Materials for organic electroluminescent devices

Abstract

The present invention relates to silicon compounds and derivatives thereof, and to electronic devices, in particular organic electroluminescent devices, containing said compounds.

Description

[0001] Materials for organic electroluminescent devices

[0002] The present invention relates to silicon compounds and derivatives of these compounds, as well as electronic devices, in particular organic electroluminescent devices, containing these compounds.

[0003] In organic electroluminescent devices (OLEDs), phosphorescent organometallic complexes are often used as emitting materials. In general, there is still room for improvement in OLEDs, especially in OLEDs exhibiting triplet emission (phosphorescence), for example, with regard to efficiency, operating voltage, and lifetime. The properties of phosphorescent OLEDs are determined not only by the triplet emitters used. The other materials used, such as matrix materials or charge-transport materials, are also of particular importance. Improvements to these materials can therefore also lead to improvements in OLED properties.

[0004] The object of the present invention is to provide compounds which are suitable for use in an OLED, in particular as matrix material for phosphorescent emitters, as hole transport material or as electron blocking material, and which lead to good properties there.

[0005] Surprisingly, it has been found that certain compounds, described in more detail below, solve this problem and are well suited for use in OLEDs. In particular, the OLEDs exhibit a long lifetime, high efficiency, and low operating voltage. These compounds and electronic devices, in particular organic electroluminescent devices containing these compounds, are therefore the subject of the present invention.

[0006] The present invention therefore relates to a compound containing a partial structure according to the following formula (1),

[0007] where the symbols used are:

[0008] M is Si, Ge, Sn, Ti, Zr or Hf;

[0009] W is at each occurrence the same or different CR or N, where per cycle a maximum of one W stands for N; or the two W together form a group of the following formula (2),

[0010] Formula (2) where one of the two dashed bonds represents the bond to N and the other of the two dashed bonds represents the bond to Z;

[0011] Z is, in each occurrence, the same or different, a single bond,

[0012] BR, CR2, C=O, SiR2, GeR2, NR, P(=O)R, 0, S or SO2;

[0013] Y is, at each occurrence, the same or different, NR, O or S; or Y, together with the explicitly drawn carbon atom and the adjacent X, forms a group according to the following formula (3) or (4),

[0014] Formula (3) Formula (4) where W, Z and X have the meanings given above, the dashed bond marked with * represents the bond to M and the two further dashed bonds represent the linkage of the structure within formula (1); X is, at each occurrence, identical or different, CR or N, where a maximum of two Xs per cycle represent N, or two adjacent Xs in formula (2) together represent CR2, NR, O or S; R is, at each occurrence, identical or different, H, D, F, Cl, Br, I, N(Ar)2, N(R 1 )2, OAr, SAr, CN, NO2, OR 1 , SR 1 , COOR 1 , C(=O)N(R 1 )2, Si(R 1 )3, B(OR 1 )2, C(=O)R 1 , P(=O)(R 1 )2, S(=O)R 1 , S(=O)2R 1 , OSO2R 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 substituted by Si(R 1 )2, C=O, NR 1 , O, S or CONR 1 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which can be substituted with one of the several radicals R 1 may be substituted; two radicals R can also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; Ar is, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted with one or more radicals R 1 can be substituted; R1 is the same or different at each occurrence: H, D, F, Cl, Br, I, N(R 2 )2, CN, NO2, OR 2 , SR 2 , Si(R 2 )3, B(OR 2 )2, C(=O)R 2 , P(=O)(R 2 )2, S(=O)R 2 , S(=O)2R 2 , OSO2R 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, with one or more non-adjacent CH2 groups being substituted by Si(R 2 )2, C=O, NR 2 , O, S or CONR 2and wherein one or more H atoms in the alkyl, alkenyl or alkynyl group may be replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted; two or more radicals R 1 form an aliphatic, aromatic or heteroaromatic ring system; R 2is, at each occurrence, identically or differently, H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may be replaced by F. In a preferred embodiment of the invention, the compound containing a partial structure of the formula (1) is a compound of the following formula (5) or (6), where the symbols used have the meanings given above and furthermore: R M is the same or different at each occurrence F, CN, OR 1 , OAr, N(R 1 )2, NAr2, Si(R 1 )3, 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 or alkoxy group is each substituted with one or more radicals R 1 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 1 )2, C=O, NR1 , O, S or CONR 1 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which can be substituted with one of the several radicals R 1 can be substituted; two radicals R M also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system, where the linkage of the two radicals R M by a single bond or by a group selected from C(R 1 )2, O, S, NR 1 or BR; furthermore, one or more R M be linked with one or more R to form a ring system.

[0015] 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 2 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.

[0016] 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 2 to 60 C atoms, preferably 2 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, such as a C, N or O atom. This is also to be understood as meaning systems in which two or more aryl or heteroaryl groups are directly linked to one another, such as, for example, a C, N or O atom. B. biphenyl, terphenyl, bipyridine or phenylpyridine.For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ethers, 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 short alkyl 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 or bipyridine, as well as fluorene or spirobifluorene.

[0017] For the purposes of the present invention, the term "alkyl group" encompasses both linear and branched and / or cyclic alkyl groups, where cyclic alkyl groups can be monocyclic, bicyclic, tricyclic, or oligocyclic. The same applies to alkenyl and alkynyl groups.

[0018] 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, neo-pentyl, cyclopentyl, n-hexyl, neo-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, Cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentinyl, hexynyl, heptynyl or octynyl. Under an alkoxy group OR 1mit 1 bis 40 C-Atomen werden bevorzugt Methoxy, Trifluormethoxy, 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 1mit 1 bis 40 C-Atomen werden insbesondere Methylthio, Ethylthio, n-Propylthio, i-Propylthio, n- Butylthio, i-Butylthio, s-Butylthio, t-Butylthio, n-Pentylthio, s-Pentylthio, n- Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclo- octylthio, 2-Ethylhexylthio, Trifluormethylthio, Pentafluorethylthio, 2,2,2- Trifluorethylthio, Ethenylthio, Propenylthio, Butenylthio, Pentenylthio, Cyclopentenylthio, Hexenylthio, Cyclohexenylthio, Heptenylthio, Cyclo- heptenylthio, Octenylthio, Cyclooctenylthio, Ethinylthio, Propinylthio, Butinylthio, Pentinylthio, Hexinylthio, Heptinylthio oder Octinylthio ver- standen.In general, alkyl, alkenyl, alkynyl, alkoxy, or thioalkyl groups according to the present invention may be straight-chain, branched, or cyclic, wherein one or more non-adjacent CH2 groups may be replaced by the above-mentioned groups; furthermore, one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, preferably by D, F, or CN.

[0019] An aromatic or heteroaromatic ring system with 5 - 60 aromatic ring atoms, which is furthermore linked to the above-mentioned radicals R 1can be substituted, are understood in particular to mean 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, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, Phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, Anthroxazole, phenanthroxazole, isoxazole, 1,2- Thiazol, 1 ,3-Thiazol, Benzothiazol, Pyridazin, Hexaazatriphenylen, Benzo- pyridazin, Pyrimidin, Benzpyrimidin, Chinazolin, Chinoxalin, 1 ,5-Diaza- anthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1 ,6-Diazapyren, 1 ,8-Diaza- pyren, 4,5-Diazapyren, 4,5,9, 10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzo- carbolin, Phenanthrolin, 1 ,2,3-Triazol, 1 ,2,4-Triazol, Benzotriazol, 1 ,2,3- Oxadiazol, 1 ,2,4-Oxadiazol, 1 ,2,5-Oxadiazol, 1 ,3,4-Oxadiazol, 1 ,2,3- Thiadiazol, 1 ,2,4-Thiadiazol, 1 ,2,5-Thiadiazol, 1 ,3,4-Thiadiazol, 1 ,3,5- Triazin, 1 ,2,4-Triazin, 1 ,2,3-Triazin, Tetrazol, 1 ,2,4,5-Tetrazin, 1 ,2,3,4- Tetrazin, 1 ,2,3,5-Tetrazin, Purin, Pteridin, Indolizin und Benzothiadiazol oder Gruppen, die abgeleitet sind von Kombination dieser Systeme.,

[0020] For the purposes of this description, the phrase "two or more residues can form a ring" 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:

[0021] Ring formation of the residues R

[0022] H,C.,CH, CH2

[0023] Analogously, the formation of a fused aromatic ring is possible when two substituents R, each representing alkenyl groups, are linked to each other by a chemical bond with formal elimination of two hydrogen atoms.

[0024] 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:

[0025] Ring formation of the residues R The compounds according to the invention can also be partially or completely deuterated.

[0026] In a preferred embodiment of the invention, Y, identically or differently on each occurrence, represents NR, or Y, together with the explicitly drawn carbon atom and the adjacent X, forms a group according to the formula (3) shown above. Very particularly preferably, Y, together with the explicitly drawn carbon atom and the adjacent X, forms a group according to the formula (3) shown above.

[0027] In a preferred embodiment of the invention, a maximum of one X per ring stands for N. Particular preference is given to compounds in which all X in the two fused six-membered rings stand for CR, where X stands for C when this together with the adjacent carbon atom and Y stands for a group of the formula (3) or (4). Particular preference is given to all X in the partial structure of formula (1) or in the compounds of formulas (5) and (6) standing for CR, where X stands for C when this together with the adjacent carbon atom and Y stands for a group of the formula (3) or (4).

[0028] Preferred embodiments of the partial structure of formula (1) are thus the structures according to the following formulas (7) and (8),

[0029] Formula (7) Formula (8) where the symbols used have the meanings given above and Y in formula (8) stands for NR, O or S, with Y = NR being preferred. Preferred embodiments of the compounds of formulas (5) and (6) are correspondingly the compounds of the following formulas (9), (10), (11) and (12),

[0030] Formula (10)

[0031] Formula (11) Formula (12) where the symbols used have the meanings given above and Y in formula (10) and (12) stands for NR, O or S, where Y = O or NR is preferred.

[0032] In a further preferred embodiment of the invention, Z, identical or different on each occurrence, represents a single bond, CR2, BR or O, particularly preferably a single bond.

[0033] In a further preferred embodiment of the invention, both groups W together represent a group of the following formula (2a), formula (2a)

[0034] Further preferred is an embodiment in which Z stands for a single bond and in the same cycle one of the two groups W stands for CR and the other group W stands for N.

[0035] Particularly preferred partial structures of the formula (1) or the partial structures (7) and (8) are the structures of the following formulas (7a), (7b), (8a) and (8b),

[0036] Formula (8a) Formula (8b) where the symbols used have the meanings given above and Y in formulas (8a) and (8b) preferably represents NR, O, or S, with Y = O or NR being particularly preferred. Z in formulas (7a) and (8a) preferably represents a single bond.

[0037] Accordingly, particularly preferred compounds are the compounds of the following formulas (9a), (9b), (10a), (10b), (11a), (11b), (12a) and (12b),

[0038] RR

[0039] Formula (9a) Formula (9b)

[0040] R

[0041] Formula (10a) Formula (10b)

[0042] Formula (11a)

[0043] Formula (12b) where the symbols used have the meanings given above and Y in formulas (10a), (10b), (12a) and (12b) preferably represents NR, O or S, with Y = O or NR being particularly preferred. Z in formulas (9a), (10a), (11a) and (12a) preferably represents a single bond. Very particular preference is given to the compounds of the following formulas (9a-1), (10a-1), (11a-1) and (12a-1),

[0044] Formula (9a-1 ) Formula (10a-1 )

[0045] Formula (11 a-1 ) Formula (12a-1) where the symbols used have the meanings given above and Y in formulas (10a-1 ) and (12a-1 ) preferably represents NR, O or S, with Y = O or NR being particularly preferred. Z preferably represents a single bond.

[0046] In a further preferred embodiment of the invention, M in the partial structure of formula (1), in the compounds of formulas (5) and (6), and in the preferred embodiments listed above and below, represents Si or Ge, particularly preferably Si.

[0047] Preferably, the partial structure of formula (1) or the preferred embodiments of this formula listed above and below have no more than four, preferably no more than two, substituents R bonded to C atoms which are different from H or D.

[0048] The compounds of formulas (5) or (6) or the preferred embodiments of these formulas listed above and below preferably have no more than four substituents R bonded to C atoms which are different from H or D. The compounds particularly preferably have no more than two substituents R bonded to C atoms which are different from H or D.

[0049] Preferred substituents R M R, R 1 and R 2 on the compounds according to the invention. In a particularly preferred embodiment of the invention, the following preferences for R M , R, R 1 and R 2 simultaneously and apply to the structures of formula (1), the compounds of formulas (5) and (6), as well as to all preferred embodiments listed above.

[0050] In a preferred embodiment of the invention, R M same or different at each occurrence N(R 1 )2, NAr2, a straight-chain alkyl group having 1 to 6 C atoms or a branched or cyclic alkyl group having 3 to 6 C atoms, in each of which one or more H atoms may be replaced by D, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, which is substituted by one or more radicals R 1can be substituted; the two radicals R M form a ring system. Particularly preferred groups R M are selected from the group consisting of methyl, iso-propyl, tert-butyl, neo-pentyl, cyclopentyl, cyclohexyl, phenyl, which may also be substituted by one or more substituents R 1 may be substituted, or ortho-, meta- or para-biphenyl, which may also be substituted by one or more substituents R 1 may be substituted, whereby the above-mentioned groups may also be partially or fully deuterated and whereby two of these groups may also form a ring with each other and with the M to which they bind. If groups R M form a ring with each other, then this ring is preferably a metallacyclopentyl, metallacyclohexyl or metallafluorene, where "metalla" stands for Si, Ge, Sn, Ti, Zr or Hf. In a further preferred embodiment of the invention, both groups R Mtogether for a group of the following formula (13), where the dashed bonds represent the bonds to M and R 1 has the meanings given above, where the two R 1 which are bonded to N, preferably identically or differently on each occurrence, represent an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, each of which may be substituted by one or more radicals R. Such a group is formed when the two groups R M each for N(R 1 )2, where a residue R 1 at one N represents an optionally substituted phenyl group and a radical R 1 at the other N is H and these radicals together form a ring system. If Y is NR, the radical R bonded to the nitrogen atom preferably represents an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is bonded to one or more radicals R 1may be substituted, particularly preferably for an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which is substituted with one or more radicals R 1 may be substituted, and most preferably an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, which is substituted by one or more radicals R 1 may be substituted, wherein phenyl, ortho-, meta- or para-biphenyl, dibenzofuranyl or carbazolyl, each of which is substituted by one or more radicals R 1 may be substituted, are particularly preferred. Preferred aromatic and heteroaromatic radicals R which are bonded to the nitrogen atom for Y = NR correspond to the preferred aromatic and heteroaromatic radicals R listed below.

[0051] In a preferred embodiment of the invention, R is selected at each occurrence, identically or differently, from the group consisting of H, D, F, N(Ar)2, OAr, SAr, CN, OR 1 , 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 1 may be substituted, but is preferably unsubstituted, and wherein one or more non-adjacent CH2 groups may be replaced by O, or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which is substituted with one or more radicals R 1may be substituted; two radicals R can also form an aliphatic, aromatic or heteroaromatic ring system with one another. Particularly preferably, R is selected, identically or differently at each occurrence, from the group consisting of H, N(Ar)2, a straight-chain alkyl group having 1 to 6 C atoms, in particular having 1, 2, 3 or 4 C atoms, a straight-chain alkenyl group having 2 to 4 C atoms, in particular having 2 C atoms, or a branched or cyclic alkyl group having 3 to 6 C atoms, where the alkyl or alkenyl 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, which is substituted by one or more radicals R 1may be substituted. Very particularly preferably, R is selected on each occurrence, identically or differently, from the group consisting of H, D or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, which is substituted with one or more radicals R 1 may be substituted. In a further preferred embodiment of the invention, Ar is identical or different and represents 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 13 aromatic ring atoms, which may each be substituted by one or more radicals R 1 can be substituted.

[0052] If R M or R represents an aromatic or heteroaromatic ring system, this is preferably combined with non-aromatic radicals R 1substituted, where R = triazine, pyrimidine, quinazoline, quinoxaline or carbazole also aromatic or heteroaromatic radicals R 1 may be preferred on this heteroaryl group. This preference also applies analogously to the substituents on Ar.

[0053] Suitable aromatic or heteroaromatic ring systems R M, R and Ar 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 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, carbazole, which may be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which may be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, which may be linked via the 1-, 2-, 3- or 4-position may be linked, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, quinoxaline, benzimidazole, phenanthrene, triphenylene or a combination of two or three of these groups,which are each substituted with one or more radicals R, 1 can be substituted.

[0054] The aromatic or heteroaromatic groups R M or R is preferably selected from the groups of the following formulas R-1 to R-83,

[0055] R-34

[0056] R-45 R-46 R-50

[0057] R-51 R-52 R-53 R ' 54

[0058] R-57 R-58

[0059] R-67 R-68

[0060] where R 1 has the meanings given above, the dashed bond represents the bond of the group and furthermore:

[0061] Ar 1 is at each occurrence, identically or differently, a bivalent aromatic or heteroaromatic ring system having 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 at each occurrence C(R 1 )2, NR1 , O or S; or in the formulas R-40, R-41 and R-42, identical or different at each occurrence, are a single bond, C(R 1 )2, NR 1 , 0 or S; n is 0 or 1 , where n = 0 means that there is no group A at this position 1 and on the corresponding carbon atoms instead of residues R 1 are bonded; m is 0 or 1 ; with the proviso that m = 1 for the structures (R-12), (R-17), (R-21 ), (R-25), (R-26), (R-30), (R-34), (R-38) and (R-39) when these groups are bonded to a nitrogen atom.

[0062] If the above mentioned groups R-1 to R-83 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 NR 1 and the other group A 1 for C(R 1 )2 or in which both groups A 1 for NR 1or in which both groups A 1 are 0. In a particularly preferred embodiment of the invention, in groups R which contain several groups A 1 have at least one group A 1 for C(R 1 )2 or for NR 1 .

[0063] If A 1 for NR 1 the substituent R 1 which 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 2 In a particularly preferred embodiment, this substituent R 1identical or different on each occurrence for an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, which does not have any condensed aryl groups or heteroaryl groups in which two or more aromatic or heteroaromatic 6-ring groups are directly condensed to one another, and which in each case also by one or more radicals R 2 Particularly preferred are phenyl, biphenyl, terphenyl and quaterphenyl with linkage patterns as listed above for R-1 to R-11, where these structures are substituted by one or more radicals R 2 may be substituted, but are preferably unsubstituted. If A 1 for C(R 1 )2, the substituents R 1which 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 2 R is particularly preferably 1 represents a methyl group or a phenyl group. The radicals R 1 also form a ring system with each other, which leads to a spiro system.

[0064] In one embodiment of the invention, at least one radical R represents an electron-rich heteroaromatic ring system. The electron-rich heteroaromatic ring system is preferably selected from the groups R-13 to R-42 shown above, wherein in the groups R-13 to R-16, R-18 to R-20, R-22 to R-24, R-27 to R-29, R-31 to R-33 and R-35 to R-37 at least one group A 1 for NR 1 where R 1 preferably represents an aromatic or heteroaromatic ring system, in particular an aromatic ring system. Particularly preferred is the group R-15 with m = 0 and A 1 = NR 1 .

[0065] In a further embodiment of the invention, at least one R radical represents an electron-poor heteroaromatic ring system. The electron-poor heteroaromatic ring system is preferably selected from the groups R-47 to R-50, R-57, R-58, and R-76 to R-83 depicted above.

[0066] In a further preferred embodiment of the invention, R 1 identically or differently at each occurrence selected from the group consisting of H, D, F, CN, OR 2 , 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 and wherein one or more non-adjacent CH2 groups may be replaced by O, or an aromatic or heteroaromatic ring system having 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, 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 with 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, but is preferably unsubstituted.

[0067] In a further preferred embodiment of the invention, R 2 identical or different on each occurrence H, 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.

[0068] Other suitable groups R are groups of the formula -Ar 4 -N(Ar 2 )(Ar 3 ), where Ar 2 , Ar 3 and Ar 4 identically or differently on each occurrence represent an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which is substituted by one or more radicals R 1 The total number of aromatic ring atoms of Ar 2 , Ar 3 and Ar 4 maximum 40.

[0069] Ar 4 and Ar 2 with each other and / or Ar 2 and Ar 3 with each other also by a group selected from C(R 1 )2, NR 1 , O or S. Preferably, the linking of Ar 4 and Ar 2 with each other or from Ar 2 and Ar 3are ortho to the position of the linkage to the nitrogen atom. In a further embodiment of the invention, none of the groups Ar 2 , Ar 3 or Ar 4 connected with each other.

[0070] Ar is preferred 4 an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 12 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted. Particularly preferred is Ar 4 selected from the group consisting of ortho-, meta- or para-phenylene or ortho-, meta- or para-biphenyl, each of which is substituted by one or more radicals R 1 may be substituted, but are preferably unsubstituted. Ar is particularly preferred 4 an unsubstituted phenylene group. This applies in particular if Ar 4 with Ar 2 is connected by a single bond.

[0071] Preference is given to Ar 2 and Ar 3 identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 1 Particularly preferred groups Ar 2 or Ar 3 are, identically or differently at each occurrence, selected from the group consisting of benzene, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spiro-bifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene, 1-, 2-

[0072] 3- or 4-carbazole, 1-, 2-, 3- or 4-dibenzofuran, 1-, 2-, 3- or 4-di-benzothiophene, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2-,

[0073] 4- or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene, triphenylene or combinations of two, three or four of these groups, each of which is substituted by one or more radicals R 1 Particularly preferred are Ar 2 and Ar 3 identical or different on each occurrence, represents an aromatic ring system having 6 to 24 aromatic ring atoms, which is substituted by one or more radicals R 1 can be substituted, in particular selected from the groups consisting of benzene, 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, in particular 1-, 2-, 3- or 4-fluorene, or spirobifluorene, in particular 1-, 2-, 3- or 4-spirobifluorene.

[0074] The alkyl groups in compounds according to the invention that are processed by vacuum evaporation preferably have no more than five carbon atoms, more preferably no more than four carbon atoms, and most preferably no more than one carbon atom. Also suitable for compounds that are processed from solution are compounds that are substituted by alkyl groups, especially branched alkyl groups, with up to 10 carbon atoms, or that are substituted by oligoarylene groups, for example ortho-, meta-, para-, or branched terphenyl or quaterphenyl groups.

[0075] When the compounds containing a partial structure of formula (1) or compounds of formula (5) or (6) or the preferred embodiments are used as matrix material for a phosphorescent emitter or as matrix material in hyperphosphorescent OLEDs or in a layer directly adjacent to a phosphorescent layer, it is further preferred if the compound does not contain any condensed aryl or heteroaryl groups in which more than two six-membered rings are directly condensed to one another. In particular, it is preferred that the groups R M , R, Ar, R 1 and R 2 do not contain fused aryl or heteroaryl groups in which two or more six-membered rings are directly fused to one another. Exceptions to this are phenanthrene, triphenylene, quinazoline, and quinoxaline, which may be preferred due to their high triplet energy despite the presence of fused aromatic six-membered rings.

[0076] The above-mentioned preferred embodiments can be combined with each other as desired within the limitations defined in claim 1. In a particularly preferred embodiment of the invention, the above-mentioned advantages occur simultaneously.

[0077] Examples of suitable compounds according to the embodiments listed above are the compounds listed in the following table.

[0078] - k£-

[0079] The 8-metalla-diindolo[1,2,3-cd:3′,2′,1′-kl]perimidines (2) according to the invention can be prepared by reacting the 13,14-dihydrocarbazolo-[1,2-a]carbazole (1) with metal electrophiles of the type (R M )2MCl2 (M = Si, Ge, Sn, Ti, Zr, Hf; R M= alkyl, aryl, heteroaryl) in the presence of a base in a dipolar aprotic solvent (Scheme 1). Particularly suitable combinations of base and solvent are alkyl lithium compounds, such as n-BuLi in ethers such as diethyl ether, di-n-butyl ether or tetrahydrofuran (THF), or sodium hydride or potassium hydride in THF, dimethylacetamide (DMAc) or dimethyl sulfoxide (DMSO). Scheme 1: If metal electrophiles of the formula MCl4 are used in a stoichiometric ratio of 1:2 to (1), the corresponding 8-metalla-spirodiindolo[1,2,3-cd:3′,2′,1′-kl]perimidines (3) are obtained (Scheme 2). If two different 13,14-dihydrocarbazolo-[1,2-a]carbazoles (1) are used, the unsymmetrical 8-metalla-spiro-diindolo-[1,2,3-cd:3′,2′,1′-kl]perimidines (3) are obtained, whereby the synthesis can be carried out statistically or sequentially.Scheme 2: The 6-metalla-diimidazolo[1,2,3-cd:3′,2′,1′-kl]-perimidines (5) according to the invention can be prepared by reacting the 1,10-dihydrodicyclopenta-[a,h]naphthalenes (4) with metal electrophiles of the type (R. M )2MCl2 (R M: Alkyl, aryl, heteroaryl) in the presence of a base in a dipolar aprotic solvent (Scheme 3), whereby base-solvent combinations as above for the 8-metalla-diindolo[1,2,3-cd:3′,2′,1′-kl]perimidines (2) can be used. 6-Metalla-spirodiimidazolo[1,2,3-cd:3′,2′,1′-kl]perimidines can be prepared analogously to the process described in Scheme 2. The 1,10-dihydrodicyclopenta[a,h]-naphthalenes (4) can be prepared from the 2,9-dibromo-1,10-dinitronaphthalenes (3) analogously to K. Miyata et al., Angew. Chem. Int. Ed. 2011, 50, 4649. Scheme 3: The compounds (8) according to the invention containing an imidazole and an indole unit bound to M are accessible from the 1-nitro-2-halo-11H-benzo[a]carbazoles (6) analogously to the process described above (Scheme 4).

[0080] 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 preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, ^-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, Cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP,p-Cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butylmethyl ether, triethylene glycol butylmethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents.

[0081] The present invention therefore further provides a formulation comprising at least one compound according to the invention and at least one further compound. The further compound can be, for example, another matrix material and / or a phosphorescent emitter and / or a fluorescent emitter and / or an emitter exhibiting TADF (thermally activated delayed fluorescence), and / or a solvent.

[0082] A further object is the use of the compounds according to the invention in an electronic device, in particular in an organic electroluminescent device.

[0083] 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 can also contain inorganic materials or layers composed entirely of inorganic materials.

[0084] Yet another subject of the invention is an electronic device, in particular an organic electroluminescent device, comprising one or more compounds according to the invention.

[0085] 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 field quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic plasmon emitting devices, but preferably organic electroluminescent devices (OLEDs), particularly preferably phosphorescent OLEDs.

[0086] The organic electroluminescent device contains a cathode, an anode, and at least one emitting layer. In addition to these layers, it 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, and / or charge-generation layers. 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 is necessarily required. The organic electroluminescent device may contain one emitting layer or it may contain multiple emitting layers.If multiple emission 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. Particular preference is given to systems with three emitting layers, 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. The compound according to the invention can be used in different layers, depending on the precise structure.

[0087] In one embodiment of the invention, the compound according to the invention can be used in an emitting layer of an organic electroluminescent device as a matrix material for phosphorescent emitters or for emitters exhibiting TADF (thermally activated delayed fluorescence), in particular for phosphorescent emitters. The organic electroluminescent device can contain one emitting layer or it can contain several emitting layers, with at least one emitting layer containing at least one compound according to the invention as a matrix material. The compounds according to the invention are particularly suitable as a matrix material for green, yellow, orange, or red phosphorescent emitters.

[0088] In a further embodiment of the invention, the compound according to the invention can be used as a hole-transport material or as an electron-blocking material in a hole-transport or electron-blocking layer of an organic electroluminescent device. This applies in particular when both Ws together represent a group of formula (2) and when all Xs represent CR.

[0089] In a further embodiment of the invention, the compound according to the invention can be used as an electron-transport material in an electron-transport layer or a hole-blocking layer of an organic electroluminescent device. This applies in particular when at least one W represents N.

[0090] If the compound according to the invention is used as a matrix material for a phosphorescent compound in an emitting layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). Phosphorescence, within the meaning of this invention, is understood to mean luminescence from an excited state with higher spin multiplicity, i.e., a spin state > 1, in particular from an excited triplet state. For the purposes of this application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum, and copper complexes, are to be considered phosphorescent compounds.

[0091] The mixture of the compound according to the invention and the emitting compound contains between 99 and 1 vol.%, preferably between 98 and 10 vol.%, particularly preferably between 97 and 60 vol.%, in particular between 95 and 80 vol.% of the compound according to the invention, based on the total mixture of emitter and matrix material. Accordingly, the mixture contains between 1 and 99 vol.%, preferably between 2 and 90 vol.%, particularly preferably between 3 and 40 vol.%, in particular between 5 and 20 vol.% of the emitter, based on the total mixture of emitter and matrix material.

[0092] A further preferred embodiment of the present invention is the use of the compound according to the invention as a matrix material for a phosphorescent emitter in combination with another matrix material. Suitable matrix materials that can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g., according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627, or WO 2010 / 006680, triarylamines, carbazole derivatives, e.g., B. CBP (N,N-biscarbazolylbiphenyl) or those in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176, indolocarbazole derivatives, e.g. according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, e.g. according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776, azacarbazole derivatives, e.g. B. according to EP 1617710, EP 1617711 , EP 1731584, JP 2005 / 347160, bipolar matrix materials, e.g.according to WO 2007 / 137725, silanes, e.g. according to WO 2005 / 111172, azaboroles or boronate esters, e.g. 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, pyrimidine derivatives, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, diazasilole or tetraazasilole derivatives, e.g. B. according to WO 2010 / 054729, diazaphosphole derivatives, e.g. B. 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. B. according to WO 2012 / 048781, or dibenzofuran derivatives, e.g. B. 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. The compounds according to the invention are generally electron-rich or hole-transporting compounds. This applies in particular when both W together represent a group of the formula (2) or when all W represent CR. Preferred co-matrix materials are therefore selected from the group of electron-transporting compounds, which are preferably triazine, pyrimidine, quinazoline, and quinoxaline derivatives.

[0093] 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.

[0094] 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 formulas (eTMM1), (eTMM2), (eTMM3), (eTMM4) and / or (eTMM5),

[0095] Formula (eTMM1 ),

[0096] Formula (eTMM2), Formula (eTMM3),

[0097] Formula (eTMM4),

[0098] Formula (eTMM5), where the symbols and indices used are:

[0099] 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 7can be substituted;

[0100] 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;

[0101] Y is the same or different at each occurrence N or CR 7 , whereby it is excluded that two adjacent Ys simultaneously represent N;

[0102] V 2 is 0 or S; R 6 is, identically or differently at each occurrence, H, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; two radicals R 6 also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with each other;

[0103] 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;

[0104] 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, B(OR 8 )2, C(=O)R 8 , P(=O)(R 8 )2, S(=O)R 8 , S(=O)2R 8 , OSO2R 8, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 8 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted; two or more radicals R 7 form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;

[0105] R 8is 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.

[0106] 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).

[0107] Preferred compounds of the formula (eTMM1 ) are the compounds of the formulas (eTMMIa), (eTMMI b), (eTMMIc), (eTMMId) and (eTMMIe),

[0108] where the symbols and indices for these formulas have the following meaning:

[0109] W, W 1 mean, the same or different at each occurrence, 0, S, C(R W )2or N-Ar 5 ;

[0110] R wis, 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 w which bind to the same carbon atom also form a ring system with each other;

[0111] A is the same or different at each occurrence CR 7or 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 bonded; a3 is, identically or differently on each occurrence, 0, 1, 2, 3 or 4; b3 is, identically or differently on each occurrence, 0, 1, 2 or 3; Ring B is derived from an aryl group having 6 to 20 ring atoms, which may be substituted by one or more substituents R#; Ring C is or ; L3 is an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R 7 may be substituted; and where L 2 , X, Ar5, R 7 and R# have the meanings given above. Preferred compounds of formula (eTMM3) are the compounds of formula (8a), formula (eTMM3a) where the symbols and indices for this formula (eTMM3a) have the following meaning: W 1 is the same or different at each occurrence O, S, C(R W)2 or N-Ar 5 ; #X is CR or NAr 5 , preferably NAr 5 ; 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; Ring B is derived from an aryl group having 6 to 20 ring atoms, which may be substituted by one or more substituents R##; Ring C is or ; where L 2 , Ar 5and R# have the meanings given above. In compounds of formula (eTMM1a) W is preferably O or N-Ar 5 In compounds of the formula (eTMM1a), A is preferably the same or different at each occurrence CR 7 , where A stands for C, if at this position L 2 In compounds of the formulas (eTMM1d) or (eTMM3a) W 1 prefers O, C(R W )2 or N-Ar 5 , particularly preferably N-Ar 5 . In compounds of the formula (eTMM1e) L 3 preferably a heteroaromatic ring system with 9 to 30 ring atoms, which is substituted with one or more radicals R 7 may be substituted. In a preferred embodiment of the compounds of the formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (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, R 7identically or differently on each occurrence selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl group is in each case substituted with one or more radicals R 8 may be substituted, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, preferably with 5 to 40 ring atoms, each substituted by one or more radicals R 8 may be substituted. In a particularly preferred embodiment of the compounds of the formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), which can be combined according to the invention with the above-mentioned compounds according to the invention, as described above, R 7identically 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 8may be substituted. The preparation of the compounds of formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5) is generally known, and some of the compounds are commercially available. Suitable compounds of the formula (eTMM1) are known, for example, from the following publications: WO2007 / 077810A1, WO2008 / 056746A1, WO2010 / 136109A1, WO2011 / 057706A2, WO2011 / 160757A1, WO2012 / 023947A1, WO2012 / 048781A1, WO2013 / 077352A1, WO2013147205A1, WO2013 / 083216A1, WO2014 / 094963A1, WO2014 / 007564A1, WO2014 / 015931A1, WO2015 / 090504A2, WO2015 / 105251A1, WO2015 / 169412A1, WO2016 / 015810A1, WO2016 / 013875A1, WO2016 / 010402A1, WO2016 / 033167A1, WO2017 / 178311A1, WO2017 / 076485A1, WO2017 / 186760A1, WO2018 / 004096A1, WO2018 / 016742A1, WO2018 / 123783A1, WO2018 / 159964A1, WO2018 / 174678A1, WO2018 / 174679A1, WO2018 / 174681A1, WO2018 / 174682A1, WO2019 / 177407A1, WO2019 / 245164A1, WO2019 / 240473A1, WO2019 / 017730A1, WO2019 / 017731A1, WO2019 / 017734A1, WO2019 / 145316A1,WO2019 / 121458A1, WO2020 / 130381A1, WO2020 / 130509A1, WO2020 / 169241A1, WO2020 / 141949A1, WO2021 / 066623A1, WO2021 / 101220A1, WO2021 / 037401A1, WO2021 / 180614A1, WO2021 / 239772A1, WO2022 / 015084A1, WO2022 / 025714A1, WO2022 / 055169A1, EP3575296A1, EP3591728A1, US2014 / 0361254A1, US2014 / 0361268A1, KR20210036304A, KR20210036857A, KR2021147993A, JP2011 / 160367A2 and JP2017 / 107992A2. 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, WO2019 / 058200A1, WO2019 / 017730A1, WO2019 / 017731A1, WO2019 / 066282A1, WO2019 / 059577A1, WO2020 / 141949A1, WO2020 / 067657A1, WO2022063744A1, WO2022 / 090108A1, WO2022 / 207678A1, KR2019035308A, KR2021147993A, CN110437241A, US2016 / 072078A1. Suitable compounds of the formula (eTMM3) are known, for example, from the following publications: WO2017 / 160089A1, WO2019 / 017730A1, WO2019 / 017731A1,WO2020 / 032424A1. Suitable compounds of the formula (eTMM5) are known, for example, from the following publications: WO2015 / 093878A1, WO2016 / 033167A1, WO2017 / 183859A1, WO2017 / 188655A1, WO2018 / 159964A1. For combination with the compounds according to the invention, as described above or preferably described, particularly suitable compounds of the formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e) and / or (eTMM2) are as described above or preferably described, or corresponding compounds of the tables below that fall under these formulas. The compounds of the formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d) and / or (eTMM1e) are particularly preferred. Further examples of suitable host materials of the formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), which can be combined according to the invention with the above-listed compounds of the invention,As previously described, the following structures are shown in Tables 1 and 2 below. Table 1:,

[0112]

[0113]

[0114]

[0115] Particularly suitable compounds of the formulas (eTMM1), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e) and / or (eTMM2), which can be combined according to the invention with the above-mentioned 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 2. Table 2:

[0116] 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), (eTMM1a), (eTMM1b), (eTMM1c), (eTMM1d), (eTMM1e), (eTMM2), (eTMM3), (eTMM3a), (eTMM4) or (eTMM5), and their preferred embodiments described in Table 1 or the compounds E1 to E40 of Table 2.

[0117] 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.

[0118] In a preferred embodiment of the matrix material, this is a mixture of deuterated compounds according to the invention or of the formula (eTMM1), (eTMMI a), (eTMMI b), (eTMMI c), (eTMMI d), (eTMMI e), (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%. Corresponding deuteration methods are known to the person skilled in the art and are described, for example, in KR2016041014, WO2017 / 122988, KR202005282, KR101978651 and WO2018 / 110887 or in Bulletin of the Chemical Society of Japan, 2021 , 94(2), 600-605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071.

[0119] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for diatoms is to treat the compound to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound containing one or more diatoms and capable of releasing them under suitable conditions.

[0120] The platinum catalyst is preferably dry platinum on carbon, preferably 5% dry platinum on carbon. The palladium catalyst is preferably dry palladium on carbon, preferably 5% dry palladium on carbon. A suitable deuterium source is D2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4, or toluene-d8. A preferred deuterium source is D2O or a combination of D2O and a fully deuterated organic solvent. A particularly preferred deuterium source is the combination of D2O with a fully deuterated organic solvent, whereby the fully deuterated solvent is not limited here. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. A particularly preferred deuterium source is a combination of D2O and toluene-d8.The reaction is preferably carried out with heating, more preferably with heating to temperatures between 100 °C and 200 °C. Furthermore, the reaction is preferably carried out under pressure.

[0121] 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 wt.% to 90 wt.%, preferably in the range from 10 wt.% to 85 wt.%, more preferably in the range from 20 wt.% to 85 wt.%, even more preferably in the range from 30 wt.% to 80 wt.%, very particularly preferably in the range from 20 wt.% to 60 wt.% and most preferably in the range from 30 wt.% to 50 wt.%, based on the entire mixture or based on the entire composition of the light-emitting layer.

[0122] The concentration of the sum of all host materials of the formulas (eTMM1), (eTMMI a), (eTMMI b), (eTMMI c), (eTMMI d), (eTMMI e), (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 wt.% to 90 wt.%, preferably in the range from 10 wt.% to 85 wt.%, more preferably in the range from 20 wt.% to 85 wt.%, even more preferably in the range from 30 wt.% to 80 wt.%, very particularly preferably in the range from 20 wt.% to 60 wt.% and most preferably in the range from 30 wt.% to 50 wt.%, based on the entire mixture or based on the entire composition of the light-emitting layer.

[0123] The present invention also relates to a mixture which, in addition to the above-mentioned 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.

[0124] Particularly suitable phosphorescent compounds (= triplet emitters) are compounds that emit light upon suitable excitation, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are preferably used as phosphorescent emitters, in particular compounds containing iridium or platinum.

[0125] Examples of the emitters described above 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 2005 / 033244, WO 2005 / 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 and 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.

[0126] Examples of phosphorescent dopants are listed below.

[0127] 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, the skilled person can use all materials known for organic electroluminescent devices in combination with the compounds according to the invention without inventive step.

[0128] Particularly suitable for use in layers with hole-transporting function of any OLEDs, not only OLEDs according to the definitions of the present application, are the following compounds (HT-1) to (HT-20):

[0129] The term “layers with hole-transporting function” refers in particular to hole injection layers, hole transport layers, electron blocking layers and also emitting layers, in particular hole injection layers, hole transport layers and electron blocking layers.

[0130] Compounds (HT-1) to (HT-20) are generally suitable for use in hole-transporting layers. Their use is not limited to specific OLEDs, such as those described in the present application.

[0131] The compounds (HT-1) to (HT-20) can be prepared according to the procedures disclosed in the published patent applications listed in the table above. The further teaching concerning the use and preparation of the compounds, which is disclosed in the published patent applications listed in the table above, is hereby explicitly incorporated and is preferably to be combined with the above-mentioned teaching regarding the use of the above-mentioned compounds as hole-transporting materials. The compounds (HT-1) to (HT-20) exhibit excellent properties when used in OLEDs, in particular excellent lifetime and efficiency. Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using a sublimation process. In this process, the materials are heated in vacuum sublimation systems at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6mbar. However, it is also possible that the initial pressure is even lower, for example less than 10 -7 mbar. Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are sublimated at a pressure between 10 -5mbar and 1 bar. A special case of this process is the OVJP (Organic Vapour Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured. Also preferred is an organic electroluminescent device, characterized in that one or more layers are produced from solution, for example by spin coating, or using any printing process, such as screen printing, flexographic printing, offset printing, LITI (Light Induced Thermal Imaging, thermal transfer printing), inkjet printing or nozzle printing. This requires soluble compounds, which are obtained, for example, by suitable substitution. Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are vapor deposited.These processes are generally known to the person skilled in the art and can be applied by him without inventive step to electronic devices, in particular organic electroluminescent devices containing the compounds according to the invention according to formula (1).

[0132] The compounds according to the invention and the electronic devices according to the invention, in particular the organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art:

[0133] 1 . OLEDs containing the compounds according to the invention as matrix material for phosphorescent emitters lead to long lifetimes.

[0134] 2. OLEDs containing the compounds of the invention achieve high efficiencies. This is especially true when the compounds are used as matrix material for a phosphorescent emitter.

[0135] 3. OLEDs containing the compounds of the invention result in low operating voltages. This is especially true when the compounds are used as matrix material for a phosphorescent emitter.

[0136] The invention is further illustrated by the following examples, without intending to limit it. From these descriptions, one skilled in the art can implement the invention within the entire scope of the disclosure and manufacture further electronic devices according to the invention without inventive step.

[0137] Examples:

[0138] Unless otherwise stated, the following syntheses were carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be obtained, for example, from Sigma-ALDRICH or ABCR. The respective information in square brackets or the numbers given for individual compounds refer to the CAS numbers of the known compounds. For compounds that can exhibit multiple enantiomeric, diastereomeric, or tautomeric forms, one form is shown as a representative example.

[0139] A) Synthesis of synthons S:

[0140] Example S1:

[0141] A well-stirred solution of 38.4 g (100 mmol) of 6-bromo-13,14-dihydro-carbazolo[1,2-a]carbazole [2271382-95-5], 21.8 g (110 mmol) of biphenyl-2-boronic acid [914675-52-8], 42.4 g (200 mmol) of tripotassium phosphate [7778-53-2], 1.16 g (1 mmol) of tetrakis(triphenylphosphine)palladium(0) [14221-01-3], 300 ml of toluene, 100 ml of dioxane and 300 ml of water is heated under reflux for 16 h. After cooling, the organic phase is separated, washed three times with 300 ml of water each time, once with 300 ml of saturated brine, and dried over magnesium sulfate. The drying agent is removed by filtration, the filtrate is evaporated to dryness, and the residue is chromatographed (Torrent column chromatography system from A. Semrau). Yield: 34.5 g (75 mmol) 75%; Purity: approximately 98% pure. 1 H-NMR.

[0142] Analogously, the following compounds can be prepared by adjusting the stoichiometry of the reactants, whereby when chlorides are used instead of tetrakis(triphenylphosphine)palladium(0), 224 mg (1 mmol) of palladium acetate and 821 mg (2 mmol) of S-Phos [657408-07-6] are used.

[0143]

[0144] Example S100:

[0145] Procedure analogous to the synthesis of 3c in T. Taisei et al., Chem. Lett., 2019, 48, 1160. Preparation: 38.4 g (100 mmol) of 6-bromo-13,14-dihydrocarbazolo[1,2-a]carbazole [2271382-95-5] and 26.7 g (110 mmol) of 3-phenyl-9H-carbazole [103012-26-6]. The crude product was purified by chromatography. Yield: 17.0 g (31 mmol), 31%; Purity: approx. 98% pure. 1 H-NMR.

[0146] The following compounds can be prepared analogously by adjusting the stoichiometry of the reactants.

[0147]

[0148] B) Synthesis of the examples according to the invention:

[0149] Example B1:

[0150] A well-stirred suspension of 30.6 g (100 mmol) of 13,14-dihydrocarbazolo[1,2-a]carbazole [1444018-85-2] in 1000 ml of diethyl ether is treated with 80 ml (200 mmol) of 2.5 molar n-butyllithium in n-hexane while stirring at room temperature. After the addition is complete and the exothermic reaction has subsided, the mixture is stirred for 1 h, then a mixture of 8.5 g (50 mmol) of silicon tetrachloride [10026-04-7] and 100 ml of diethyl ether is added dropwise. After the addition is complete and the exothermic reaction has subsided, the mixture is stirred under reflux for 5 h, then the diethyl ether is removed in vacuo, the residue is taken up in approximately 300 ml of dichloromethane (DCM) and chromatographed on aluminum oxide, basic, activity level 1. Further purification of the crude product is carried out by chromatography and / or repeated hot extraction crystallization (usual organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv), as well as fractional sublimation orAnnealing in high vacuum. Yield:

[0151] 22.2 g (70 mmol), 70%; Purity: approx. 99.9% according to HPLC.

[0152] Analogously, the following compounds can be obtained by adjusting the stoichiometry of the reactants.

[0153]

[0154] Example: Production of OLEDs

[0155] The production of OLEDs according to the invention, as well as OLEDs according to the prior art, is carried out according to a general process according to WO 2004 / 058911, which is adapted to the conditions described here (layer thickness variation, materials used). The following examples present the results for various OLEDs. Cleaned glass plates (cleaned in a Miele laboratory dishwasher, Merck Extran cleaner) coated with structured ITO (indium tin oxide) with a thickness of 50 nm are pretreated with UV ozone for 25 minutes (UV ozone generator PR-100, UVP). These coated glass plates form the substrates onto which the OLEDs are applied. a) Blue Fluorescence OLED Components - BF

[0156] The compounds according to the invention can be used in the hole injection layer (HIL), hole transport layer (HTL), and / or electron blocking layer (EBL). All materials are thermally vapor-deposited in a vacuum chamber. The emission layer (EML) always consists of at least one matrix material (host material) SMB (see Table 1) and an emitting dopant (emitter) D, which is admixed to the matrix material(s) by co-evaporation in a specific volume fraction. A value such as SMB:D (97:3%) means that the SMB material is present in the layer in a volume fraction of 97% and the dopant D in a volume fraction of 3%. Analogously, the electron transport layer can also consist of a mixture of two materials (see Table 1). The materials used to produce the OLEDs are shown in Table 5.

[0157] OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, current efficiency (measured in cd / A), power efficiency (measured in λ / W), and external quantum efficiency (EQE, measured in percent) are determined as a function of luminance, calculated from current-voltage-luminance (IUL) curves assuming a Lambertian radiation pattern. The EQE (%) and voltage (V) are expressed at a luminance of 1000 cd / m². 2 .

[0158] The OLEDs have the following layer structure:

[0159] Substrate Hole injection layer (HIL) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm Hole transport layer (HTL), see Table 1 Electron blocking layer (EBL), see Table 1 Emission layer (EML), see Table 1 Electron transport layer (ETL), see Table 1 Electron injection layer (EIL) made of ETM2, 1 nm Cathode made of aluminum, 100 nm.

[0160] Table 1 : Structure of blue fluorescent OLED components

[0161] Table 2: Results of blue fluorescent OLED devices b) Phosphorescence OLED components

[0162] The compounds according to the invention can be used in the hole injection layer (HIL), the hole transport layer (HTL), the electron blocking layer (EBL), and / or in the emission layer (EML) as matrix material (host material) M (see Table 5). For this purpose, all materials are thermally vapor-deposited in a vacuum chamber. The emission layer always consists of at least one or more matrix materials M and a phosphorescent dopant Ir, which is admixed to the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as M1:M2:Ir (55%:35%:10%) means that the material M1 is present in the layer in a volume fraction of 55%, M2 in a volume fraction of 35%, and Ir in a volume fraction of 10%. Analogously, the electron transport layer can also consist of a mixture of two materials. The exact structure of the OLEDs can be found in Table 3.The materials used to manufacture the OLEDs are shown in Table 5.

[0163] OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, current efficiency (measured in cd / A), power efficiency (measured in λ / W), and external quantum efficiency (EQE, measured in percent) are determined as a function of luminance, calculated from current-voltage-luminance (IUL) curves assuming a Lambertian radiation pattern. The EQE (%) and voltage (V) are expressed at a luminance of 1000 cd / m². 2 .

[0164] The OLEDs have the following layer structure:

[0165] Substrat

[0166] Hole injection layer (HIL) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm hole transport layer (HTL), see Table 3 Electron blocking layer (EBL), see Table 3 Emission layer (EML), see Table 3 Hole blocking layer (HBL), see Table 3 Electron transport layer (ETL), made of ETMTETM2 (50%:50%), 30 nm Electron injection layer (EIL) made of ETM2, 1 nm Cathode made of aluminum, 100 nm.

[0167] Table 3: Structure of phosphorescent OLED components

[0168]

[0169] Table 4: Results of phosphorescent OLED devices

[0170]

[0171] Table 5: Structural formulas of the materials used

Claims

Patent claims 1 . A compound containing a partial structure according to formula (1 ), X II X Formula (1) where the symbols used are: M is Si, Ge, Sn, Ti, Zr or Hf; W is at each occurrence the same or different CR or N, where per cycle a maximum of one W stands for N; or the two W together form a group of the formula (2), Formula (2) where one of the two dashed bonds represents the bond to N and the other dashed bond represents the bond to Z; Z is, at each occurrence, the same or different, a single bond, BR, CR2, C=O, SiR2, GeR2, NR, P(=O)R, O, S or SO2; Y is, at each occurrence, the same or different, NR, O or S; or Y, together with the explicitly drawn carbon atom and the adjacent X, forms a group according to formula (3) or (4), Formula (3) Formula (4) where W, Z and X have the meanings given above, the dashed bond marked with * represents the bond to M and the two further dashed bonds represent the linkage of the structure within the formula (1); X is, at each occurrence, the same or different, CR or N, where a maximum of two X per cycle stand for N, or two adjacent X in formula (2) together stand for CR2, NR, O or S; R is the same or different at each occurrence: H, D, F, CI, Br, I, N(Ar)2, N(R 1 )2, OAr, SAr, CN, NO2, OR 1 , SR 1 , COOR 1 , C(=O)N(R 1 )2, Si(R 1 )3, B(OR 1 )2, C(=O)R 1 , P(=O)(R 1 )2, S(=O)R 1 , S(=O)2R 1 , OSO2R 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 substituted by Si(R 1 )2, C=O, NR 1 , O, S or CONR 1 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is substituted with one of the several radicals R 1 can be substituted; two radicals R can also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system with each other; Ar is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which with one or more radicals R 1 can be substituted; R 1 is the same or different at each occurrence H, D, F, CI, Br, I, N(R 2 )2, CN, NO2, OR 2 , SR 2 , Si(R 2 )3, B(OR 2 )2, C(=O)R 2 , P(=O)(R 2 )2, S(=O)R 2 , S(=O)2R 2 , OSO2R 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 with one or more radicals R 2 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 2 )2, C=O, NR 2 , O, S or CONR 2and wherein one or more H atoms in the alkyl, alkenyl or alkynyl group may be replaced by D, F, CI, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted; two or more radicals R 1 form an aliphatic, aromatic or heteroaromatic ring system; R 2 is, at each occurrence, identically or differently, H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may be replaced by F.

2. A compound according to claim 1, selected from the compounds of formula (5) or formula (6), Formula (5) Formula (6) where the symbols used have the meanings given in claim 1 and furthermore: R M is the same or different at each occurrence F, CN, OR 1 , OAr, N(R 1 )2, NAr2, Si(R 1 )3, 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 or alkoxy group is each substituted with one or more radicals R 1 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 1 )2, C=O, NR 1 , O, S or CONR 1 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is substituted with one of the several radicals R 1 can be substituted; two radicals R M also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system, where the linkage of the two radicals R Meither by a single bond or by a group selected from C(R 1 )2, O, S, NR 1 or BR; furthermore, one or more R M be linked to one or more R to form a ring system.

3. A compound according to claim 1 or 2, characterized in that Y, identical or different on each occurrence, represents NR or that Y together with the explicitly drawn carbon atom and the adjacent X forms a group according to formula (3).

4. A compound according to one or more of claims 1 to 3, characterized in that the partial structure of formula (1) is selected from the structures according to formulas (7) and (8), where the symbols used have the meanings given in claim 1 and Y in formula (8) stands for NR, O or S.

5. A compound according to one or more of claims 1 to 4, selected from the compounds of the formulae (9), (10), (11) and (12), where the symbols used have the meanings given in claim 1 and 2 and Y in formulae (10) and (12) stands for NR, O or S.

6. A compound according to one or more of claims 1 to 5, characterized in that Z, identical or different on each occurrence, stands for a single bond, CR2, BR or O.

7. A compound according to one or more of claims 1 to 6, characterized in that both groups W together represent a group of formula (2a), or that Z represents a single bond and in the same cycle, one of the two groups W represents CR and the other of the two groups W represents N.

8. A compound according to one or more of claims 1 to 7, characterized in that the partial structure of formula (1) is selected from the structures of formulas (7a), (7b), (8a) and (8b), wherein the symbols used have the meanings given in claim 1, Y in formulas (8a) and (8b) stands for NR, O or S and Z in formulas (7a) and (8a) preferably stands for a single bond.

9. A compound according to one or more of claims 1 to 8, selected from the compounds of formulas (9a), (9b), (10a), (10b), (11a), (11b), (12a) and (12b), Formula (9b) Formula (10b) Formula (11b) Formula (11a) Formula (12a) Formula (12b) wherein the symbols used have the meanings given in claims 1 and 2, Y in formulas (10a), (10b), (12a) and (12b) stands for NR, O or S and Z in formulas (9a), (10a), (11a) and (12a) preferably stands for a single bond.

10. A compound according to one or more of claims 1 to 9, selected from the compounds of formulas (9a-1), (10a-1), (11a-1) and (12a-1), Formula (9a-1) Formula (10a-1) Formula (11 a-1 ) Formula (12a-1) wherein the symbols have the meanings given in claims 1 and 2, Y in the formulas (10a-1 ) and (12a-1 ) stands for NR, O or S and Z preferably stands for a single bond.

11. A compound according to one or more of claims 1 to 10, characterized in that M stands for Si or Ge, preferably for Si.

12. A compound according to one or more of claims 1 to 11, characterized in that the compound has not more than four substituents R bonded to C atoms which are different from H or D.

13. A compound according to one or more of claims 1 to 12, characterized in that R M is selected, identically or differently at each occurrence, from the group consisting of a straight-chain alkyl group having 1 to 6 C atoms or a branched or cyclic alkyl group having 3 to 6 C atoms, where in the alkyl group one or more H atoms may be replaced by D, or an aromatic or heteroaromatic tic ring system with 6 to 13 aromatic ring atoms, which is substituted by one or more radicals R 1 can be substituted; the two radicals R M form a ring system; or the two groups R M together represent a group of formula (13), Formula (13) where the dashed bonds represent the bonds to M and R 1 has the meanings given in claim 1.

14. A formulation comprising at least one compound according to one or more of claims 1 to 13 and at least one further compound, wherein the further compound is a further matrix material and / or a phosphorescent emitter and / or a fluorescent emitter and / or an emitter exhibiting thermally activated delayed fluorescence and / or a solvent.

15. Use of a compound according to one or more of claims 1 to 13 in an electronic device.

16. An electronic device comprising one or more compounds according to one or more of claims 1 to 13.

17. Electronic device according to claim 16, which is an organic electroluminescent device, characterized in that the compound according to one or more of claims 1 to 13 is used in an emitting layer as a matrix material for phosphorescent emitters or for emitters which exhibit TADF (thermally activated delayed fluorescence), or as a hole transport material or as an electron blocking material in a hole transport or electron blocking layer or as an electron transport material in an electron transport layer or a hole blocking layer.

18. A mixture comprising at least one compound according to one or more of claims 1 to 13 and at least one compound according to formula (eTMM1), (eTMM2), (eTMM3), (eTMM4) or (eTMM5), Formula (eTMM1 ), Formula (eTMM2), Formula (eTMM4), where the symbols and indices used are: 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; 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; Y is the same or different at each occurrence N or CR 7 , whereby it is excluded that two adjacent Ys simultaneously mean N; V 2 is 0 or S; R 6is, identically or differently at each occurrence, H, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; two radicals R 6 also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with each other; Ar 5represents, 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; 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, B(OR 8 )2, C(=O)R 8 , P(=O)(R 8 )2, S(=O)R 8 , S(=O)2R 8 , OSO2R 8 , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted 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 8may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is replaced 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.

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