Materials for organic light-emitting devices

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

[0001] Materials for organic light-emitting devices

[0002] 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.

[0003] Electronic devices containing organic and / or organometallic semiconductors will be used in many commercial products, for example, organic light-emitting diodes (OLEDs). There is a great need to improve their performance, particularly lifetime, efficiency, and operating voltage. This is especially true for blue-phosphorescent OLEDs and hyperphosphorescent OLEDs.

[0004] The object of the present invention is to provide compounds that are suitable for use in an electronic device, in particular an OLED, in particular as electron-blocking materials and / or as host materials, and that lead to good properties there. WO 2010 / 054729 discloses diaza- and tetraazasilane derivatives that are used as electron-blocking materials and / or as matrix materials for green or blue phosphorescent compounds. Even though good results have already been achieved with these compounds, further improvements are desirable, particularly with regard to efficiency, voltage, and / or lifetime.

[0005] Surprisingly, it has been found that certain tetraazasilane derivatives described in more detail below, which are substituted with electron-rich heteroaromatics and / or benzimidazobenzimidazole groups, achieve this object and are well suited for use in electronic devices, in particular OLEDs. In particular, the OLEDs have an improved lifetime, higher efficiency and / or lower operating voltage compared to OLEDs that do not contain such heteroaryl groups. These compounds and electronic devices, in particular organic electroluminescent devices containing these compounds, are therefore the subject of the present invention. The present invention relates to a compound according to formula (1), formula (1) where the following applies to the symbols used: X is, on each occurrence, identically or differently, CR or N, with the proviso that no more than two Xs per cycle represent N; Ar 1 , Ar 2, Ar 3 , Ar 4 is, at each occurrence, identically or differently, 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, at each occurrence, identically or differently, H, D, F, Cl, 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, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1may be substituted, with one or more non-adjacent CH2 groups being replaced by -R 1 C=CR 1 - , -C≡C-, Si(R 1 )2, CONR 1 , C=O, C=S, -C(=O)O-, 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 may be substituted; two or more R radicals may form a ring system with each other;

[0006] R 1 is the same or different at 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, NO2, P(=O)(R 2 )2, OSO2R 2 , SR 2 , S(=O)R 2 , S(=O)2R 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, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 2 and wherein one or more CH2 groups in the above-mentioned groups are substituted 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 where one or more H atoms in the above-mentioned groups can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, where two or more radicals R 1 can form a ring system with each other;

[0007] R 2is, identically or differently at each occurrence, 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 may be replaced by D or F; two or more substituents R 2 linked together to form a ring; characterized in that at least one of the groups Ar 1 , Ar 2 , Ar 3 and Ar 4 represents an electron-rich heteroaryl group or a benzimidazobenzimidazole bonded via a carbon atom, each of which may be substituted by one or more radicals R, and / or that at least one group X represents CR and this R represents an electron-rich heteroaryl group or a benzimidazobenzimidazole bonded via a carbon atom, each of which may be substituted by one or more radicals R 1may be substituted, and / or that at least two adjacent groups X are CR and the two radicals R together with the carbon atoms to which they are bonded form an electron-rich heteroaryl group which can be substituted by one or more radicals R 1 can be substituted.

[0008] Benzimidazobenzimidazole has the following structure:

[0009] This structure can, if used for Ar 1 to Ar 4 also by one or more radicals R, or if it stands for R, also by one or more radicals R 1 be substituted. If one or more of Ar 1 to Ar 4have this structure, then this structure is bonded to the nitrogen atom in formula (1 ) via a carbon atom and to the one nitrogen atom is bonded a radical R. If one or more R stand for benzimidazobenzimidazole, then this structure is bonded to the carbon atom via a carbon atom or a nitrogen atom, wherein in the case of bonding via a carbon atom, another radical R 1 to which a nitrogen atom is bonded.

[0010] An aryl group within the meaning of this invention contains 6 to 40 C atoms; a heteroaryl group within the meaning of this invention contains 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 an aromatic ring system.

[0011] An aromatic ring system within the meaning of this invention contains 6 to 60 C atoms, preferably 6 to 40 C atoms in the ring system. A heteroaromatic ring system within the meaning 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 within the meaning of this invention is to be understood as a system which does not necessarily contain only 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 orHeteroaryl groups are directly linked to one another, such as, for example, 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 within the meaning of this invention, as are systems in which two or more aryl groups are linked, 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.

[0012] An electron-rich heteroaryl group is characterized by the fact that it is a heteroaryl group that contains no 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 oxygen, sulfur, or a substituted nitrogen atom, to which further aryl or heteroaryl groups may be fused. 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 may be fused.Examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indolocarbazole and indenocarbazole.

[0013] In the context of the present invention, the term "alkyl group" is used as a generic term for both linear and branched alkyl groups and cyclic alkyl groups. Analogously, the terms "alkenyl group" and "alkynyl group" are used as generic terms for both linear and branched alkenyl and alkynyl groups, as well as for cyclic alkenyl and alkynyl groups. A cyclic alkyl, alkoxy, or thioalkoxy group, for the purposes of this invention, is understood to mean a monocyclic, bicyclic, or polycyclic group.

[0014] In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which may contain 1 to 40 C atoms and in which individual H atoms or CH2 groups may be substituted by the above-mentioned 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 und l -(n-Decyl)- cyclohex-1 -yl, Ethenyl, Propenyl, Butenyl, Pentenyl, Cyclopentenyl, Hexenyl, Cyclohexenyl, Heptenyl, Cycloheptenyl, Octenyl, Cyclooctenyl, Cyclooctadienyl, Ethinyl, Propinyl, Butinyl, Pentinyl, Hexinyl, Heptinyl oder Octinyl verstanden. Unter einer Alkoxygruppe OR, 1mit 1 bis 40 C-Atomen werden bevorzugt Methoxy, Trifluorm ethoxy, Ethoxy, n-Propoxy, i-Propoxy, n-Butoxy, i-Butoxy, s-Butoxy, t-Butoxy, n-Pentoxy, s-Pentoxy, 2-Methyl- butoxy, n-Hexoxy, Cyclohexyloxy, n-Heptoxy, Cycloheptyloxy, n-Octyloxy, Cyclooctyloxy, 2-Ethylhexyloxy, Pentafluorethoxy und 2,2,2-Trifluorethoxy verstanden. Unter einer Thioalkylgruppe SR 1 mit 1 bis 40 C-Atomen werden insbesondere Methylthio, Ethylthio, n-Propylthio, i-Propylthio, n-Butylthio,

[0015] 1-Butylthio, s-Butylthio, t-Butylthio, n-Pentylthio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclooctylthio,

[0016] 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 above-mentioned groups; furthermore, one or more H atoms can also be replaced by D, F, Cl, Br, I, CN, or NO2, preferably D, F, Cl, or CN, particularly preferably D, F, or CN.

[0017] An aromatic or heteroaromatic ring system with 5 - 60 aromatic ring atoms, preferably 5 - 40 aromatic ring atoms, which may also be substituted by the above-mentioned radicals or a hydrocarbon radical and which may be linked to the aromatic or heteroaromatic ring via any desired positions, is understood to mean, in particular, groups 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,Indol, Isoindol, Carbazol, Pyridin, Chinolin, Iso- chinolin, Acridin, Phenanthridin, Benzo-5,6-chinolin, Benzo-6,7-chinolin, Benzo-7,8-chinolin, Phenothiazin, Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazin- imidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1 ,2-Thiazol, 1 ,3-Thiazol, Benzo- thiazol, Pyridazin, Hexaazatriphenylen, Benzopyridazin, Pyrimidin, Benz- pyrimidin, Chinoxalin, 1 ,5-Diazaanthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1 ,6-Diazapyren, 1 ,8-Diazapyren, 4,5-Diazapyren, 4,5,9, 10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1 ,2,3-Triazol, 1 ,2,4-Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1 ,2,4-Oxadiazol, 1 ,2,5-Oxadiazol, 1 ,3,4- Oxadiazol, 1 ,2,3-Thiadiazol, 1 ,2,4-Thiadiazol, 1 ,2,5-Thiadiazol, 1 ,3,4- Thiadiazol, 1 ,3,5-Triazin, 1 ,2,4-Triazin, 1 ,2,3-Triazin,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.

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

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

[0020] 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. Therefore, preferred compounds are those of the following formula (2), (3) and (4), with the compounds of formula (2) being particularly preferred, where the symbols used have the meanings given above.

[0021] These can be symmetric or asymmetric structures. Symmetric structures are characterized by the fact that all four groups Ar 1 , Ar 2 , Ar 3 and Ar 4 are identical and that the two cycles containing the groups X are identical. Asymmetric structures are characterized by the fact that not all four groups Ar 1 , Ar 2, Ar 3 and Ar 4 are identical and / or in that the two cycles containing the X groups are different, as is the case, for example, in the compounds of formula (4). Compounds in which the two cycles containing the X groups are different also exist when, for example, as in formula (2), all Xs are CR, but the R radicals on the two cycles are chosen differently and / or are bonded in different positions. Asymmetric structures are preferred.

[0022] When substituents are bonded to the two phenylene rings in structures of formula (2), preferred structures are the compounds of the following formulas (2a) to (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 formulas (2a), (2b) and (2d) are preferred.

[0023] For the groups Ar 1 , Ar 2 , Ar 3 and Ar 4 Various combinations and designs are suitable: (1 ) Ar 1 = Ar 2 = Ar 3 = Ar 4

[0024] (2) Ar 1 = Ar 2 and Ar 3 = Ar 4 , but Ar 1 + Ar 3

[0025] (3) Ar 1 = Ar 3 and Ar 2 = Ar 4 , but Ar 1 + Ar 2

[0026] (4) Ar 1 = Ar 2 = Ar 3 and Ar 4 + Ar 1

[0027] (5) Ar 1 = Ar 2 and Ar 3 + Ar 4 + Ar 1

[0028] (6) Ar 1 = Ar 3 and Ar 2 + Ar 4 + Ar 1

[0029] (7) Ar 1 + Ar 2 + Ar 3 + Ar 4 .

[0030] Embodiments (1), (2), (3) and (7) are particularly preferred. Different groups of Ar 1 to Ar 4 different aromatic or heteroaromatic ring systems, and / or they are the same aromatic or heteroaromatic ring systems, but differently substituted.

[0031] According to the invention, at least one of the groups Ar 1 , Ar 2 , Ar 3 and Ar 4 represents an electron-rich heteroaryl group or benzimidazobenzimidazole, each of which may be substituted by one or more radicals R, and / or at least one group X represents CR and this R represents an electron-rich heteroaryl group or benzimidazobenzimidazole, each of which may be substituted by one or more radicals R 1may be substituted, and / or at least two adjacent groups X are CR and the two radicals R together with the carbon atoms to which they are bound form an electron-rich heteroaryl group which is substituted by one or more radicals R 1 can be substituted.

[0032] In a preferred embodiment of the invention, the compound contains one, two, three or four groups Ar 1 to Ar 4 or R, which represent an electron-rich heteroaryl group or benzimidazobenzimidazole, particularly preferably one, two or three groups Ar 1 to Ar 4 or R and most preferably one or two groups Ar 1 to Ar 4 or R.

[0033] If two adjacent X groups represent CR and the two R radicals, together with the carbon atoms to which they are bonded, form a fused electron-rich heteroaryl group, it is preferred if such a fused electron-rich heteroaryl group is present once or twice, particularly preferably once. Preferred embodiments for this are the compounds of the following formulas (2g), (2h), (2i) and (2j), where the structure may also be partially or completely deuterated, the symbols used have the meanings given above and A 1 for NR 1 , 0 or S, preferably NR 1 or 0.

[0034] Preferred electron-rich heteroaryl groups or benzimidazobenzimidazole groups which are present according to the invention in the compound of formula (1) or the preferred embodiments are described below.

[0035] If one or more of the groups Ar1 to Ar 4 represents an electron-rich heteroaryl group or benzimidazobenzimidazole, this group is preferably selected from the group consisting of 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, benzimidazobenzimidazole, indenocarbazole, which is linked via a C atom, or indolocarbazole, which is linked via a C atom, where the aforementioned structures can each also be substituted by one or more radicals R. Particularly preferred are these groups Ar 1 to Ar 4 which represent an electron-rich heteroaryl group or benzimidazobenzimidazole selected from the structures of the following formulas (Ar-a) to (Ar-j), where the dashed bond represents the bond to the nitrogen atom, the symbols used have the meanings given above and A 1 stands for NR, O or S, preferably for NR or O.

[0036] If one or more of the groups R represent an electron-rich heteroaryl group or benzimidazobenzimidazole, this group is preferably selected from the group consisting of 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 or via N, dibenzothiophene, which can be linked via the 1-, 2-, 3- or 4-position, benzimidazobenzimidazole, which can be linked via a C or an N atom, indenocarbazole, which can be linked via a C or an N atom, or indolocarbazole, which can be linked via a C or an N atom, where the aforementioned structures can each also be linked via one or more radicals R 1Particularly preferred are those groups R which represent an electron-rich heteroaryl group or benzimidazobenzimidazole selected from the structures of the following formulas (Ra) to (Rl), where the dashed bond represents the bond to the carbon atom, the symbols used have the meanings given above and A 1 for NR 1 , 0 or S, preferably NR 1 or 0.

[0037] Preferred embodiments for Ar 1 to Ar 4 In a preferred embodiment of the invention, Ar 1 to Ar 4identically or differently on each occurrence 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 each 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 at least 12 aromatic ring atoms. Particularly preferably, at least two of the groups Ar 1 to Ar 4 at least 12 aromatic ring atoms each.

[0038] If all groups Ar 1 to Ar 4each 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 has at least two aromatic or heteroaromatic substituents R.

[0039] Suitable aromatic or heteroaromatic ring systems Ar 1 to Ar 4are selected, identically or differently at each occurrence, 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 may be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which may be linked via the 1-, 2-, 3- or 4-position, naphthalene, which may be linked via the 1- or 2-position, indole, benzofuran, benzothiophene, which may be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which may be linked via the 1-, 2-, 3- or 4-position, carbazole, which may be linked via the 1-, 2-, 3- or 4-position, Dibenzothiophene, which can be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, benzimidazole, benzimidazobenzimidazole,Phenanthrene, triphenylene or a combination of two or three of these groups, each of which may be substituted by one or more R radicals, preferably non-aromatic R radicals. If Ar, 1 to represents a heteroaryl group, in particular triazine, pyrimidine, quinazoline or carbazole, aromatic or heteroaromatic radicals R on this heteroaryl group may also be preferred. Preferred groups Ar 1 to Ar 4 are, identically or differently at each occurrence, selected from the groups of the following formulas (Ar-1 ) to

[0040] (Ar-144),

[0041] Ar-31 Ar-32

[0042] Ar-42

[0043] Ar-43

[0044] Ar-53

[0045] Ar-56 Ar ' 57

[0046] R

[0047] Ar-61

[0048] Ar-70 Ar-71

[0049] R

[0050] Ar-82 Ar -83

[0051] R

[0052] Ar-84 Ar-85 Ar-86 Ar-87

[0053] Ar-94 Ar-95 Ar-96

[0054] RRRRRR |- R

[0055] RRR

[0056] Ar-97 Ar-98 Ar-99 Ar-100

[0057] RR ? ?

[0058] -

[0059] Ar-101 Ar-102

[0060] Ar-107 Ar-108

[0061] Ar-112

[0062] -4; Ar-127

[0063] Ar-128

[0064] where R has the meanings given above, the dashed bond represents the bond to a nitrogen atom in formula (1 ) and furthermore:

[0065] 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;

[0066] A 1is, identically or differently at each occurrence, BR, C(R)2, C=O, NR, O 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 is present at this position 1 and R residues are bonded to the corresponding carbon atoms instead.

[0067] In a preferred embodiment, Ar 1 to Ar 4 no condensed aryl groups. Conversely, condensed heteroaryl groups in which no six-membered rings are directly condensed to one another may be suitable, for example, carbazole, dibenzofuran, or dibenzothiophene.

[0068] Particularly preferred groups Ar 1 to Ar 4are, identical or different at each occurrence, selected from the group consisting of the following structures Ar-a to Ar-n, Ar-e where the dashed bond represents the bond to the nitrogen atom and these structures can also be partially or completely deuterated.

[0069] Examples of particularly preferred combinations of Ar 1 , Ar 2 , Ar 3 and Ar 4 are the combinations listed in the following table:

[0070] Ar 1 Ar 2 Ar 3 Ar 4

[0071] Ar-a Ar-a Ar-g Ar-g

[0072] Ar-a Ar-g Ar-a Ar-g

[0073] Ar-a Ar-a Ar-j Ar-a

[0074] Ar-a Ar-a Ar-k Ar-a

[0075] Ar-a Ar-a Ar-n Ar-a

[0076] Ar-a Ar-a Ar-j Ar-a

[0077] Ar-a Ar-a Ar-k Ar-a

[0078] Ar-a Ar-a Ar-n Ar-a

[0079] Ar-a Ar-a Ar-j Ar-g

[0080] Ar-a Ar-a Ar-k Ar-g

[0081] Ar-a Ar-a Ar-n Ar-g

[0082] Ar-a Ar-a Ar-j Ar-j

[0083] Ar-a Ar-a Ar-k Ar-k

[0084] Ar-a Ar-j Ar-j Ar-a

[0085] Preferred substituents R, R 1 and R 2 In a particularly preferred embodiment of the invention, the following preferences for R, R 1 and R 2 simultaneously and apply to the structures of formula (1 ) as well as to all preferred embodiments.

[0086] Preferred substituents R attached to Ar 1 to Ar 4 are, at each occurrence, identically or differently selected from the group consisting of H, D, F, CN, Si(R 1 )s, Ge(R 1)s, a straight-chain alkyl group with 1 to 10 C atoms or cyclic alkyl group with 3 to 10 C atoms, wherein the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, but is preferably unsubstituted, and wherein one or more non-adjacent CH2 groups may be replaced by 0; two adjacent R radicals may form a ring system with each other. Particularly preferred is R which is attached to Ar 1 to Ar 4 bonded, is selected at 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, wherein the alkyl group is in each case substituted with one or more radicals R 1may be substituted, but is preferably unsubstituted; two adjacent R can form a ring system with each other. Very particular preference is given to R which is attached to Ar 1 to Ar 4 is bonded, is selected, identically or differently at each occurrence, from the group consisting of H, D, F, CN, Si(C6Hs)3, where the phenyl group may optionally be deuterated and / or substituted with one or more optionally deuterated methyl groups, or optionally deuterated methyl. Preferred substituents R which bond 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, wherein the alkyl group is in each case substituted with one or more radicals R 1may be substituted, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, each substituted by one or more radicals R 1 may be substituted. Particularly preferably, R, which for X = CR bonds to the carbon atom, 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, wherein the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 1 , preferably non-aromatic residues R 1, may be substituted. Very particularly preferably, R, which for X = CR bonds to the carbon atom, is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, Si(C6Hs)3, where the phenyl group may optionally be deuterated and / or substituted by one or more optionally deuterated methyl groups, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, particularly preferably having 6 to 18 aromatic ring atoms, each substituted by one or more radicals R 1 , preferably non-aromatic residues R 1 , can be substituted.

[0087] 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, 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 is optionally deuterated and / or with one or more radicals R, 1 , preferably non-aromatic residues R 1 , may be substituted. If R represents a heteroaryl group, in particular triazine, pyrimidine, quinazoline or carbazole, aromatic or heteroaromatic radicals R 1 at this heteroaryl group may be preferred.

[0088] 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,

[0089] R-19 R-20 R-21

[0090] R-33 R-34 R-35

[0091] R-53

[0092] 35 R-70 R-71 R-73 R-74 R ' 75

[0093] R-78 R ' 79

[0094] R 1

[0095] R-80

[0096] R-83

[0097] R-92 R-93

[0098] R-94 R-95 R-96

[0099] R-109 R-110 R-111 R-112

[0100] where R 1 has the meanings given above, the dashed bond represents the bond of the group and furthermore:

[0101] Ar* is at each occurrence, identically or differently, a bivalent aromatic or heteroaromatic ring system with 6 to 18 aromatic ring atoms, each of which is substituted by one or more radicals R 1 can be substituted; A 1 is the same or different each time it occurs 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 bound to the corresponding carbon atom; r is 0 or 1 , where r = 0 means that no group A is present at this position 1and the corresponding carbon atoms are instead bound to residues R 1 are bound.

[0102] If the above-mentioned groups Ar-1 to Ar-144 for Ar or R-1 to R-144 for R contain several groups A 1 , all combinations from the definition of A 1 Preferred embodiments are then those in which a group A 1 for C(R)2, NR, O or S and the other group A 1 represents C(R)2, NR, 0 or S, if it is a group Ar, or in which a group A 1 for C(R 1 )2, NR 1 , 0 or S and the other group A 1 for C(R 1 )2, NR 1 , 0 or S if it is a group R.

[0103] If A 1 for NR or NR 1 the substituent R or R 1which is bonded to the nitrogen atom, preferably represents 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 identically or differently on each occurrence represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, and which can each also be substituted by one or more radicals R 1 or R 2 may be substituted. 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 are substituted by one or more radicals R or R 1 may be substituted, but are preferably unsubstituted. If A 1 for C(R)2 or C(R 1)2, the substituents R and R 1 which are bonded to this carbon atom, preferably identically or differently on each occurrence, represent a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 1 or R 2 can be substituted. R or R 1 represents a methyl group or a phenyl group. The radicals R and R 1 also form a ring system with each other, which leads to a spiro system.

[0104] In a further preferred embodiment of the invention, R 1 identically or differently on each occurrence 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, wherein the alkyl or alkenyl group is each substituted with one or more radicals R 2 may be substituted, or an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, each substituted by one or more radicals R 2 may be substituted; two or more radicals R 1 together form an aliphatic ring system. In a particularly preferred embodiment of the invention, R 1identically or differently on each occurrence selected from the group consisting of H, D, Si(C6Hs)3, where the phenyl group may be substituted in each case by one or more methyl groups, 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 is substituted by one or more radicals R 2 may be substituted, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 2 can be substituted.

[0105] In a further preferred embodiment of the invention, R 2identical or different on each occurrence 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.

[0106] In a further preferred embodiment of the invention, all radicals R 1 , as long as they represent an aromatic or heteroaromatic ring system, selected from the groups R-1 to R-144, which, however, are then each substituted accordingly with R 2 instead of R 1 are substituted.

[0107] 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%, especially 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 that contains hydrogen in the natural isotopic distribution. In a fully deuterated compound, all H atoms are exchanged for D.

[0108] In a further embodiment of the invention, the compounds according to the invention are undeuterated, ie they contain hydrogen in the natural isotope distribution.

[0109] 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, most particularly preferably no more than 1 C atom.

[0110] The compounds according to the invention can be used as racemates or as pure enantiomers. The formation of enantiomers is possible, for example, if the groups Ar 1 , Ar 2 , Ar 3 and Ar 4 all chosen differently.

[0111] 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 preferences occur simultaneously. Examples of preferred compounds according to the above-mentioned embodiments are the compounds listed in the table below. 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.

[0112] 

[0113]

[0114]

[0115] 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 the person skilled in the art, e.g. B. the Buchwald-Hartwig or Ullmann coupling, starting from Ar-Hal with Hal = Cl, Br, I in the presence of a base (e.g. alkyllithium, such as n-BuLi or n-HexLi, 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 preferentially electron-rich phosphine (e.g. DPPF, BiNap, P(t-Bu)3, S-Phos, X-Phos, AmPhos, etc.) or a copper source (e.g. Cu, CuCl, Cul, CuOTf, etc.) in combination with an amine (e.g. pyridine, bipyridine, phenanthroline, glycine, DACH, etc.) in anhydrous Solvents (e.g.B. toluene, xylene, THF, dioxane, DMF, DMAc, NMP, DMSO, etc.). In addition, the coupling can be carried out via a SIShAr reaction with Ar-Hal with Hal = F, CI in the presence of a base (e.g. alkylithium, such as n-BuLi or n-HexLi, 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 to be introduced are Ar. 1 and Ar 2identical, the coupling can be carried out in one step according to the above-mentioned 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 SiCk, to give the intermediate (3). At a reactant stoichiometry of (2) to SiCh of 1:1, the reaction proceeds selectively to intermediate (3), since this exhibits a significantly reduced reactivity compared to further conversion to (5). In a third step, intermediate (3) is reacted with the bis-ithiated diamine (4) to form the product (5) according to the invention.If the diamines (2) to be introduced are identical, ie residues 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 SiCk of 2:1.

[0116] Scheme 1 :

[0117]

[0118] A further subject of the present invention is therefore a process for preparing the compounds according to the invention, characterized by the following steps:

[0119] (A) Providing a benzene derivative or corresponding heteroaromatic derivative which is ortho-linked 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 is substituted; and

[0120] (B) Reaction of SiHak, in particular SiCk, with the benzene derivative or corresponding heteroaromatic derivative which is in ortho-position to each other with a group -NHAr 1 and and a group -NHAr 2 is substituted, 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 is substituted.

[0121] A further subject of the present invention is an oligomer, polymer or dendrimer comprising one or more compounds according to formula (1), wherein instead of one or more radicals R there is a bond to the polymer chain.

[0122] For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be 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.

[0123] The present invention therefore further provides 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, for example, be a solvent and / or another organic or inorganic compound that is also used in the electronic device, for example an emitting compound and / or a matrix material.

[0124] 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. The present invention therefore further relates to the use of a compound according to the invention in an electronic device.

[0125] A further subject of the present invention is an electronic device comprising at least one compound according to the invention.

[0126] An electronic device within the meaning of the present invention is a device that contains at least one layer containing at least one organic compound. The component may also contain inorganic materials or layers composed entirely of inorganic materials.

[0127] 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 (OPDs), organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic plasmon-emitting devices.

[0128] The device is particularly preferably an organic electroluminescent device (OLED) comprising a cathode, an 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 may contain further layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers, and / or organic or inorganic p / n junctions. Interlayers, which, for example, have an exciton-blocking function, may also be introduced between two emitting layers. It should be noted, however, that not every one of these layers necessarily has to be present.The organic electroluminescent device can contain one emitting layer or multiple emitting layers. If multiple emitting layers are present, they preferably have a total of multiple emission maxima between 380 nm and 750 nm, resulting in overall white emission. This means that different emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. Systems with three emitting layers are particularly preferred, with the three layers exhibiting blue, green, and orange or red emission. The organic electroluminescent device according to the invention can also be a tandem OLED, particularly for white-emitting OLEDs.

[0129] The compound according to formula (1) is preferably 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 precise structure.

[0130] In a preferred embodiment of the invention, the compounds of formula (1) are used as hole-transporting materials. 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.

[0131] A hole-transport layer, as defined in the present application, is a layer with a hole-transporting function between the anode and the emitting layer. An exciton-blocking layer, as defined in 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.

[0132] 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, ie in a proportion of 100% in the layer, or it can be used in combination with one or more other compounds.

[0133] 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.

[0134] A hyperphosphorescent emission layer is a layer that typically contains one or more matrix materials, one or more phosphorescent compounds used as sensitizers and whose luminescence is not observed or not observed to a significant extent, and one or more fluorescent emitters that are responsible for the emission of the OLED.

[0135] 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, phosphorescent compounds are considered to be luminescent complexes with transition metals or lanthanides, particularly if they contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, indium, palladium, platinum, silver, gold, or europium, especially compounds containing indium, platinum, or copper. For the purposes of the present invention, all luminescent indium, platinum, or copper complexes are considered to be phosphorescent emitting compounds. Indium or platinum complexes are particularly preferred.

[0136] 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 according to the prior art for phosphorescent OLEDs and as known to the person skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art can use further phosphorescent complexes without inventive step.It is possible for the skilled person, even without inventive step, 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 exhibit high triplet energy depending on the substitution, it is particularly possible to use them as matrix material for blue-phosphorescent emitters.

[0137] 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.

[0138] In this case, the proportion of matrix material in the emitting layer 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.

[0139] 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.

[0140] An emissive 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 generally those with the smaller proportion in the system, and the matrix materials those with the larger proportion. 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.

[0141] 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 which 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.

[0142] Examples of phosphorescent compounds are listed below.

[0143]

[0144] 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, more preferably >2.65 eV, most preferably >2.75 eV, as defined by quantum mechanical calculations.

[0145] 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 using 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). TD-DFT singlet and triplet excitations (vertical excitations) are then calculated using the same method (B3LYP / 6-31 G(d)) and the optimized ground-state geometry. The default 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:

[0146] HOMO_corr = 0.90603 * HOMO (in eV) - 0.84836 LUMO_corr = 0.99687 * LUMO (in eV) - 0.72445 These values ​​are to be regarded as HOMO or LUMO energy levels of the materials in the sense of this application.

[0147] The lowest triplet state Ti is defined as the energy of the triplet state with the lowest energy, resulting from the described quantum chemical calculation. The lowest excited singlet state Si is defined as the energy of the excited singlet state with the lowest energy, resulting from the described quantum chemical calculation.

[0148] 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.

[0149] The compounds of formula (Pt-1 ) are very suitable as blue phosphorescent metal complexes according to the following definition: where:

[0150] Y 1 , Y 2 , Y 3 , Y 4 , Y 5 same or different at each occurrence for 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, each of which can also be substituted by one or more radicals R; E 50 at each occurrence, the same or different for C(R C0 )2, NR N0 , 0 or S;

[0151] Ar 50 at each occurrence, identically or differently, is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may also be substituted by one or more radicals R;

[0152] Ar 51 , Ar 52 , Ar 53 identical or different represent a condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms, each of which may also be substituted by one or more radicals R;

[0153] R Yat 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)2Ar, N(R)2, NO2, Si(R)3, B(OR)2, OSO2R, 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 CH2 groups may be replaced by RC=CR, C=C, Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, P(=O)(R), SO, SO2, O, S or CONR and where one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, 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 an aryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R, where two radicals RY together may form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R';

[0154] R co at 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 may form an aliphatic, aromatic or heteroaromatic ring system substituted by one or more radicals R;

[0155] R N0at 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.

[0156] Preferably, Ar 50 at each occurrence, identically or differently, 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.

[0157] Preferably, Ar 51 , Ar 52 , Ar 53identical or different, represent a condensed aryl or heteroaryl ring with 6 aromatic ring atoms, which may also be substituted by one or more radicals R.

[0158] Preferably, R Yat each occurrence, identically or differently, 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 radicals R.

[0159] Preferably, R coat each occurrence, identically or differently, represents 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 substituted by one or more radicals R.

[0160] Preferably, R N0 at 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.

[0161] Examples of suitable blue phosphorescent platinum complexes are shown below: / ° yl)

[0162] / \ NN Q-wyX

[0163] , X y O^ ö-vy > ö-Y

[0164] 2567761-13-9 2567761-57-1

[0165] 2460488-29-1

[0166] P yJ

[0167] 10 cfx:D ypy

[0168] KW öy y ö v nCQ JUCXJ yy vlVy X / _ vy \ A y

[0169] D O_ZJ )J^ D D \ D / ~ D \ / D D O

[0170] 20 ^ 6^ V

[0171] 7,

[0172] 25 ^05^ ( y VN TX : Q < Vj

[0173] ” <Ä % c5yyv

[0174] 35 X b

[0175] Other suitable blue phosphorescent compounds that can be used as sensitizers are those listed in the following table:

[0176] 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. B. according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776, azacarbazole derivatives, e.g. B. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, e.g. B. according to WO 2007 / 137725, silanes, e.g. B. according to WO 2005 / 111172, azaboroles or boronic esters, e.g. B. according to WO 2006 / 117052, triazine derivatives, e.g.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.

[0177] Since the compound of formula (1) or the preferred embodiments has hole-transporting properties, this compound is preferably combined with a compound having electron-transporting properties when used in a mixed matrix system.

[0178] 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).

[0179] 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.

[0180] A further subject 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),

[0181] Formula (eTMM1), Formula (eTMM2),

[0182] (R 7 )bi

[0183] Formula (eTMM3), where the symbols and indices used are:

[0184] L 2 is at each occurrence, identically or differently, a single bond or an aromatic or heteroaromatic ring system with 5 to 24 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted;

[0185] R# is, identically or differently at each occurrence, D, F, CN or an aromatic ring system with 6 to 24 ring atoms, which is substituted by one or more radicals R 6 can be substituted;

[0186] Y is the same or different at each occurrence N or CR 7, whereby it is excluded that two adjacent Y simultaneously mean N; V 2 is 0 or S;

[0187] R 6 is the same or different at each occurrence: H, D, F, CN, Si(R 7 )3, Ge(R 7 )3, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; two radicals R 6also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with each other;

[0188] Ar 5 represents, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is substituted by one or more radicals R 7 can be substituted;

[0189] R 7 is the same or different at each occurrence H, D, F, CI, Br, I, N(R 8 )2, CN, NO2, 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)2R 8 , OSO2R 8 , a straight-chain alkyl group with 1 to 20 C atoms or an alkenyl or alkynyl group with

[0190] 2 to 20 C atoms or a branched or cyclic alkyl group with

[0191] 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted with one or more radicals R 8 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted; two or more radicals R 7 form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R 8 is at each occurrence, identically or differently, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may also be replaced by F; b1 is 0, 1, 2, 3 or 4; b2 is 0, 1, 2 or 3.

[0192] 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).

[0193] Preferred compounds of the formula (eTMM1 ) are the compounds of the formulas (eTMMI a), (eTMMI b), (eTMMI c), (eTMMId) and (eTMMI e),

[0194] Ar 5

[0195] Formula (eTMMI a) 9£

[0196] OS

[0197] 92 gJV

[0198] L 2

[0199] I

[0200] Ar 5Formula (eTMMIe), where the symbols and indices for these formulas have the following meaning:

[0201] W, W 1 mean, the same or different at each occurrence, 0, S, C(R W )2 or N-Ar 5 ;

[0202] R w is, on each occurrence, identically or differently, 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 wwhich bind to the same carbon atom also form a ring system with each other;

[0203] A is the same or different at each occurrence CR 7 or N, where a maximum of two groups A per cycle stand for N and where A stands for C, if at this position L 2 is bound; a3 is, at each occurrence, the same or different, 0, 1, 2, 3 or 4; b3 is, at each occurrence, the same or different, 0, 1, 2 or 3;

[0204] Ring B is derived from an aryl group with 6 to 20 ring atoms, which may be substituted with one or more substituents R#;

[0205] L3 is an aromatic ring system with 6 to 40 ring atoms or a heteroaromatic ring system with 5 to 40 ring atoms, which are linked to one or more residues R 7 can be substituted;

[0206] L 2 , X, Ars, R 7 and R# have the meanings given above.

[0207] Particularly preferred matrix materials for blue phosphorescent OLEDs or hyperphosphorescent OLEDs are the compounds of the following formula (eTMMIc*),

[0208] Formula (eTMMIc*) where the symbols and indices used have the meanings given above and the compound may also be partially or fully deuterated. Particularly preferred groups are Ar 5 identically or differently at each occurrence selected from phenyl, meta-biphenyl or N-carbazolyl, each of which can also be substituted by one or more radicals R 7 may be substituted. Furthermore, at least one and particularly preferably exactly one of the substituents which is attached to the N-carbazolyl group or to Ar 5 are bonded, a triphenylsilyl group. The compound of the formula (eTMMIc*) particularly preferably has a group Ar 5 which represents a phenyl group substituted in the meta position with a triphenylsilyl group.

[0209] Preferred compounds of formula (eTMM3) are the compounds of formula (eTMM3a),

[0210] Formula (eTMM3a) where the symbols and indices for this formula (eTMM3a) have the following meaning:

[0211] W 1 is the same or different at each occurrence 0, S, C(R W )2 or N-Ar 5 ;

[0212] #X is CR or NAr 5 , preferably NAr 5 ;

[0213] R wis, on each occurrence, the same or different, 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, on each occurrence, the same or different, 0, 1, 2, 3 or 4;

[0214] Ring B l B J 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 5and R# have the meanings given above.

[0215] In compounds of formula (eTMM1 a) W is preferably 0 or N-Ar 5 .

[0216] In compounds of the formula (eTMMI a) A is preferably the same or different at each occurrence CR 7 , where A stands for C, if at this position L 2 is bound.

[0217] In compounds of the formulas (eTMMI d) or (eTMM3a) W 1 preferably 0, C(R W )2or N-Ar 5 , particularly preferably N-Ar 5 .

[0218] In compounds of the formula (eTMMI e) L 3 preferably a heteroaromatic ring system with 9 to 30 ring atoms, which is substituted with one or more radicals R 7 can be substituted.

[0219] In a preferred embodiment of the compounds of the formulas (eTMM1), (eTMMIa), (eTMMIb), (eTMMIe), (eTMMId), (eTMMIe), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), R 7identically or differently at each occurrence 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, wherein the alkyl group is in each case substituted with one or more radicals R 8 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, preferably having 5 to 40 ring atoms, each substituted by one or more radicals R 8 can be substituted.

[0220] In a particularly preferred embodiment of the compounds of the formulas (eTMM1), (eTMMIa), (eTMMIb), (eTMMIc), (eTMMId), (eTMMIe), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), R 7 identically or differently on each occurrence selected from the group consisting of H, D or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which is substituted with one or more radicals R 8can be substituted.

[0221] The preparation of the compounds of formulas (eTMM1), (eTMMIa), (eTMMIb), (eTMMIc), (eTMMId), (eTMMIe), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5) are generally known and some of the compounds are commercially available.

[0222] Suitable compounds of the formula (eTMM1 ) are known, for example, from the following publications: W02007 / 077810A1 , W02008 / 056746A1 , WO201 0 / 136109A1 , WO2011 Z057706A2, WO2011 Z160757A1 , WO2012 / 023947A1 , WO2012 / 048781 A1 , WO2013 / 077352A1 , WO2013147205A1 , WO2013 / 083216A1 , WO2014 / 094963A1 , WO201 4 / 007564A1 , WO2014 / 015931 A1 , WO2015 / 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, WO2020 / 130509A1, W02020 / 169241 A1, WO2020 / 141949A1 , WO2021 / 066623A1, W02021 / 101220A1, W02021 / 037401A1, W02021 / 180614A1, WO2021 / 239772A1, W02022 / 015084A1,WO2022 / 025714A1 , WO2022 / 055169A1 , EP3575296A1 , EP3591728A1 , US2014 / 0361254A1 , US2014 / 0361268A1 , KR20210036304A, KR20210036857A, KR2021147993A, JP2011 / 160367A2 and JP2017 / 107992A2.,

[0223] Suitable compounds of the formula (eTMM2) are known, for example, from the following publications: WO2015 / 182872A1, WO2015 / 105316A1, WO2017 / 109637A1, WO2018 / 060307A1, WO2018 / 151479A2, WO2018 / 088665A2, WO2018 / 060218A1, WO2018 / 234932A1, W02019 / 058200A1, WO2019 / 017730A1, WO2019 / 017731A1, WO2019 / 066282A1, WO2019 / 059577A1, W02020 / 141949A1 , W02020 / 067657A1, WO2022063744A1, W02022 / 090108A1, WO2022 / 207678A1, KR2019035308A, KR2021147993A, CN110437241A, US2016 / 072078A1.

[0224] Suitable compounds of the formula (eTMM3) are known, for example, from the following publications: WO2017 / 160089A1 , WO2019 / 017730A1 , WO201 9 / 017731 A1 , W02020 / 032424A1 .

[0225] Suitable compounds of the formula (eTMM5) are known, for example, from the following publications: WO2015 / 093878A1 , WO2016 / 033167A1 , WO201 7 / 183859A1 , WO2017 / 188655A1 , WO2018 / 159964A1 .

[0226] For combination with the compounds according to the invention, as described above or preferably described, compounds of the formulas (eTMM1), (eTMMIa), (eTMMIb), (eTMMIc), (eTMMId), (eTMMIe) and / or (eTMM2) are particularly suitable, as described above or preferably described, or corresponding compounds from the tables below that fall under these formulas. The compounds of the formulas (eTMM1), (eTMMIa), (eTMMIb), (eTMMIc), (eTMMId) and / or (eTMMIe) are particularly preferred.

[0227] 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-mentioned compounds of the invention, as described above, are the structures mentioned below in Tables A and B below.

[0228]  cn cn cn o

[0229]

[0230] o CXI co co

[0231]

[0232] Particularly suitable compounds of the formulas (eTMM1), (eTMMIa), (eTMMIb), (eTMMIc), (eTMMId), (eTMMIe), (eTMMIf) and / or (eTMM2), which can be combined according to the invention with the above-listed compounds of the invention, as described above, and are used in the electroluminescent device or mixture according to the invention, are the compounds E1 to E40 of Table B.

[0233] Table B: eV

[0234] O

[0235] ^o^ E1 E2 E3

[0236] D ° RD

[0237] D- <Z Ä D v eto D [P'Ä D D TÄr D

[0238] W U D

[0239] N>AN

[0240] D > [f D D-Ö" D 0

[0241] D D 0

[0242] E4 E5 E6

[0243] 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), (eTMMIb), (eTMMIc), (eTMMId), (eTMMIe), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), and their preferred embodiments described in Table 1 or the compounds E1 to E45 of Table 2.

[0244] 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.

[0245] 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), (eTMMIb), (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%.

[0246] 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.

[0247] The concentration of the sum of all host materials of the formulas (eTMM1), (eTMMIa), (eTMMIb), (eTMMIc), (eTMMId), (eTMMIe), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), 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.

[0248] The present invention also relates to a mixture which, in addition to the aforementioned host materials according to the invention and the host material of at least one of the formulas (eTMM1), (eTMMIa), (eTMMIb), (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:

[0249] D ■? D ? 9^

[0250] W :

[0251] -

[0252] D

[0253] ZZ>

[0254] NO yb

[0255] D Qr

[0256] Ci N J'"\H = = /

[0257] O aZ g ö ? ö Ö

[0258] N^NN^N

[0259] OTO O~rO ö 6

[0260]

[0261] Preferably, the at least one fluorescent emitter in the composition has a peak emission wavelength between 420-550 nm, preferably between 420-470 nm.

[0262] 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 containing three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a condensed ring system, particularly preferably having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysenamines, or aromatic chrysenediamines. An aromatic anthracenam 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 a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably in the 9- and 10-positions. Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, in which the diarylamino groups are preferably bonded to the pyrene in the 1- 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 benzofluorenediamines, for example according to WO 2008 / 006449, and dibenzoindenofluorenamines or diamines, for example according to WO 2007 / 140847, as well as the indenofluorene derivatives with fused aryl groups disclosed in WO 2010 / 012328. Likewise preferred are the pyrenarylamines disclosed in WO 2012 / 048780 and WO 2013 / 185871.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 WO 2017 / 036574, the phenoxazines disclosed in WO 2017 / 028940 and WO 2017 / 028941, and the fluorine derivatives bonded to furan units or thiophene units disclosed in WO 2016 / 150544. Furthermore, boron compounds according to

[0263] 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.

[0264] Preferably, the at least one fluorescent emitter has a full width at half maximum (FWHM) of < 50 nm, preferably FWHM of < 40 nm, more preferably FWHM of < 30 nm.

[0265] 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.

[0266] 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.

[0267] In a preferred embodiment of the invention, the fluorescent emitter is selected from structures of the following formula (F-1 ),

[0268] Formula (F-1) where R has the meanings given above and the other symbols and indices used are:

[0269] Ar 30 , Ar 31 , Ar 32 is, identically or differently on each occurrence, a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms;

[0270] Y 30 is B or N;

[0271] Y 31 Y 32 , Y 33 is the same or different at 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, SeÜ2 or a chemical bond, with the proviso that when Y 30 for B, at least one of the groups Y 31 , Y 32 , Y 33 stands for NR°, and if Y 30represents N, at least one of the group Y 31 , Y 32 , Y 33 stands for BR°;

[0272] R° is, identical or different at each occurrence, H, D, F, a straight-chain alkyl group having 1 to 20, preferably having 1 to 10, C atoms or a branched or cyclic alkyl group having 3 to 20, preferably having 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 having 5 to 30, particularly preferably having 6 to 18 aromatic ring atoms, each of which may be substituted by one or more substituents R; Two adjacent substituents R° can form an aliphatic or aromatic ring system which can be substituted by one or more substituents R; q is 0 or 1.

[0273] Particularly preferred are compounds where:

[0274] - q = 0; Y 30 = B; and Y 31 , Y 32 = NR°; or

[0275] - q = 0; Y 30 = B; and Y 31 , Y 32 = NR°; or

[0276] - q = 1 ; Y 30 = N; and Y 31 , Y 32 = BR°; Y 33 = chemical bond.

[0277] Examples of suitable fluorescent emitters are shown in the following

[0278] -US-

[0279] Suitable charge transport materials which 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 described in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials which are used in these layers according to the prior art.

[0280] All materials that are currently used 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 (e.g. according to WO 2006 / 122630 or WO 2006 / 100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (e.g. 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), phenanthrenediarylamines (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.,

[0281] 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.

[0282] 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 in 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. Further 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.

[0283] The device is structured, contacted and finally sealed accordingly (depending on the application) to exclude harmful influences from water and air.

[0284] In the further layers of the organic electroluminescent device according to the invention, all materials commonly used in the prior art can be used. Therefore, without inventive effort, the skilled person can use all materials known for organic electroluminescent devices in combination with the compounds according to the invention according to formula (1) or the preferred embodiments described above.

[0285] Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10' 5mbar, preferably less than 10' 6 mbar. However, it is also possible that the initial pressure is even lower, for example less than 10' 7 mbar.

[0286] Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are sublimated at a pressure between 10' 5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured.

[0287] Also preferred is an organic electroluminescent device characterized in that one or more layers are produced from solution, such as by spin coating, or by any printing process, such as screen printing, flexographic printing, offset printing, LITI (Light Induced Thermal Imaging, thermal transfer printing), inkjet printing, or nozzle printing. Soluble compounds are required for this, which are obtained, for example, by suitable substitution.

[0288] 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.

[0289] 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.

[0290] 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:

[0291] 1. The compounds of the invention exhibit a high glass transition temperature. This is desirable for the construction of stable OLEDs.

[0292] 2. The compounds according to the invention lead to an improvement in lifetime compared to compounds according to the prior art which do not have an electron-rich heteroaryl group.

[0293] 3. The compounds of the invention result in improved power efficiency compared to prior art compounds that do not contain an electron-rich heteroaryl group.

[0294] 4. The compounds according to the invention result in a reduced operating voltage compared to compounds according to the prior art which do not have an electron-rich heteroaryl group.

[0295] The invention is further illustrated by the following examples, without intending to limit it. From these descriptions, one skilled in the art can practice the invention within the entire disclosed scope and, without inventive step, prepare further compounds according to the invention and use them in electronic devices or apply the method according to the invention.

[0296] Examples:

[0297] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. Solvents and reagents are available from ALDRICH and ABCR, respectively.

[0298] 1) Synthesis of synthons:

[0299] Synthon S1 :

[0300] NH HN

[0301] A well-stirred mixture of 18.4 g (100 mmol) of N-phenyl-o-phenylenediamine [534-85-0], 24.7 g (100 mmol) of 4-bromodibenzofuran [89827-45-2], 65.2 g (200 mmol) of cesium carbonate, 411 mg (1 mmol) of S-Phos [657408-07-6], 224 mg (1 mmol) of palladium(II) acetate, 300 g of glass beads (3 mm diameter), and 500 ml of toluene is stirred at 70 °C for 12 h. After cooling, 200 ml of saturated ammonium chloride solution is added, followed carefully by 40 ml of acetic acid (foaming!). The mixture is stirred briefly, the aqueous phase is separated, and the organic phase is washed. The phase is washed twice with 200 ml of saturated sodium chloride solution each time, dried over magnesium sulfate, filtered off, and the filtrate is concentrated to dryness. The crude product is taken up in 200 ml of dichloromethane (DCM) and chromatographed with DCM on 500 g of silica gel. The resulting product is then extracted with 150 ml of ethanol. Yield: 30.5 g (87 mmol), 87%, purity: > 99% by HPLC.

[0302] 2) Synthesis of the compounds according to the invention:

[0303] Example B1:

[0304] A well-stirred mixture of 70.1 g (200 mmol) of S1 in 1200 mL of tetrahydrofuran (THF), cooled to 0 °C, was treated dropwise with 37.3 mL (400 mmol) of n-butyllithium, 10.6 M in n-hexane, over 20 min. The mixture was then allowed to warm to room temperature and stirred for 1 h. The reaction mixture was cooled again to 0 °C, and 11.5 mL (100 mmol) of silicon tetrachloride [10026-04-7] was added dropwise over 30 min., and the mixture was heated to reflux. After 16 hours, the mixture is allowed to cool, then 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 vigorous stirring. Stir for 5 hours, then 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 fractionated twice under high vacuum (p ~ 10'). 5 mbar, T ~ 270 - 285 °C). Yield: 45.7 g (63 mmol), 63%, purity: > 99.9% by HPLC.

[0305] The following connections can be represented analogously.

[0306] B3

[0307] Example B100:

[0308] A well-stirred mixture of 26.0 g (100 mmol) of N,N-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. Subsequently, 11.5 ml (100 mmol) of silicon tetrachloride [10026-04-7] is poured into the well-stirred reaction mixture, and the mixture is heated under reflux for 3 h. After cooling, the mixture is filtered through a bed of Celite pre-slurried with toluene, and the filtrate is then concentrated to dryness in vacuo, final temperature ~ 100 °C, final pressure ~ 0.1 mbar. The resulting dichlorosilane is dissolved in 500 ml of THF; this dichlorosilane solution is used in the next step.

[0309] A well-stirred mixture of 42.6 g (100 mmol) N cooled to 0 °C was added. 1 -Phenyl-N 218.7 ml (200 mmol) of n-butyllithium, 10.6 M in n-hexane, is added dropwise over 20 min to -(9-phenyl-9H-carbazol-3-yl)-1,2-phenylenediamine [2226920-05-2] in 500 ml of tetrahydrofuran (THF). The reaction mixture is allowed to warm to room temperature and stirred for 1 h. The dichlorosilane solution is then added with vigorous stirring and the mixture is stirred for 16 h at room temperature. 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 evaporated to dryness in vacuo. The crude product is dissolved in 200 ml of DCM and the solution is slowly added dropwise to 600 ml of ethanol at room temperature while stirring vigorously. Stir for 5 h, then the crystallized solid is filtered off with suction and dried in vacuo. The crystallization is repeated two more times with ethanol and then three times with 600 ml of acetonitrile.

[0310] Finally, the product is fractionated twice in high vacuum (p ~ 10' 5 mbar, T ~ 260 - 280 °C). Yield: 32.8 g (46 mmol), 46%, purity: > 99.9% by HPLC.

[0311] The following connections can be represented analogously.

[0312] Comparison of glass transition temperatures

[0313] 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 the Ar 1 to Ar 4 represent 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.

[0314] OLED examples

[0315] The production of OLEDs has 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 variations, layer sequences, and materials. Examples of OLEDs according to preferred embodiments of the invention are described below.

[0316] All exemplary OLED components are characterized by the following layer structure:

[0317] - glass plate (hereinafter also glass substrate or substrate),

[0318] - Indium tin oxide (hereinafter ITO) as anode,

[0319] - Hole injection layer (hereinafter HIL)

[0320] - Hole transport layer (hereinafter HTL), - Electron blocking layer (hereinafter EBL),

[0321] - Emission layer (hereinafter EML),

[0322] - Hole blocking layer (hereinafter HBL),

[0323] - Electron transport layer (ETL),

[0324] - Electron injection layer (hereinafter EIL), - Aluminium (hereinafter cathode).

[0325] The glass substrates with the patterned 50 nm thick ITO are pretreated with an oxygen plasma followed by an argon plasma. The materials for the HIL, HTL, EBL, EML, HBL, ETL, and EIL are then applied to the pretreated glass substrate by thermal evaporation in a vacuum chamber. Detailed information on the HIL, HTL, EBL, EML, HBL, ETL, and EIL of the OLED devices is provided in Table 1. The materials used in these examples are listed in Table 2. The cathode consists of a 100 nm thick aluminum layer.

[0326] 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 specific 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 a specific volume fraction (vol%) in the mixture. For example, the composition of an EML comprising a hole-transporting host material (HH) at 40 vol%, an electron-transporting host material (EH) at 40 vol%, and a phosphorescent metal complex (D) at 10 vol% is referred to in Table 1 as HH:EH:D (45%:45%:10%).This notation is analogous to describing the composition of an EML, which comprises two or four different materials, and also for HIL, HTL, EBL, HBL, ETL and EIL of the OLED, if these layers each comprise more than one material.

[0327] The performance of OLED devices can be measured using standard methods. For this purpose, the electroluminescence (EL) spectra and the external quantum efficiency (EQE) can be determined from current / voltage / luminance (IUL) characteristics, assuming a Lambertian emission profile. The EL spectra can be measured at a luminance of 1000 cd / m 2 and the CIE 1931 x- and y-coordinates are calculated from the EL spectrum. The operating voltage U is defined as the voltage required for a current density of 10 mA / cm 2is required. In Table 1, the voltage U is shown as a relative voltage (rel. U), whereby the voltage of the reference component in the comparison example (SdT1 ) was set to 100% rel. U. The power efficiency EffP is the ratio of the radiated luminous flux (luminous power) in lumens (lm) 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 decreases during operation at a constant current density of 5 mA / cm 2to 90% of the initial luminance. In Table 1, the lifetime LT90 is shown as a relative lifetime (rel. LT90), whereby the lifetime of the reference component in the comparison example (SdT1) was set to 100% rel. LT.

[0328] The following embodiment 1 corresponds to a preferred embodiment of the invention. SdT1 is an example of an OLED containing 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 2B. HTM is a fluorenamine.

[0329] 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 with an OLED according to Example SdT1 from Table 1, which contains a material according to the prior art. The two devices differ with regard to the hole-transporting host material used in the respective EML, i.e. H-2 in the case of SdT1 and H-1 in the case of Example 1. The inventive OLED according to Example 1 has a better lifetime (LT90), a better power efficiency (EffP), and a better operating voltage (U) than the OLED according to SdT1, which contains a material according to the prior art.

[0330] Table 1 : Structure and results of the OLEDs (V)

[0331] Eg. HIL HTL EBL EML HBL ETL ji QF EIL Rel. Rel. Rel. [nm] [nm] [nm] [nm] [nm] [nm] [nm] LT EffP U

[0332] H-2:E-1 :D-1 E-1 ETM:fLiW [%] [%] [%]

[0333] SdT HTM:PD HTM EBM Q © ■ LiQ 100 100 100

[0334] 1 (95%:5%) 150 20 nm (36%:54%: 10 nm (50%:50%) 1 nm 20nm nm 10%) 30nm 30nm

[0335] 1 HTM:PD HTM EBM H-1 :E-1 :D-1 E-1 ETM:LiQ LiQ 136 106 94 (95%:5%) 150 20 nm (36%:54%: 10 nm (50%:50%) 1 nm 20nm nm 10%) 30nm 30nm

[0336] 2 HTM:PD HTM EBM H-3:E-1 :D-1 E-1 ETM:LiQ LiQ 1 16 103 97 (95%:5%) 150 20 nm (40%:50%: 10 nm (50%:50%) 1 nm 20nm nm 10%) 30nm 30nm

[0337] 3 HTM:PD HTM EBM H-4:E-1 :D-1 E-1 ETM:LiQ LiQ 1 12 107 92 (95%:5%) 150 20 nm (36%:54%: 10 nm (50%:50%) 1 nm 20nm nm 10%) 30nm 30nm

[0338] 4 HTM:PD HTM EBM H-5:E-1 :D-1 E-1 ETM:LviQ LiQ 133 107 93 (95%:5%) 150 20nm (30%:60%: 10nm (50%:50%) 1 nm 20nm nm 10%) 30nm 30nm

[0339] 5 HTM:PD HTM EBM H-6:E-1 :D-1 E-1 ETM:LiQ LiQ 130 109 93 (95%:5%) 150 20nm (30%:60%: 10nm (50%:50%) 1 nm 20nm nm 10%) 30nm 30nm

[0340] 6 HTM:PD HTM EBM H-7:E-1 :D-1 E-1 ETM:LiQ LiQ ooo 124 106 91 (95%:5%) 150 20nm (30%:60%: 10nm (50%:50%) 1 nm 20nm nm 10%) 30nm 30nm

[0341] Table 2: Structural formulas of OLED materials

[0342] NFFN

[0343] / ={ /

[0344] NFFN

[0345] PD EBM

[0346] QQ öö

[0347] H-1 H-2 (comparison)

Claims

Patent claims 1 . Compound according to formula (1 ), Formula (1 ) where the symbols used are: X is, at each occurrence, the same or different, CR or N, with the proviso that not more than two X per cycle represent N; Ar 1 , Ar 2 , Ar 3 , Ar 4 is at each occurrence, identically or differently, 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 the same or different at 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, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted, with one or more non-adjacent CH2 groups being replaced by -R 1 C=CR 1 -, -CEC-, Si(R 1 )2, CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), -O-, -S-, 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 is substituted by one or more radicals R 1 substitute can be tuiert; two or more radicals R can form a ring system with each other; R 1 is the same or different at each occurrence H, D, F, CI, Br, I, B(OR 2 )2, CHO, C(=O)R 2 , CR2 =C(R 2 )2, CN, C(=O)OR 2 , Si(R 2 )3, Ge(R 2 )3, NO2, P(=O)(R 2 )2, OSO2R 2 , SR 2 , S(=O)R 2 , S(=O)2R 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, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 2 may be substituted and wherein one or more CH2 groups in the above-mentioned groups are substituted 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 where one or more H atoms in the above-mentioned groups can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, where two or more radicals R 1 can form a ring system with each other; R 2 is, identically or differently at each occurrence, 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 may be replaced by D or F; two or more substituents R 2 linked together to form a ring; characterized in that at least one of the groups Ar 1 , Ar 2 , Ar 3 and Ar 4represents an electron-rich heteroaryl group or a benzimidazobenzimidazole bonded via a carbon atom, each of which may be substituted by one or more radicals R, and / or that at least one group X represents CR and this R represents an electron-rich heteroaryl group or a benzimidazobenzimidazole bonded via a carbon atom, each of which may be substituted by one or more radicals R 1 may be substituted, and / or that at least two adjacent groups X are CR and the two radicals R together with the carbon atoms to which they are bound, form an electron-rich heteroaryl group which is substituted by one or more radicals R 1 can be substituted.

2. A compound according to claim 1, selected from the structures of formulas (2), (3) or (4), Formula (2) Formula (3) Formula (4) wherein the symbols used 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) Ar 1 Ar 3 i , i , Ar 2 Ar 4 Formula (2c) Formula (2d) Ar 2 Ar 4 Ar 2 Ar 4 Formula (2e) Formula (2f) where the structures 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 for the groups Ar 1 , Ar 2 , Ar 3 and Ar 4 applies: (1 ) Ar 1 = Ar 2 = Ar 3 = Ar 4 ; (2) Ar 1 = Ar 2 and Ar 3 = Ar 4 , but Ar 1 + Ar 3 ; (3) Ar 1 = Ar 3 and Ar 2= Ar 4 , but Ar 1 + Ar 2 ; (4) Ar 1 = Ar 2 = Ar 3 and Ar 4 + Ar 1 ; (5) Ar 1 = Ar 2 and Ar 3 + Ar 4 + Ar 1 ; (6) Ar 1 = Ar 3 and Ar 2 + Ar 4 + Ar 1 ; or (7) Ar 1 + Ar 2 + Ar 3 + Ar 4 .

5. A compound according to one or more of claims 1 to 4, selected from the compounds of formulas (2g), (2h), (2i) and (2j), Formula (2i) Formula (2j) where the structure may also be partially or completely deuterated, the symbols used have the meanings given in claim 1 and A 1 for NR 1 , 0 or S.

6. A compound according to one or more of claims 1 to 5, characterized in that if one or more of the groups Ar 1 to Ar4 represent an electron-rich heteroaryl group or benzimidazobenzimidazole, this group is selected from the group consisting of dibenzofuran, which is linked via the 1-, 2-, 3- or 4-position, carbazole, which is linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, which is linked via the 1-, 2-, 3- or 4-position, benzimidazobenzimidazole, indenocarbazole, which is linked via a C atom, or indolocarbazole, which is linked via a C atom, where the structures can each also be substituted by one or more radicals R; and characterized in that, when one or more of the groups R represent an electron-rich heteroaryl group or benzimidazobenzimidazole, this group is selected from the group consisting of dibenzofuran, which is linked via the 1-, 2-, 3- or 4-position, carbazole, which is linked via the 1-, 2-, 3- or 4-position or via N, dibenzothiophene, which is linked via the 1-, 2-, 3- or 4-position, benzimidazobenzimidazole, which is linked via a C or an N atom, indenocarbazole, which is linked via a C or an N atom, or indolocarbazole, which can be linked via a C or an N atom, wherein the structures can each also be linked by one or more radicals R 1 can be substituted.

7. A compound according to one or more of claims 1 to 6, characterized in that if one or more of Ar 1 to Ar 4 represent an electron-rich heteroaryl group or benzimidazobenzimidazole, these are selected from the structures of the formulas (Ar-a) to (Ar-j), where the dashed bond represents the bond to the nitrogen atom, the symbols have the meanings given in claim 1 and A 1represents NR, O or S; and that when one or more of the groups R represent an electron-rich heteroaryl group or benzimidazobenzimidazole, these are selected from the structures of the formulas (Ra) to (Rl), where the dashed bond represents the bond to the carbon atom, the symbols have the meanings given in claim 1 and A 1 for NR 1 , 0 or S.

8. Compound according to one or more of claims 1 to 7, characterized in that Ar 1 to Ar 4are selected, identically or differently at each occurrence, from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, dibenzofuran, carbazole, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, benzimidazole, phenanthrene or triphenylene, which may each be substituted by one or more radicals R.

9. A compound according to one or more of claims 1 to 8, characterized in that the compound is at least 30% deuterated.

10. A process for preparing a compound according to one or more of claims 1 to 9, characterized by the following steps: (1 ) Providing a benzene derivative or corresponding heteroaromatic derivative which is ortho-linked to each other with a group -NHAr 1 and -NHAr 2is substituted 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 is substituted; and (2) Reaction of SiHak, where Hal is a halogen, with the benzene derivative or corresponding heteroaromatic derivative, which is ortho-connected to each other with a group -NHAr 1 and and a group -NHAr 2 is substituted, 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 is substituted.

11. Mixture containing at least one compound according to one or more of claims 1 to 9 and at least one further compound.

12. Use of a compound according to one or more of claims 1 to 9 in an electronic device.

13. Electronic device comprising at least one compound according to one or more of claims 1 to 9.

14. Electronic device according to claim 13, which is an organic electroluminescent device, characterized in that the compound according to one or more of claims 1 to 9 is used in a hole transport layer and / or an exciton blocking layer and / or as matrix material in an emitting layer.

15. Electronic device according to claim 14, characterized in that the emitting layer is a phosphorescent or hyperphosphorescent layer.

16. Electronic device according to claim 15, characterized in that the emitting layer contains a blue phosphorescent iridium or platinum complex as emitting compound or as sensitizer.

17. Electronic device according to one or more of claims 14 to 16, characterized in that the compound according to one or more of claims 1 to 9 is used as matrix material in combination with an electron-transporting matrix material.

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