-N ² -phenyl-1 ,2-benzenediamine [2773945-46-1] in 1200 ml of diethyl ether, cooled to 0 °C, is treated dropwise over 20 min with 37.3 ml (400 mmol) of n-butyllithium, 10.6 M in n-hexane, and then stirred for 10 min. Then 11.5 ml (100 mmol) of silicon tetrachloride [10026-04-7] are added dropwise over 30 min and then allowed to warm to room temperature with stirring. After 16 hours, all volatile components are removed in vacuo, the residue is taken up in 1200 ml of dichloromethane (DCM), filtered through a silica gel column (15 cm diameter) pre-slurried with DCM, washed with 300 ml of DCM and the eluate is concentrated to dryness in vacuo. The crude product is taken up in 200 ml of DCM and the solution is slowly added dropwise to 600 ml of ethanol at room temperature with good stirring. Stir for 5 hours, the crystallized solid is filtered off with suction and dried in vacuo. The crystallization is repeated twice more with ethanol and then three times with 600 ml of acetonitrile. Finally, the product is fractionally sublimated twice in a high vacuum (p ~ 10' ⁵ mbar, T ~ 260 - 280 °C). Yield: 31.5 g (45 mmol), 45%, purity: > 99.9% by HPLC.

The following connections can be represented analogously.

Example B100:

A well-stirred mixture of 26.0 g (100 mmol) of N ¹ ,N ² -diphenyl-o-phenylenediamine [28394-83-4] in 500 ml of toluene, cooled to 0 °C, is treated dropwise over 20 min with 18.7 ml (200 mmol) of n-butyllithium, 10.6 M in n-hexane. The reaction mixture is allowed to warm to room temperature and stirred for 1 h. Then 11.5 ml (100 mmol) of silicon tetrachloride [10026-04-7] are poured into the well-stirred reaction mixture and then heated under reflux for 3 h. After cooling, the mixture is filtered through a Celite bed pre-slurried with toluene and the filtrate is then concentrated to dryness in a vacuum (final temperature ~ 100 °C, final pressure ~ 0.1 mbar). The resulting dichlorosilane is dissolved in 500 ml THF; this dichlorosilane solution is used in the next step.

A well-stirred mixture of 41.3 g (100 mmol) of N ¹ ,N ² -bis([1 ,1 '-biphenyl]-3-yl)-1 ,2-phenylenediamine [1225231 -02-6] in 500 ml of tetrahydrofuran (THF) cooled to 0 °C is treated dropwise over 20 min with 18.7 ml (200 mmol) of n-butyllithium, 10.6 M in n-hexane. The reaction mixture is allowed to warm to room temperature and stirred for 1 h. The dichlorosilane solution is then added with good stirring and the mixture is stirred for 16 hours. All volatile components are removed under vacuum, the residue is taken up in 1200 ml of dichloromethane (DCM), filtered through a silica gel column (15 cm diameter) pre-slurried with DCM, washed with 300 ml of DCM and the eluate is evaporated to dryness under vacuum. The crude product is taken up in 200 ml of DCM and the solution is slowly added dropwise to 600 ml of ethanol at room temperature with good stirring. The mixture is stirred for 5 hours, the crystallized solid is filtered off with suction and dried under vacuum. The crystallization is repeated twice more with ethanol and then three times with 600 ml of acetonitrile. Finally, the product is fractionally sublimated twice under high vacuum (p ~ 10' ⁵ mbar, T ~ 260 - 280 °C). Yield: 30.2 g (43 mmol), 43%, purity: > 99.9% by HPLC.

Vergleich der Glasübergangstemperaturen The following connections can be represented analogously.

Comparison of glass transition temperatures

The following table lists the glass transition temperatures Tg of materials according to the prior art (WO 2010/054729) and compounds according to the invention. Since the compound SdT, in which Ar ¹ to Ar ⁴ are phenyl groups, has a Tg of only 64 °C, which is too low for the commercial production of OLEDs, in the following OLED examples compounds according to the invention are compared with the material H-2 according to the prior art.

OLED examples

The production of OLEDs has already been described several times in the literature, e.g. in WO 2004/058911 . The process is adapted to the conditions described below, ie layer thickness variation, layer sequences and materials. Examples are given below for OLED devices according to preferred embodiments of the invention.

All exemplary OLED components are characterized by the following layer structure:

- glass plate (hereinafter also glass substrate or substrate),

- Indium tin oxide (hereinafter ITO) as anode,

- Hole injection layer (hereinafter HIL)

- hole transport layer (hereinafter HTL),

- electron blocking layer (hereinafter EBL),

- Emission layer (hereinafter EML),

- hole blocking layer (hereinafter HBL),

- electron transport layer (ETL),

- electron injection layer (hereinafter EIL), - aluminium (hereinafter cathode).

The glass substrates with the patterned 50 nm thick ITO are pretreated with an oxygen plasma followed by an argon plasma. Afterwards, the materials for the HIL, HTL, EBL, EML, HBL, ETL and EIL are applied to the pretreated glass substrate by thermal evaporation in a vacuum chamber. Detailed information about the HIL, HTL, EBL, EML, HBL, ETL and EIL of the OLED devices is given in Table 1. The materials used in these examples are listed in Table 2. The cathode consists of an aluminum layer with a thickness of 100 nm.

According to one embodiment of the invention, the EML comprises a hole-transporting host material, an electron-transporting host material and a phosphorescent metal complex. All materials of the EML are deposited in parallel at a certain deposition rate, i.e. by co-evaporation, to form a homogeneous, amorphous mixture. The deposition rate of the individual materials can be selected so that each material is present in the mixture at a certain volume fraction (vol%). For example, the composition of an EML containing a hole-transporting host material (HH) with 40 vol%, an electron-transporting host material (EH) with 40 vol.% and a phosphorescent metal complex (D) with 10 vol.% is referred to as HH:EH:D (45%:45%:10%) in Table 1. This notation is analogous to describing the composition of an EML comprising two or four different materials and also for HIL, HTL, EBL, HBL, ETL and EIL of the OLED device if these layers each comprise more than one material.

The performance of the OLED devices can be measured using standard methods. For this purpose, the electroluminescence spectra (EL) and the external quantum efficiency (EQE) can be determined from current/voltage/luminance characteristics (IUL characteristics) assuming a Lambertian emission profile. The EL spectra can be recorded at a luminance of 1000 cd/m ² and the CIE 1931 x and y coordinates can be calculated from the EL spectrum. The operating voltage U is defined as the voltage required for a current density of 10 mA/cm ² . In Table 1, the voltage U is shown as a relative voltage (rel. U), whereby the voltage of the reference device in the comparison example (SdT1 ) was set to 100% rel. U. The power efficiency EffP is the ratio of the emitted luminous flux (light output) in lumens (Im) to the supplied electrical power in watts (W) at a luminance of 1000 cd/m ² . In Table 1, the power efficiency EffP is shown as relative power efficiency (rel. EffP), whereby the power efficiency of the reference component in the comparison example (SdT1 ) was set to 100% rel. EffP. The lifetime LT90 is defined as the time after which the luminance drops to 90% of the initial luminance during operation at a constant current density of 5 mA/cm ^2. In Table 1, the lifetime LT90 is shown as relative lifetime (rel. LT90), whereby the lifetime of the reference component in the comparison example (SdT1 ) was set to 100% rel. LT.

The following embodiment 1 corresponds to a preferred embodiment of the invention. SdT1 is an example of an OLED device with a material according to the prior art. The details of the respective HIL, HTL, EBL, EML, HBL, ETL and EIL are given in Table 1. The molecular structures used are given in Table 2. HTM is a fluorenamine. Example 1: The EML comprises a hole-transporting host material H-1 , an electron-transporting host material E-1 and a phosphorescent metal complex D-1 . This OLED can be compared to an OLED according to Example SdT1 (Table 1 ). The two devices differ in terms of the hole-transporting host material used in the respective EML, i.e. H-2 according to the state of the art in the case of SdT1 and H-1 in the case of Ex. 1. The OLED according to Ex. 1 has a better lifetime (LT90), a better power efficiency (EffP) and a better operating voltage (U) than the OLED according to SdT1.

Table 1 : Structure and results of the OLEDs

Table 2: Structural formulas of OLED materials

Claims

patent claims 1 . Compound according to formula (1 ),

Formula (1 ) where the symbols used are: X is the same or different at each occurrence and is CR or N, with the proviso that not more than two Xs per cycle represent N; Ar ¹ , Ar ² , Ar ³ , Ar ⁴ is, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms which may be substituted by one or more radicals R; R is, identically or differently on each occurrence, H, D, F, CI, Br, I, OR ¹ , SR ¹ , B(OR ¹ ) ₂ , CHO, C(=O)R ¹ , CR ¹ =C(R ¹ ) ₂ , CN, C(=O)OR ¹ , C(=O)NR ¹ , Si(R ¹ ) ₃ , Ge(R ¹ ) ₃ , NO2, P(=O)(R ¹ ) ₂ , OSO2R ¹ , OR ¹ , N(R ¹ )2, S(=O)R ¹ , S(=O)2R ¹ , SR ¹ , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group can each be substituted by one or more radicals R ¹ , where one or more non-adjacent CH2 groups are substituted by

P(=O)(R ¹ ), -O-, -S-, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ring atoms, each substituted by one or more radicals R ¹ can be substituted; two or more R radicals can form a ring system with each other; R ¹ is, identically or differently on each occurrence, H, D, F, CI, Br, I, B(OR ² )2, CHO, C(=O)R ² , CR ² =C(R ² )2, CN, C(=O)OR ² , Si(R ² ) ₃ , Ge(R ² ) ₃ , NO ₂ , P(=O)(R ² ) ₂ , OSO2R ² , SR ² , S(=O)R ² , S(=O) ₂ R ² , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted with one or more radicals R ² can be substituted and wherein one or more CH2 groups in the abovementioned groups can be replaced by -R ² C=CR ² -, -C=C-, Si(R ² ) ₂ , C=O, C=S, -C(=O)O-, CONR ² , P(=O)(R ² ), -S-, SO or SO2 and wherein one or more H atoms in the abovementioned groups can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ² , where two or more radicals R ¹ can form a ring system with one another; R ² is, on each occurrence, identically or differently, H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms can also be replaced by D or F; two or more substituents R ² can be linked to one another and form a ring; characterized in that not all of the groups Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are identical and/or that the two cycles containing X are different and/or the two cycles containing X are differently substituted; the following compound is excluded from the invention:

2. A compound according to claim 1, selected from the compounds of Formulas (2), (3) and (4),

Formula (4) wherein the symbols have the meanings given in claim 1. 3. A compound according to claim 1 or 2, selected from the compounds of formulas (2a) to (2f),

Formula (2a) Formula (2b)

Formula (2e) Formula (2f) where the structure can also be partially or completely deuterated, and Ar ¹ to Ar ⁴ and R have the meanings given in claim 1. 4. A compound according to one or more of claims 1 to 3, characterized in that Ar ¹ to Ar ⁴ are: Ar ¹ = Ar ² and Ar ³ = Ar ⁴ and Ar ¹ + Ar ³ ; or Ar ¹ = Ar ³ and Ar ² = Ar ⁴ and Ar ¹ + Ar ² ; or Ar ¹ = Ar ² = Ar ³ and Ar ⁴ + Ar ¹ ; or Ar ¹ = Ar ² and Ar ³ + Ar ⁴ + Ar ¹ ; or Ar ¹ = Ar ³ and Ar ² + Ar ⁴ + Ar ¹ ; or Ar ¹ + Ar ² + Ar ³ + Ar ⁴ ; different groups Ar ¹ to Ar ⁴ can be different aromatic or heteroaromatic ring systems, or they can be the same aromatic or heteroaromatic ring systems but differently substituted. 5. A compound according to one or more of claims 1 to 4, characterized in that Ar ¹ to Ar ⁴ , identical or different on each occurrence, are selected from an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, preferably having 6 to 24 aromatic ring atoms and particularly preferably having 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R. 6. A compound according to one or more of claims 1 to 5, characterized in that at least one of the groups Ar ¹ to Ar ⁴ contains at least 12 aromatic ring atoms and/or that the compound has at least one aromatic or heteroaromatic substituent R which contains at least 12 aromatic ring atoms and/or that the compound has at least two aromatic or heteroaromatic substituents R. 7. Compound according to one or more of claims 1 to 6, characterized in that Ar ¹ to Ar ⁴ are selected, identically or differently on each occurrence, from the group consisting of phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which can be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which can be linked via the 1-, 2-, 3- or 4-position, naphthalene, which can be linked via the 1- or 2-position, indole, benzofuran, benzothiophene, which can be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, carbazole, which can be linked via the 1-, 2-, 3- or 4-position, Dibenzothiophene, which may be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, benzimidazole, phenanthrene, triphenylene or a combination of two or three of these groups, each of which may be substituted by one or more radicals R. 8. A compound according to one or more of claims 1 to 7, characterized in that Ar ¹ to Ar ⁴ are the same or different on each occurrence and are selected from the group consisting of the following structures Ar-a to Ar-I,

where the dashed bond represents the bond to the nitrogen atom and these structures can also be partially or completely deuterated. 9. A compound according to one or more of claims 1 to 8, characterized in that the substituents R which are bonded to Ar ¹ to Ar ⁴ are selected, identically or differently on each occurrence, from the group consisting of H, D, F, CN, Si(R ¹ ) s, Ge(R ¹ ) s, a straight-chain alkyl group having 1 to 10 C atoms or cyclic alkyl group having 3 to 10 C atoms, where the alkyl group can in each case be substituted by one or more radicals R ¹ , but is preferably unsubstituted, and where one or more non-adjacent CH2 groups can be replaced by O; two adjacent radicals R can form a ring system with one another; and that the R which bind to the carbon atom for X = CR are selected, identically or differently, on each occurrence from the group consisting of H, D, F, CN, OR ¹ , N(R ¹ )2, Si(R ¹ )3, Ge(R ¹ )s, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl group may be substituted in each case by one or more radicals R ¹ , but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ . 10. A compound according to one or more of claims 1 to 9, characterized in that the compound is at least 30% deuterated. 11. A process for preparing a compound according to one or more of claims 1 to 10, characterized by the following steps: (1 ) providing a benzene derivative or corresponding heteroaromatic derivative which is substituted in the ortho position to each other with a group -NHAr ¹ and -NHAr ² and optionally providing a benzene derivative or corresponding heteroaromatic derivative which is substituted in the ortho position to each other with a group -NHAr ³ and -NHAr ⁴ ; and (2) Reaction of SiHak, where Hal is a halogen, with the benzene derivative or corresponding heteroaromatic derivative which is substituted in ortho-position to each other with a group -NHAr ¹ and a group -NHAr ² , optionally followed by reaction with the benzene derivative or corresponding heteroaromatic derivative which is substituted in ortho-position to each other with a group -NHAr ³ and a group -NHAr ⁴ . 12. Mixture containing at least one compound according to one or more of claims 1 to 10 and at least one further compound. 13. Use of a compound according to one or more of claims 1 to 10 in an electronic device. 14. Electronic device comprising at least one compound according to one or more of claims 1 to 10. 15. Electronic device according to claim 14, which is an organic electroluminescent device, characterized in that the compound according to one or more of claims 1 to 10 is used in a hole transport layer and/or an exciton blocking layer and/or as matrix material in an emitting layer. 16. Electronic device according to claim 15, characterized in that the emitting layer is a phosphorescent or hyperphosphorescent layer. 17. Electronic device according to claim 16, characterized in that the emitting layer contains a blue phosphorescent iridium or platinum complex as emitting compound or as sensitizer. 18. Electronic device according to one or more of claims 15 to 17, characterized in that the compound according to one or more of claims 1 to 10 is used as a matrix material in combination with an electron-transporting matrix material.