Materials for organic electroluminescent devices

Abstract

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

Description

[0001] The present invention relates to silicon compounds and derivatives of these compounds, as well as electronic devices, in particular organic electroluminescent devices, comprising these compounds.

[0002] The luminescent materials used in organic electroluminescent devices (OLEDs) are typically phosphorescent organometallic complexes. Generally speaking, OLEDs, especially those exhibiting triplet emission (phosphorescence), continue to require improvements, for example in terms of efficiency, operating voltage, and lifetime. The properties of phosphorescent OLEDs are not only determined by the triplet emitter used. More particularly, the other materials used, such as the matrix material or the charge transport material, are also particularly important. Therefore, improvements in these materials can also lead to improved OLED properties.

[0003] It was an object of the present invention to provide compounds which are suitable for use in OLEDs, in particular as matrix materials for phosphorescent emitters, as hole-transport materials or as electron-blocking materials, and which bring about good properties therein.

[0004] It has been found that, surprisingly, this object is achieved by specific compounds, described in detail below, which are very suitable for use in OLEDs. These OLEDs have, in particular, a long lifetime, high efficiency and a low operating voltage. The present invention therefore provides these compounds and electronic devices, in particular organic electroluminescent devices, containing them.

[0005] Therefore, the present invention provides a compound comprising the substructure of the following formula (1),

[0006]

[0007] The symbols used are as follows:

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

[0009] W is identical or different in each case and is CR or N, wherein not more than one W in each ring is N; or two W together form a group of the following formula (2),

[0010]

[0011] wherein one of the two dashed bonds represents a bond to N, and the other of the two dashed bonds represents a bond to Z;

[0012] Z is identical or different in each case and is a single bond, BR, CR2, C=O, SiR2, GeR2, NR, P(=O)R, O, S or SO2;

[0013] Y is identical or different in each case and is NR, O or S; or Y together with the explicitly indicated carbon atom and the adjacent X forms a radical of the following formula (3) or (4),

[0014]

[0015] wherein W, Z and X have the definitions given above, the dashed bond marked with * represents the bond to M, and the other two dashed bonds represent the connection of the structure within formula (1);

[0016] X is identical or different in each case and is CR or N, wherein not more than two X in each ring are N, or two adjacent X in formula (2) are taken together CR2, NR, O or S;

[0017] R is identical or different in each case and is 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 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by Si(R 1 )2、C=O、NR 1 , O, S, or CONR 1 or having 5 to 40 aromatic ring atoms and may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group; at the same time, the two R groups together can also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system;

[0018] Ar is identical or different in each case and is an aromatic ring having 5 to 40 atoms and may be replaced by one or more R 1 group-substituted aromatic or heteroaromatic ring systems;

[0019] R 1are identical or different in each case and are 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 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group can be replaced by one or more R 2 group, wherein one or more non-adjacent CH2 groups may be replaced by Si(R 2 )2、C=O、NR 2 , O, S, or CONR 2 and wherein one or more hydrogen atoms in the alkyl, alkenyl or alkynyl group may be replaced by D, F, Cl, Br, I or CN, or have 5 to 40 aromatic ring atoms and in each case by one or more R 2 An aromatic or heteroaromatic ring system substituted with a group; at the same time, two or more R 1 The groups together may also form an aliphatic, aromatic or heteroaromatic ring system;

[0020] R 2 are in each case identical or different and are H, D, F, CN, or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in particular a hydrocarbon radical, in which one or more hydrogen atoms may also be replaced by F.

[0021] In a preferred embodiment of the present invention, the compound containing the substructure of formula (1) is a compound of the following formula (5) or formula (6),

[0022]

[0023] The symbols used have the definitions given above, and:

[0024] R M are the same or different in each case and are F, CN, OR 1 ,OAr,N(R 1 )2,NAr2,Si(R 1)3, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl or alkoxy group may be replaced by one or more R 1 group and one or more non-adjacent CH2 groups may be replaced by Si(R 1 )2、C=O、NR 1 , O, S, or CONR 1 or having 5 to 40 aromatic ring atoms and may be replaced by one or more R 1 substituted aromatic or heteroaromatic ring system; at the same time, both R M The groups together may also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system, wherein the two R M The group may be connected by a single bond or by a 1 )2, O, S, NR 1 and BR groups; in addition, one or more R M It may be linked to one or more R to form a ring system.

[0025] In the context of the present invention, an aryl group contains 6 to 40 carbon atoms; in the context of the present invention, a heteroaryl group contains 2 to 40 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. Aryl or heteroaryl groups are understood here to mean simple aromatic rings, i.e. benzene, or simple heteroaromatic rings, such as pyridine, pyrimidine, thiophene, etc., or fused (annulated) aryl or heteroaryl groups, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatic compounds linked to one another by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

[0026] In the context of the present invention, aromatic ring system contains 6 to 60 carbon atoms in the ring system, preferably contains 6 to 40 carbon atoms. In the context of the present invention, heteroaromatic ring system contains 2 to 60 carbon atoms in the ring system, preferably 2 to 40 carbon atoms, and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. Heteroatoms are preferably selected from N, O and / or S. In the context of the present invention, aromatic or heteroaromatic ring system is understood to refer to following system, it is not necessarily only containing aryl or heteroaryl groups, but wherein two or more aryl or heteroaryl groups can also be connected by non-aromatic units, such as carbon, nitrogen or oxygen atoms. These are also understood to refer to systems in which two or more aryl or heteroaryl groups are directly connected to each other, such as biphenyl, terphenyl, bipyridine or phenylpyridine. For example, in the context of the present invention, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are also to be considered as aromatic ring systems, as are systems in which two or more aryl groups are linked, for example, via short alkyl groups. Preferred aromatic or heteroaromatic ring systems are simple aryl or heteroaryl groups and groups in which two or more aryl or heteroaryl groups are directly linked to one another, for example biphenyl or bipyridine, and fluorene or spirobifluorene.

[0027] In the context of the present invention, the term "alkyl group" encompasses straight-chain as well as branched and / or cyclic alkyl groups, wherein the cyclic alkyl groups may be monocyclic, bicyclic, tricyclic or oligocyclic. The same applies to alkenyl and alkynyl groups.

[0028] In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl radical or an alkenyl or alkynyl radical which may contain 1 to 40 carbon atoms and in which individual hydrogen atoms or CH2 groups may also be replaced by the above-mentioned radicals is preferably understood to mean a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl radical. An alkoxy radical having 1 to 40 carbon atoms OR 1 These are preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. Thioalkyl radicals SR having 1 to 40 carbon atoms1 In particular it is methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. In general, according to the present invention, the alkyl, alkenyl, alkynyl, alkoxy or thioalkyl groups may be linear, branched or cyclic, wherein one or more non-adjacent CH2 groups may be replaced by the above groups; in addition, one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, preferably by D, F or CN.

[0029] More particularly, a radical having 5 to 60 aromatic ring atoms and in each case also replaced by the above-mentioned R 1The aromatic or heteroaromatic ring system substituted by a radical refers to a radical derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, lettuce, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylidene, terphenyl, biphenylidene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, trimerized indene, isotrimerized indene, spirotrimerized indene, spiroisotrimerized indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzofuran, Thiophene, 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, phenanthimidazole, pyridinimidazole, pyrazinimidazole, quinoxalinoimidazole, oxadiazole, benzoxadiazole, naphthimidazole, anthraquinone, phenanthriazole, isoxadiazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine , hexaazaterphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinazoline, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorescent red ring, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1 ,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole radicals, or radicals derived from combinations of these systems.

[0030] In the context of the present invention, the expression "two or more radicals together can form a ring" is to be understood as meaning that, in particular, two radicals are linked to one another via a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0031] .

[0032] Similarly, when two substituents R, each an alkenyl group, are linked to each other by a chemical bond with the formal elimination of two hydrogen atoms, a fused aromatic ring can be formed.

[0033] Furthermore, the above wording should also be understood to mean that if one of the two groups is hydrogen, the second group is bound to the position where the hydrogen atom is bound, thereby forming a ring. This will be illustrated by the following scheme: .

[0034] The compounds of the invention may also be partially or fully deuterated.

[0035] In a preferred embodiment of the invention, Y is identical or different in each case and is NR, or Y together with the explicitly indicated carbon atom and the adjacent X forms a group of formula (3) as shown above. Most preferably, Y together with the explicitly indicated carbon atom and the adjacent X forms a group of formula (3) as shown above.

[0036] In a preferred embodiment of the present invention, no more than one X in each ring is N. Particularly preferred are compounds wherein all X in the two fused six-membered rings are CR, wherein when X together with the adjacent carbon atom and Y is a group of formula (3) or (4), X is C. More preferably, all X in the substructure of formula (1) or the compounds of formula (5) and formula (6) are CR, wherein when X together with the adjacent carbon atom and Y is a group of formula (3) or (4), X is C.

[0037] Therefore, preferred embodiments of the substructure of formula (1) are the structures of formula (7) and formula (8) below,

[0038]

[0039] The symbols used therein have the definitions given above, and Y in formula (8) is NR, O or S, wherein Y=NR is preferred.

[0040] Therefore, preferred embodiments of the compounds of formula (5) and formula (6) are the compounds of formula (9), formula (10), formula (11) and formula (12) below,

[0041]

[0042] The symbols used therein have the definitions given above, and Y in formula (10) and formula (12) is NR, O or S, wherein preferably Y=O or NR.

[0043] In another preferred embodiment of the present invention, Z is identical or different at each occurrence and is a single bond, CR2, BR or O, more preferably a single bond.

[0044] In another preferred embodiment of the present invention, the two W groups together are a group of the following formula (2a),

[0045] .

[0046] Another preferred embodiment is one in which Z is a single bond and one of the two W groups in the same ring is CR and the other W group is N.

[0047] Particularly preferred substructures of formula (1) or substructures of formula (7) and formula (8) are the following structures of formula (7a), formula (7b), formula (8a) and formula (8b),

[0048]

[0049] The symbols used therein have the definitions given above, and Y in formula (8a) and formula (8b) is preferably NR, O or S, with Y═O or NR being more preferred. Z in formula (7a) and formula (8a) is preferably a single bond.

[0050] Therefore, particularly preferred compounds are the compounds of the following formulas (9a), (9b), (10a), (10b), (11a), (11b), (12a), and (12b),

[0051] The symbols used herein have the definitions given above, and Y in formula (10a), formula (10b), formula (12a) and formula (12b) is preferably NR, O or S, with Y=O or NR being more preferred. Z in formula (9a), formula (10a), formula (11a) and formula (12a) is preferably a single bond.

[0052] Very particular preference is given to compounds of the formulae (9a-1), (10a-1), (11a-1) and (12a-1),

[0053]

[0054] The symbols used have the definitions given above, and Y in formula (10a-1) and formula (12a-1) is preferably NR, O or S, with Y═O or NR being more preferred. Z is preferably a single bond.

[0055] In another preferred embodiment of the present invention, M in the substructure of formula (1), the compounds of formula (5) and formula (6) and the preferred embodiments detailed above and below is Si or Ge, more preferably Si.

[0056] Preferably, the substructures of the formula (1) or the preferred embodiments of the formula detailed above and below have not more than four, preferably not more than two, substituents R other than H or D bonded to a carbon atom.

[0057] Preferably, the compounds of formula (5) and formula (6) or the preferred embodiments of these formulae detailed above and below have not more than four substituents R other than H or D bonded to a carbon atom. More preferably, the compounds have not more than two substituents R other than H or D bonded to a carbon atom.

[0058] Preferred substituents R in the compounds of the present invention are described below. M , R, R 1 and R 2 In a particularly preferred embodiment of the present invention, the following is for R M , R, R 1 and R 2 The preferences described are simultaneous and apply to the structure of formula (1), the compounds of formula (5) and formula (6), and all preferred embodiments detailed above.

[0059] In a preferred embodiment of the present invention, R M are the same or different in each case and are N(R 1 )2, NAr2, a linear alkyl group having 1 to 6 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms, one or more hydrogen atoms in each of which may also be replaced by D, or a group having 6 to 13 aromatic ring atoms and which may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group; at the same time, two R M The groups together may also form a ring system. Particularly preferred R M The group is selected from methyl, isopropyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, and may be substituted by one or more substituents R 1 The substituted phenyl group may be further substituted with one or more substituents R 1 Substituted o-biphenyl, m-biphenyl or p-biphenyl, wherein the aforementioned groups may also be partially or completely deuterated and wherein two of these groups may also form a ring with each other and with the M to which they are bonded. M When the groups together form a ring, the ring is preferably a metallocyclopentyl, metallocyclohexyl or metallofluorene, wherein "metal" means Si, Ge, Sn, Ti, Zr or Hf.

[0060] In another preferred embodiment of the present invention, the two R M The groups together are a group of the following formula (13),

[0061]

[0062] Where the dotted bond represents the bond to M and R 1 has the definitions given above, wherein the two R bonded to N 1Preferably, the two radicals R are identical or different in each case and are aromatic or heteroaromatic ring systems having 6 to 30 aromatic ring atoms and which may be substituted in each case by one or more R radicals. M Each is N(R 1 )2, a group is formed in which R 1 The group is an optionally substituted phenyl group, and R on the other N 1 The group is H, and these groups together form a ring system.

[0063] If Y is NR, the R group bonded to the nitrogen atom preferably has 5 to 40 aromatic ring atoms and may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, more preferably having 6 to 24 aromatic ring atoms and substituted with one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, most preferably having 6 to 13 aromatic ring atoms and substituted with one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals, particularly preferably phenyl, o-biphenyl, m-biphenyl or p-biphenyl, dibenzofuranyl or carbazolyl, each of which may be substituted with one or more R 1 When Y═NR, the preferred aromatic and heteroaromatic R groups bonded to the nitrogen atom correspond to the preferred aromatic and heteroaromatic R groups listed below.

[0064] In a preferred embodiment of the present invention, R is identical or different in each case and is selected from the group consisting of H, D, F, N(Ar) 2 , OAr, SAr, CN, OR 1 , a linear alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group can be replaced by one or more R 1 substituted with, but preferably unsubstituted with, groups, and wherein one or more non-adjacent CH2 groups may be replaced by O, or having 6 to 30 aromatic ring atoms and may be replaced by one or more R 1 At the same time, the two R groups together can also form an aliphatic, aromatic or heteroaromatic ring system. More preferably, R is in each case identical or different and is selected from H, N(Ar)2, a linear alkyl group having 1 to 6 carbon atoms, in particular a linear alkyl group having 1, 2, 3 or 4 carbon atoms, a linear alkenyl group having 2 to 4 carbon atoms, in particular 2 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl or alkenyl group can in each case be replaced by one or more R 1 substituted, but preferably unsubstituted, or having 6 to 24 aromatic ring atoms and may be replaced by one or more R 1Most preferably, R is identical or different in each case and is selected from H, D or a substituted aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms which may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0065] In another preferred embodiment of the present invention, Ar is identical or different and is an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, more preferably 6 to 24 aromatic ring atoms, most preferably 6 to 13 aromatic ring atoms, each of which may be replaced by one or more R 1 Group substitution.

[0066] When R M When R is an aromatic or heteroaromatic ring system, it is preferably replaced by a non-aromatic R 1 When R = triazine, pyrimidine, quinazoline, quinoxaline or carbazole, the aromatic or heteroaromatic R on the heteroaryl group 1 The same preference also applies to the substituents on Ar.

[0067] Suitable aromatic or heteroaromatic ring systems R M , R or Ar is selected from phenyl, biphenyl (especially o-biphenyl, m-biphenyl or p-biphenyl), terphenyl (especially o-terphenyl, m-terphenyl or p-terphenyl or branched terphenyl), quaterphenyl (especially o-quaterphenyl, m-quaterphenyl or p-quaterphenyl or branched quaterphenyl), fluorene which may be attached via the 1-, 2-, 3- or 4-position, spirobifluorene which may be attached via the 1-, 2-, 3- or 4-position, naphthalene which may be attached via the 1- or 2-position, Indole, benzofuran, benzothiophene, carbazole which may be attached via the 1, 2, 3 or 4 position, dibenzofuran which may be attached via the 1, 2, 3 or 4 position, dibenzothiophene which may be attached via the 1, 2, 3 or 4 position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, quinoxaline, benzimidazole, phenanthrene, terphenylidene, or a combination of two or three of these groups, each of which may be substituted by one or more R 1 Group substitution.

[0068] Aromatic or heteroaromatic R M The R group is preferably selected from the following groups of the formulae R-1 to R-83:

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091] where R 1 Having the definitions given above, the dotted bonds represent bonds of the groups in question, and in addition:

[0092] Ar 1 are identical or different in each case and are aromatic rings having 6 to 18 atoms and may be replaced by one or more R 1 a divalent aromatic or heteroaromatic ring system substituted with a group;

[0093] A 1 are identical or different in each case and are C(R 1 )2、NR 1, O or S; or in formula R-40, formula R-41 and formula R-42, are the same or different in each case and are a single bond, C(R 1 )2、NR 1 , O or S;

[0094] n is 0 or 1, where n=0 means there is no A 1 The group is bonded at this position, but R 1 The groups are bonded to the corresponding carbon atoms;

[0095] m is 0 or 1; provided that when these groups are bonded to a nitrogen atom, for structures (R-12), (R-17), (R-21), (R-25), (R-26), (R-30), (R-34), (R-38) and (R-39), m=1.

[0096] When the above R-1 to R-83 groups have two or more A 1 Groups, the possible options for these groups include A 1 The preferred embodiment in this case is one of A 1 The group is NR 1 And another A 1 The group is C(R 1 )2 or two Aces 1 The groups are all NR 1 or two A's 1 In a particularly preferred embodiment of the present invention, in the case of a group having two or more A 1 In the R group of the group, at least one A 1 The group is C(R 1 )2 or NR 1 .

[0097] When A 1 NR 1 When the substituent R bonded to the nitrogen atom 1 Preferably, the aromatic ring has 5 to 24 atoms and may be further replaced by one or more R 2 In a particularly preferred embodiment, the R 1 The substituents are identical or different in each case and are an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms, without any fused aryl or heteroaryl groups in which two or more aromatic or heteroaromatic 6-membered ring groups are fused directly to one another, and the aromatic or heteroaromatic ring system may in each case be further substituted by one or more R 2Particularly preferred are phenyl, biphenyl, terphenyl and quaterphenyl groups having the bonding modes listed above for R-1 to R-11, wherein these structures may be substituted by one or more R 2 The group is substituted, but is preferably unsubstituted.

[0098] When A 1 C(R 1 )2, the substituent R bonded to the carbon atom 1 are preferably identical or different in each case and are straight-chain alkyl radicals having 1 to 10 carbon atoms or branched or cyclic alkyl radicals having 3 to 10 carbon atoms or aromatic or heteroaromatic ring systems having 5 to 24 aromatic ring atoms, which may also be replaced by one or more R 2 Most preferably, R 1 is a methyl group or a phenyl group. In this case, R 1 The groups together may also form a ring system, thereby giving rise to a spiro ring system.

[0099] In one embodiment of the present invention, at least one R group is an electron-rich heteroaromatic ring system. The electron-rich heteroaromatic ring system is preferably selected from the above-mentioned R-13 to R-42 groups, wherein, among the 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 groups, at least one A 1 The group is NR 1 , where R 1 Preferred are aromatic or heteroaromatic ring systems, especially aromatic ring systems. Particularly preferred are R-15 groups where m=0 and A 1 =NR 1 .

[0100] In another embodiment of the present invention, at least one R group is an electron-deficient heteroaromatic ring system. The electron-deficient heteroaromatic ring system is preferably selected from the above-mentioned R-47 to R-50, R-57, R-58 and R-76 to R-83 groups.

[0101] In another preferred embodiment of the present invention, R 1 are identical or different in each case and are selected from H, D, F, CN, OR 2 , a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group may in each case be replaced by one or more R 2 and wherein one or more non-adjacent CH2 groups may be replaced by O, or having 6 to 30 aromatic ring atoms and in each case by one or more R 2An aromatic or heteroaromatic ring system substituted with a group; at the same time, two or more R 1 The groups together can form an aliphatic ring system. In a particularly preferred embodiment of the present invention, R 1 are in each case identical or different and are selected from H, a straight-chain alkyl group having 1 to 6 carbon atoms, in particular having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl group may be replaced by one or more R 2 substituted, but preferably unsubstituted, or having 6 to 24 aromatic ring atoms and in each case substituted by one or more R 2 The aromatic or heteroaromatic ring system is substituted with or preferably is unsubstituted.

[0102] In another preferred embodiment of the present invention, R 2 are identical or different in each case and are H, F, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be substituted by an alkyl group having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0103] A more suitable R group is of the formula -Ar 4 -N(Ar 2 )(Ar 3 ) group, wherein Ar 2 、Ar 3 and Ar 4 are identical or different in each case and have 5 to 24 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group. 2 、Ar 3 and Ar 4 The total number of aromatic ring atoms does not exceed 40.

[0104] In this case, by selecting C(R 1 )2、NR 1 , O or S group, Ar 4 and Ar 2 They may also be bonded to each other and / or Ar 2 and Ar 3 Preferably, Ar is bonded to the nitrogen atom at the corresponding ortho position. 4 and Ar 2 connected to each other and Ar 2 and Ar 3 In another embodiment of the present invention, Ar 2 、Ar 3 and Ar 4 The groups are not bonded to each other.

[0105] Preferably, Ar 4 is a cyclic aromatic ring having 6 to 24 aromatic ring atoms, in particular having 6 to 12 aromatic ring atoms and which can in each case be replaced by one or more R 1 More preferably, Ar 4 Selected from o-phenylene, m-phenylene or p-phenylene or o-biphenylene, m-biphenylene or p-biphenylene, each of which may be replaced by one or more R 1 Groups are substituted, but preferably are unsubstituted. Most preferably, Ar 4 is an unsubstituted phenylene group. 4 Through a single bond with Ar 2 This is especially true when bonding.

[0106] Preferably, Ar 2 and Ar 3 are identical or different in each case and are aromatic rings having 6 to 24 atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with groups. Particularly preferred are Ar 2 and Ar 3 The radicals are in each case identical or different and are selected from benzene, o-, m- or p-biphenyl, o-, m- or p-terphenyl or branched terphenyl, o-, m- or p-terphenyl or branched terphenyl, o-, m- or p-terphenyl or branched terphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene, 1-carbazole, 2-carbazole, oxazole, 3-carbazole or 4-carbazole, 1-dibenzofuran, 2-dibenzofuran, 3-dibenzofuran or 4-dibenzofuran, 1-dibenzothiophene, 2-dibenzothiophene, 3-dibenzothiophene or 4-dibenzothiophene, indenocarbazole, indolocarbazole, 2-pyridine, 3-pyridine or 4-pyridine, 2-pyrimidine, 4-pyrimidine or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene, terphenylidene, or a combination of two, three or four of these groups, each of which may be replaced by one or more R 1 More preferably, Ar 2 and Ar 3 are identical or different in each case and are aromatic rings having 6 to 24 atoms and may be replaced by one or more R 1The radically substituted aromatic ring system is especially selected from benzene, biphenyl (especially o-, m- or p-biphenyl), terphenyl (especially o-, m- or p-terphenyl or a branched terphenyl), quaterphenyl (especially o-, m- or p-quaterphenyl or a branched quaterphenyl), fluorene (especially 1-, 2-, 3- or 4-fluorene) or spirobifluorene (especially 1-, 2-, 3- or 4-spirobifluorene).

[0107] At the same time, the alkyl groups in the compounds of the present invention 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. For compounds processed from solution, suitable compounds are also compounds substituted with alkyl groups having up to 10 carbon atoms, especially branched alkyl groups, or with oligomeric arylene groups, such as o-, m- or p-terphenyl or branched terphenyl or quaterphenyl groups.

[0108] When the compound containing the substructure of formula (1) or the compound of formula (5) or formula (6) or the preferred embodiments is used as a matrix material for a phosphorescent emitter or as a matrix material in a superphosphorescent OLED or in a layer directly adjacent to a phosphorescent layer, it is more preferred that the compound does not contain any fused aryl or heteroaryl groups in which more than two six-membered rings are directly fused to each other. Particularly preferred is R M , R, Ar, R 1 and R 2 The radical does not contain any fused aromatic or heteroaryl groups in which two or more six-membered rings are directly fused to each other. Exceptions to this are formed by phenanthrene, terphenylidene, quinazoline, and quinoxaline, which may be preferred despite the presence of fused aromatic six-membered rings due to their high triplet energy.

[0109] The above-mentioned preferred embodiments can be combined with one another as desired within the limits defined in claim 1. In a particularly preferred embodiment of the present invention, the above-mentioned preferences exist simultaneously.

[0110] Examples of suitable compounds according to the embodiments detailed above are the compounds detailed in the table below.

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127] The 8-metal diindolo[1,2,3-cd:3',2',1'-kl]perylene (2) of the present invention can be prepared by reacting 13,14-dihydrocarbazo-[1,2-a]carbazole (1) with (R M )2MCl2 type metal electrophilic reagent (M = Si, Ge, Sn, Ti, Zr, Hf; R M =alkyl, aryl, heteroaryl) in a bipolar aprotic solvent in the presence of a base (Scheme 1). Particularly suitable base and solvent combinations 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).

[0128] Option 1:

[0129]

[0130] If the metal electrophile of formula MC14 is used in a stoichiometric ratio of 1:2 relative to (1), the corresponding 8-metal spirodiindolo[1,2,3-cd:3',2',1'-kl]perylene meta-diazine (3) is obtained (Scheme 2). If two different 13,14-dihydrocarbazolo-[1,2-a]carbazoles (1) are used, among the compounds obtained are asymmetric 8-metal spirodiindolo[1,2,3-cd:3',2',1'-kl]perylene meta-diazine (3), wherein the synthesis can be statistical or sequential.

[0131] Option 2:

[0132]

[0133] The 6-metal diimidazo[1,2,3-cd:3',2',1'-kl]perylene meta-diazine (5) of the present invention can be prepared by reacting 1,10-dihydrodicyclopenta[a,h]naphthalene (4) with (R M )2MCl2 type (R M alkyl, aryl, heteroaryl) metal electrophiles are prepared by reacting in a bipolar aprotic solvent in the presence of a base (Scheme 3), wherein the base-solvent combination used above for 8-metal diindolo[1,2,3-cd:3',2',1'-kl]perylene (2) can be used. 6-metal spirobiimidazo[1,2,3-cd:3',2',1'-kl]perylene can be prepared similarly to the method described in Scheme 2. 1,10-dihydrodicyclopenta[a,h]naphthalene (4) can be prepared from 2,9-dibromo-1,10-dinitronaphthalene (3) in a similar manner to K. Miyata et al., Angew. Chem. Int. Ed. 2011, 50, 4649.

[0134] Option 3:

[0135]

[0136] Compounds according to the invention (8) containing an imidazole unit and an indole unit bonded to M can be obtained analogously to the above-described method (Scheme 4) from 1-nitro-2-halogen-11H-benzo[a]carbazole (6).

[0137] Option 4:

[0138]

[0139] In order to process the compound of the present invention from the liquid phase, for example, by spin coating or by printing methods, a preparation of the compounds of the present invention is needed. These preparations can be, for example, solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents can preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene (especially 3-phenoxytoluene), (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, Cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, diphenyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate, or a mixture of these solvents.

[0140] Therefore, the present invention also provides a formulation comprising at least one compound of the present invention and at least one further compound. The further compound may, for example, be a further 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.

[0141] A further aspect of the subject matter is the use of the compounds according to the invention in electronic devices, in particular in organic electroluminescent devices.

[0142] In the context of the present invention, an electronic device is a device comprising at least one layer comprising at least one organic compound. The component may also comprise inorganic materials or layers formed entirely of inorganic materials.

[0143] The present invention also provides an electronic device, especially an organic electroluminescent device, comprising one or more compounds according to the present invention.

[0144] The electronic device is preferably selected from the group consisting of an organic electroluminescent device (OLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic light emitting transistor (O-LET), an organic solar cell (O-SC), a dye-sensitized organic solar cell (DSSC), an organic optical detector, an organic photoreceptor, an organic field quenching device (O-FQD), a light emitting electrochemical cell (LEC), an organic laser diode (O-laser) and an organic plasma light emitting device, but is preferably an organic electroluminescent device (OLED), more preferably a phosphorescent OLED.

[0145] The organic electroluminescent device comprises a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also comprise other layers, for example, in each case 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. Similarly, an interlayer, for example, having an exciton-blocking function, may be introduced between the two light-emitting layers. However, it should be noted that not every one of these layers necessarily needs to be present. In this case, the organic electroluminescent device may contain a single light-emitting layer, or it may contain multiple light-emitting layers. If multiple light-emitting layers are present, these light-emitting layers generally preferably have multiple emission maxima between 380 nm and 750 nm, so that the overall result is white emission; in other words, a variety of fluorescent or phosphorescent light-emitting compounds are used in the light-emitting layers. Particularly preferred are systems having three light-emitting layers, wherein the three layers exhibit blue, green, and orange or red emission. The organic electroluminescent device of the present invention may also be a tandem OLED, particularly for white-emitting OLEDs. Depending on the exact structure, the compounds of the present invention may be used in different layers.

[0146] In one embodiment of the present invention, the compounds of the present invention can be used as a host material for a phosphorescent emitter or an emitter exhibiting TADF (thermally activated delayed fluorescence), in particular a host material for a phosphorescent emitter, in the emitting layer of an organic electroluminescent device. The organic electroluminescent device may contain one emitting layer, or it may contain a plurality of emitting layers, at least one of which contains at least one compound of the present invention as a host material. The compounds of the present invention are particularly suitable as host materials for green, yellow, orange or red phosphorescent emitters.

[0147] In another embodiment of the present invention, the compounds of the present invention can be used as hole transport materials or electron blocking materials in a hole transport layer or electron blocking layer of an organic electroluminescent device. This is especially true when both W together are a group of formula (2) and when all X are CR.

[0148] In another embodiment of the present invention, the compounds of the present invention can be used as electron transport materials in an electron transport layer or a hole blocking layer of an organic electroluminescent device, in particular when at least one W is N.

[0149] When the compounds according to the invention are used as matrix materials for phosphorescent compounds in an emitting layer, they are preferably used in combination with one or more phosphorescent materials (triplet emitters). In the context of the present invention, phosphorescence is understood to mean luminescence from excited states with a higher spin multiplicity, i.e., spin states > 1, in particular luminescence from excited triplet states. In the context of this application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum and copper complexes, are to be regarded as phosphorescent compounds.

[0150] The mixture of the compound according to the invention and the emitting compound contains from 99% to 1% by volume, preferably from 98% to 10% by volume, more preferably from 97% to 60% by volume, and in particular from 95% to 80% by volume of the compound according to the invention, based on the total mixture of emitter and matrix material. Correspondingly, the mixture contains from 1% to 99% by volume, preferably from 2% to 90% by volume, more preferably from 3% to 40% by volume, and in particular from 5% to 20% by volume of the emitter, based on the total mixture of emitter and matrix material.

[0151] Another preferred embodiment of the present invention is the use of the compounds according to the invention as matrix materials for phosphorescent emitters in combination with further matrix materials. Suitable matrix materials which can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680; triarylamines; carbazole derivatives, for example CBP (N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176; indolocarbazole derivatives, for example according to WO 2007 / 063754 or WO 2008 / 056746; indenocarbazole derivatives, for example according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776; azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP2005 / 347160; bipolar matrix materials, for example according to WO 2007 / 137725; silanes, for example according to WO 2005 / 111172; borazolidines or boric acid esters, for example according to WO 2006 / 117052; triazine derivatives, for example 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, for example according to EP 652273 or WO 2009 / 062578; siladiazacyclopentaine or silatetraazacyclopentaine derivatives, for example according to WO 2010 / 054729; phosphadiazacyclopentaine derivatives, for example according to WO 2010 / 054730; bridged carbazole derivatives, for example according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080; terphenylidene derivatives, for example according to WO 2012 / 048781; or dibenzofuran derivatives, for example according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565.Likewise, further phosphorescent emitters having a shorter emission wavelength than the actual emitter may be present in the mixture as cohosts, or compounds which do not participate to a significant extent in charge transport, as described, for example, in WO 2010 / 108579.

[0152] The compounds of the present invention are generally electron-rich compounds or hole-transporting compounds. This is particularly true when both W together are a group of formula (2) or when all W are CR. Therefore, preferred co-host materials are selected from electron-transporting compounds, preferably triazine derivatives, pyrimidine derivatives, quinazoline derivatives and quinoxaline derivatives.

[0153] Particularly suitable matrix materials that can be advantageously combined with the compounds of the present invention in mixed matrix systems can be selected from compounds of formula (eTMM1), formula (eTMM2), formula (eTMM3), formula (eTMM4) or formula (eTMM5), as described below.

[0154] Therefore, the present invention also provides a mixture comprising at least one compound of the present invention and at least one compound of formula (eTMM1), formula (eTMM2), formula (eTMM3), formula (eTMM4) and / or formula (eTMM5),

[0155] Formula (eTMM1),

[0156] Formula (eTMM2),

[0157] Formula (eTMM3),

[0158] Formula (eTMM4),

[0159] Formula (eTMM5),

[0160] The symbols and notations used are as follows:

[0161] L 2 are identical or different in each case and are a single bond or have 5 to 24 ring atoms and may be replaced by one or more R 7 group-substituted aromatic or heteroaromatic ring systems;

[0162] R# is identical or different in each case and is D, F, CN or has 6 to 24 ring atoms and may be replaced by one or more R 6 group-substituted aromatic ring systems;

[0163] Y is the same or different in each instance and is N or CR 7, which excludes the possibility that two adjacent Ys are both N;

[0164] V 2 O or S;

[0165] R 6 are identical or different in each case and are H, D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may be replaced by one or more R 7 group and one or more non-adjacent CH2 groups may be replaced by Si(R 7 )2、C=O、NR 7 , O, S, or CONR 7 or having 5 to 60 ring atoms and in each case being replaced by one or more R 7 Aromatic or heteroaromatic ring system substituted with a group; wherein the two R 6 The groups may also be taken together to form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;

[0166] Ar 5 are identical or different in each case and have 5 to 40 ring atoms and may be replaced by one or more R 7 group-substituted aromatic or heteroaromatic ring systems;

[0167] R 7 are identical or different in each case and are H, D, F, Cl, Br, I, N(R 8 )2,CN,NO2,OR 8 , SR 8 ,Si(R 8 )3,B(OR 8 )2,C(=O)R 8 ,P(=O)(R 8 )2,S(=O)R 8 , S(=O)2R 8 , OSO2R 8 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 8 group and one or more non-adjacent CH2 groups may be replaced by Si(R 8 )2、C=O、NR 8 , O, S, or CONR 8 or having 5 to 40 ring atoms and in each case being replaced by one or more R8 An aromatic or heteroaromatic ring system substituted with a group; at the same time, two or more R 7 The groups together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;

[0168] R 8 are in each case identical or different and are H, D, F, or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in particular a hydrocarbon radical, in which one or more hydrogen atoms may also be replaced by F;

[0169] b1 is 0, 1, 2, 3, or 4;

[0170] b2 is 0, 1, 2, or 3.

[0171] The present invention also provides an organic electronic device, in particular an organic electroluminescent device, comprising an anode, a cathode and at least one organic layer, wherein the at least one organic layer comprises at least one light-emitting layer, wherein the at least one light-emitting layer comprises the above-mentioned mixture of at least one compound of the present invention and at least one compound of formula (eTMM1), formula (eTMM2), formula (eTMM3), formula (eTMM4) and / or formula (eTMM5).

[0172] Preferred compounds of formula (eTMM1) are compounds of formula (eTMM1a), formula (eTMM1b), formula (eTMM1c), formula (eTMM1d) and formula (eTMM1e),

[0173] Formula (eTMM1a)

[0174] Formula (eTMM1b)

[0175] Formula (eTMM1c)

[0176] Formula (eTMM1d)

[0177] Formula (eTMM1e),

[0178] The symbols and notations used in these formulas are defined as follows:

[0179] W, W 1 are the same or different in each case and are O, S, C(R W )2 or N-Ar 5 ;

[0180] R Ware identical or different in each case and are a linear alkyl radical having 1 to 20 carbon atoms or a branched or cyclic alkyl radical having 3 to 20 carbon atoms, in which one or more hydrogen atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may be replaced by one or more substituents selected from D, F, CN, a linear alkyl radical having 1 to 20 carbon atoms or a branched or cyclic alkyl radical having 3 to 20 carbon atoms, in which one or more hydrogen atoms in the alkyl radical of the aromatic or heteroaromatic ring system may be replaced by D, F or CN; at the same time, two R W The groups may also form together a ring system;

[0181] A is the same or different in each case and is CR 7 or N, wherein no more than two A groups in each ring are N and wherein when L 2 When bonded to this position, A is C;

[0182] a3 is the same or different in each case and is 0, 1, 2, 3 or 4;

[0183] b3 is the same or different in each case and is 0, 1, 2 or 3;

[0184] Ring B derived from an aryl group having 6 to 20 ring atoms and which may be substituted by one or more substituents R#;

[0185] Ring C yes or ;

[0186] L3 is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be replaced by one or more R 7 group substitution; and

[0187] Among them L 2 、X、Ar5、R 7 and R# have the definitions given above.

[0188] A preferred compound of formula (eTMM3) is a compound of formula (8a),

[0189] Formula (eTMM3a)

[0190] The symbols and notations used in the formula (eTMM3a) are defined as follows:

[0191] W 1 are the same or different in each case and are O, S, C(R W)2 or N-Ar 5 ;

[0192] #X is CR or NAr 5 , preferably NAr 5 ;

[0193] R W are identical or different in each case and are a linear alkyl radical having 1 to 20 carbon atoms or a branched or cyclic alkyl radical having 3 to 20 carbon atoms, in which one or more hydrogen atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may be substituted by one or more substituents selected from the group consisting of D, F, CN, a linear alkyl radical having 1 to 20 carbon atoms or a branched or cyclic alkyl radical having 3 to 20 carbon atoms, in which one or more hydrogen atoms in the alkyl radical of the aromatic or heteroaromatic ring system may be replaced by D, F or CN;

[0194] a3 is the same or different in each case and is 0, 1, 2, 3 or 4;

[0195] Ring B derived from an aryl group having 6 to 20 ring atoms which may be substituted by one or more substituents R##;

[0196] Ring C yes or ;

[0197] Among them L 2 、Ar 5 and R# have the definitions given above.

[0198] In the compound of formula (eTMM1a), W is preferably O or N-Ar 5 .

[0199] In the compounds of formula (eTMM1a), A is preferably identical or different in each case and is CR 7 , where L 2 When bonded to this position, A is C.

[0200] In the compound of formula (eTMM1d) or formula (eTMM3a), W 1 Preferably O, C(R W )2 or N-Ar 5 , more preferably N-Ar 5 .

[0201] In the compound of formula (eTMM1e), L 3 Preferably, it has 9 to 30 ring atoms and may be replaced by one or more R 7Group-substituted heteroaromatic ring systems.

[0202] In a preferred embodiment of the compounds of formula (eTMM1), formula (eTMM1a), formula (eTMM1b), formula (eTMM1c), formula (eTMM1d), formula (eTMM1e), formula (eTMM2), formula (eTMM3), formula (eTMM3a), formula (eTMM4) and formula (eTMM5) according to the present invention, which can be combined with the compounds of the present invention described in detail above, R 7 are identical or different in each case and are selected from H, D, F, CN, straight-chain alkyl radicals having 1 to 20 carbon atoms or branched or cyclic alkyl radicals having 3 to 20 carbon atoms, wherein the alkyl radicals may be replaced by one or more R 8 or having 5 to 60 ring atoms, preferably 5 to 40 ring atoms and in each case being substituted by one or more R 8 Aromatic or heteroaromatic ring systems substituted with radicals.

[0203] In a particularly preferred embodiment of the compounds of formula (eTMM1), formula (eTMM1a), formula (eTMM1b), formula (eTMM1c), formula (eTMM1d), formula (eTMM1e), formula (eTMM2), formula (eTMM3), formula (eTMM3a), formula (eTMM4) and formula (eTMM5) as described above, which can be combined with the compounds of the present invention as described in detail above, R 7 are identical or different in each case and are selected from H, D or a ring having 6 to 30 ring atoms and which may be replaced by one or more R 8 Aromatic or heteroaromatic ring systems substituted with radicals.

[0204] The preparation of compounds of Formula (eTMM1), Formula (eTMM1a), Formula (eTMM1b), Formula (eTMM1c), Formula (eTMM1d), Formula (eTMM1e), Formula (eTMM2), Formula (eTMM3), Formula (eTMM3a), Formula (eTMM4) and Formula (eTMM5) is generally known, and some compounds are commercially available.

[0205] 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 / W O2017 / 076485A1, WO2017 / 186760A1, WO2018 / 004096A1, WO2018 / 016742A1, WO2018 / 123783A1, WO2018 / 159964A1, WO2018 / 174678A1, WO2018 / 17467 9A1, WO2018 / 174681A1, WO2018 / 174682A1, WO2019 / 177407A1, WO2019 / 245164A1, WO2019 / 240473A1, WO2019 / 017730A1, WO2019 / 017731A1, WO2019 W O2021 / 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.

[0206] Suitable compounds of 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 / 01773 0A1, WO2019 / 017731A1, WO2019 / 066282A1, WO2019 / 059577A1, WO2020 / 141949A1, WO2020 / 067657A1, WO20220637 44A1, WO2022 / 090108A1, WO2022 / 207678A1, KR2019035308A, KR2021147993A, CN110437241A, US2016 / 072078A1.

[0207] Suitable compounds of the formula (eTMM3) are known, for example, from the following publications: WO 2017 / 160089 A1, WO 2019 / 017730 A1, WO 2019 / 017731 A1, WO 2020 / 032424 A1.

[0208] Suitable compounds of the formula (eTMM5) are known, for example, from the following publications: WO 2015 / 093878 A1, WO 2016 / 033167 A1, WO 2017 / 183859 A1, WO 2017 / 188655 A1, WO 2018 / 159964 A1.

[0209] Suitable compounds for combination with the compounds of the present invention as described above or as preferred are in particular compounds of formula (eTMM1), formula (eTMM1a), formula (eTMM1b), formula (eTMM1c), formula (eTMM1d), formula (eTMM1e) and / or formula (eTMM2) as described above or as preferred, or the corresponding compounds encompassed by these formulae in the following table. Compounds of formula (eTMM1), formula (eTMM1a), formula (eTMM1b), formula (eTMM1c), formula (eTMM1d) and / or formula (eTMM1e) are particularly preferred.

[0210] Other examples of suitable host materials of formula (eTMM1), formula (eTMM1a), formula (eTMM1b), formula (eTMM1c), formula (eTMM1d), formula (eTMM1e), formula (eTMM2), formula (eTMM3), formula (eTMM3a), formula (eTMM4) and formula (eTMM5) that can be combined with the compounds of the present invention described in detail above according to the present invention are the structures shown below in Tables 1 and 2 below.

[0211] Table 1:

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241] Particularly suitable compounds of formula (eTMM1), formula (eTMM1a), formula (eTMM1b), formula (eTMM1c), formula (eTMM1d), formula (eTMM1e) and / or formula (eTMM2) as described above, which according to the invention can be combined with the compounds according to the invention described in detail above and used in the electroluminescent device or mixture according to the invention, are compounds E1 to E40 in Table 2.

[0242] Table 2:

[0243]

[0244]

[0245]

[0246]

[0247]

[0248] The above-mentioned host materials of the present invention and their preferred embodiments described above can be combined in any desired manner in the devices of the present invention with the above-mentioned matrix materials / host materials, matrix materials / host materials of formula (eTMM1), formula (eTMM1a), formula (eTMM1b), formula (eTMM1c), formula (eTMM1d), formula (eTMM1e), formula (eTMM2), formula (eTMM3), formula (eTMM3a), formula (eTMM4) or formula (eTMM5) from Table 1 and their preferred embodiments described above or compounds E1 to E40 from Table 2.

[0249] If the matrix material is a deuterated compound, the matrix material may be a mixture of deuterated compounds having the same basic chemical structure and differing only in the level of deuteration.

[0250] In a preferred embodiment of the matrix material, the latter is a deuterated compound of the present invention or a mixture of formula (eTMM1), formula (eTMM1a), formula (eTMM1b), formula (eTMM1c), formula (eTMM1d), formula (eTMM1e), formula (eTMM2), formula (eTMM3), formula (eTMM3a), formula (eTMM4) or formula (eTMM5) as described above, wherein the deuteration level of these compounds is at least 50% to 90%, preferably 70% to 100%. Corresponding deuteration methods are known to those skilled in the art and are described, for example, in KR2016041014, WO2017 / 122988, KR202005282, KR101978651 and WO2018 / 110887, or in Bulletin of the Chemical Society of Japan, 2021, 94(2), 600-605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071.

[0251] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for deuterium atoms is to treat the compound to be deuterated in the presence of a platinum catalyst or a palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound that contains one or more deuterium atoms and is capable of releasing them under suitable conditions.

[0252] 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. Suitable deuterium sources are DO, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4, or toluene-d8. Preferred deuterium sources are DO or a combination of DO and a fully deuterated organic solvent. A particularly preferred deuterium source is a combination of DO and a fully deuterated organic solvent, wherein the fully deuterated solvent is not limited herein. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. A particularly preferred deuterium source is a combination of DO and toluene-d8. The reaction is preferably carried out under heating, more preferably under heating to a temperature between 100°C and 200°C. Furthermore, the reaction is preferably carried out under pressure.

[0253] In the mixture according to the invention or in the light-emitting layer of the device according to the invention, the total concentration of all host materials according to the invention as described above or as preferred is generally in the range from 5% to 90% by weight, preferably in the range from 10% to 85% by weight, more preferably in the range from 20% to 85% by weight, even more preferably in the range from 30% to 80% by weight, very particularly preferably in the range from 20% to 60% by weight, most preferably in the range from 30% to 50% by weight, based on the total mixture or on the total composition of the light-emitting layer.

[0254] In the mixture of the present invention or in the light-emitting layer of the device of the present invention, the total concentration of all host materials of formula (eTMM1), formula (eTMM1a), formula (eTMM1b), formula (eTMM1c), formula (eTMM1d), formula (eTMM1e), formula (eTMM2), formula (eTMM3), formula (eTMM3a), formula (eTMM4) and formula (eTMM5) as described above or as preferred is typically in the range of 5% by weight to 90% by weight, preferably in the range of 10% by weight to 85% by weight, more preferably in the range of 20% by weight to 85% by weight, even more preferably in the range of 30% by weight to 80% by weight, very particularly preferably in the range of 20% by weight to 60% by weight, most preferably in the range of 30% by weight to 50% by weight.

[0255] The present invention also relates to a mixture, which, on the basis of the above-mentioned host material of the present invention and a host material of at least one of formula (eTMM1), formula (eTMM1a), formula (eTMM1b), formula (eTMM1c), formula (eTMM1d), formula (eTMM1e), formula (eTMM2), formula (eTMM3), formula (eTMM3a), formula (eTMM4) and formula (eTMM5) as described above or as preferably described, also contains at least one phosphorescent light-emitting body.

[0256] Suitable phosphorescent compounds (= triplet emitters) are, in particular, compounds which emit light upon appropriate excitation, preferably in the visible region, and which furthermore contain at least one atom, in particular a metal, having an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. Preferred phosphorescent emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or platinum.

[0257] Examples of such emitters may be found in the following 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 used in phosphorescent OLEDs according to the prior art and as known to those skilled in the art in the field of organic electroluminescence are suitable, and those skilled in the art will be able to use other phosphorescent complexes without exercising inventive skill.

[0258] Examples of phosphorescent dopants are listed below.

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266] In the other layers of the organic electroluminescent device of the present invention, any materials commonly used according to the prior art can be used. Therefore, those skilled in the art will be able to use all materials known for organic electroluminescent devices in combination with the compounds of the present invention without applying creative skills.

[0267] Compounds which are particularly suitable for use in the layer having a hole-transport function in any OLED, not just in the OLED according to the definition of the present application, include the following compounds (HT-1) to (HT-20):

[0268]

[0269]

[0270] The term “layer having a hole-transport function” here more particularly refers to hole-injection layers, hole-transport layers, electron-blocking layers and light-emitting layers, in particular hole-injection layers, hole-transport layers and electron-blocking layers.

[0271] 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 the OLEDs described in this application.

[0272] Compounds (HT-1) to (HT-20) can be prepared by the methods disclosed in the publications cited in the table above. Further teachings regarding the use and preparation of the compounds disclosed in the publications cited in the table above are expressly incorporated herein by reference and are preferably combined with the teachings given above regarding the use of these compounds as hole-transporting materials. Compounds (HT-1) to (HT-20) exhibit excellent properties, particularly excellent lifetime and efficiency, when used in OLEDs.

[0273] Furthermore, an organic electroluminescent device is preferred, characterized in that one or more layers are applied by a sublimation process. In this case, the organic electroluminescent device is applied by sublimation in a vacuum sublimation system at a temperature of less than 10 -5 mbar, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of 10 mbar. However, the initial pressure can also be even lower, for example less than 10 -7 millibar.

[0274] Likewise preferred is an organic electroluminescent device, characterized in that one or more layers are applied by the OVPD (Organic Vapor Phase Deposition) method or by means of carrier gas sublimation. -5 The material is applied at a pressure between mbar and 1 bar. A special case of this method is the OVJP (Organic Vapor Jet) method, in which the material is applied directly through a nozzle and thereby structured.

[0275] Furthermore, preference is given to an organic electroluminescent device, characterized in that one or more layers are produced from solution, for example by spin coating, or by any printing method such as screen printing, flexographic printing, offset printing, LITI (light-induced thermography, thermal transfer printing), inkjet printing or nozzle printing. For this purpose, soluble compounds, obtained, for example, by suitable substitution, are required.

[0276] Furthermore, hybrid methods are possible in which, for example, one or more layers are applied from solution and one or more other layers are applied by vapor deposition.

[0277] 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, comprising the compounds according to the invention of the formula (1).

[0278] Compared to the prior art, the compounds according to the invention and the electronic devices according to the invention, in particular the organic electroluminescent devices, are notable for one or more of the following surprising advantages:

[0279] 1. OLEDs which contain the compounds according to the invention as matrix material for phosphorescent emitters have a long lifetime.

[0280] 2. OLEDs containing the compounds according to the invention have high efficiencies. This is particularly the case when the compounds are used as matrix material for phosphorescent emitters.

[0281] 3. OLEDs containing the compounds according to the invention have a low operating voltage. This is particularly true when the compounds are used as matrix material for phosphorescent emitters.

[0282] The present invention is illustrated in detail by the following examples, which are in no way intended to limit the present invention. A person skilled in the art will be able to use the information given to implement the present invention within the entire scope disclosed and to manufacture other electronic devices of the present invention without exercising inventive skill. Example

[0283] Unless otherwise stated, the following syntheses were carried out in dry solvents under a protective gas atmosphere. Solvents and reagents can be purchased from, for example, Sigma-ALDRICH or ABCR. The corresponding numbers in square brackets or the numbers quoted for individual compounds are related to the CAS numbers of the compounds known from the literature. In the case of compounds that can have multiple enantiomeric, diastereomeric or tautomeric forms, one form is shown in a representative manner.

[0284] A) Synthesis of Synthon S:

[0285] Example S1:

[0286]

[0287] A well-stirred solution of 38.4 g (100 mmol) 6-bromo-13,14-dihydrocarbazo[1,2-a]carbazole [2271382-95-5], 21.8 g (110 mmol) biphenyl-2-boronic acid [914675-52-8], 42.4 g (200 mmol) tripotassium phosphate [7778-53-2], 1.16 g (1 mmol) tetrakis(triphenylphosphine)palladium(0) [14221-01-3], 300 ml toluene, 100 ml dioxane, and 300 ml water was heated under reflux for 16 hours. After cooling, the organic phase was separated and washed three times with 300 ml of water each time, once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The drying agent was filtered off, the filtrate was concentrated to dryness, and the residue was chromatographed (Torrent automated column system from A. Semrau). Yield: 34.5 g (75 mmol), 75%; Purity: about 98%, according to 1 H NMR.

[0288] Similarly, by adjusting the stoichiometry of the reactants, the following compounds can be prepared; when the chloride is used instead of tetrakis(triphenylphosphine)palladium(0), 224 mg (1 mmol) palladium acetate and 821 mg (2 mmol) S-Phos [657408-07-6] are used.

[0289]

[0290]

[0291]

[0292]

[0293]

[0294] Example S100:

[0295]

[0296] A procedure similar to the synthesis of 3c in T. Taisei et al., Chem. Lett., 2019, 48, 1160 was used. Starting materials: 38.4 g (100 mmol) 6-bromo-13,14-dihydrocarbazo[1,2-a]carbazole [2271382-95-5] and 26.7 g (110 mmol) 3-phenyl-9H-carbazole [103012-26-6]. The crude product was purified by chromatography. Yield: 17.0 g (31 mmol), 31%; purity: approximately 98%, according to 1 H NMR.

[0297] Similarly, by adjusting the stoichiometry of the reactants, the following compounds can be prepared.

[0298]

[0299] B) Synthesis of Inventive Examples:

[0300] Example B1:

[0301]

[0302] To a well-stirred suspension of 30.6 g (100 mmol) of 13,14-dihydrocarbazo[1,2-a]carbazole [1444018-85-2] in 1000 ml of diethyl ether at room temperature was added 80 ml (200 mmol) of a 2.5 M n-butyllithium / n-hexane solution with stirring. After the addition was complete and the exothermic reaction had subsided, the mixture was stirred for a further hour, after which a mixture of 8.5 g (50 mmol) of silicon tetrachloride [10026-04-7] in 100 ml of diethyl ether was added dropwise. After the addition was complete and the exothermic reaction had subsided, the mixture was stirred at reflux for 5 hours, after which the diethyl ether was removed under reduced pressure, and the residue was dissolved in approximately 300 ml of dichloromethane (DCM) and chromatographed on basic alumina with an activity level of 1. In each case, the crude product was further purified by chromatography and / or repeated hot extractive crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 v / v) and fractionated sublimation or thermal treatment under high vacuum. Yield: 22.2 g (70 mmol), 70%; purity: approximately 99.9% according to HPLC.

[0303] Similarly, by adjusting the stoichiometry of the reactants, the following compounds can be obtained.

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320] Example: OLED Manufacturing

[0321] The OLEDs according to the invention and the OLEDs according to the prior art are produced by the general process according to WO 2004 / 058911, which is adapted to the circumstances described there (variation of layer thicknesses, materials used).

[0322] In the following examples, results for various OLEDs are presented. Clean glass plates coated with 50 nm thick structured ITO (indium tin oxide) (cleaned in a Miele laboratory glasswasher, Merck Extran detergent) were pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator). These coated glass plates formed the substrate for the OLED application.

[0323] a) Blue Fluorescent OLED Component – ​​BF

[0324] The compounds of the present invention can be used in hole injection layers (HILs), hole transport layers (HTLs) and / or electron blocking layers (EBLs). All materials are applied by thermal vapor deposition in a vacuum chamber. The light-emitting layer (EML) is always composed of at least one matrix material (host material) SMB (see Table 1) and a luminescent dopant (dopant, luminophore) D added to one or more matrix materials in a specific volume ratio by co-evaporation. Details given in the form of SMB:D (97:3%) mean that the material SMB is present in the layer at a volume ratio of 97%, and the dopant D is present in the layer at a volume ratio of 3%. Similarly, the electron transport layer can also be composed of a mixture of two materials (see Table 1). The materials used to manufacture OLEDs are shown in Table 5.

[0325] The OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in percentage) were determined and calculated from the current-voltage-luminous density characteristic (IUL characteristic) as a function of the luminous density assuming Lambertian emission. The values ​​at 1000 cd / m 2 EQE (%) and voltage (V) at luminous density.

[0326] OLEDs have the following layer structure:

[0327] base

[0328] Hole injection layer (HIL), composed of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0329] Hole transport layer (HTL), see Table 1

[0330] Electron blocking layer (EBL), see Table 1

[0331] Emission layer (EML), see Table 1

[0332] Electron transport layer (ETL), see Table 1

[0333] Electron injection layer (EIL), composed of ETM2, 1 nm

[0334] Aluminum cathode, 100 nm

[0335] Table 1: Structure of blue fluorescent OLED components

[0336]

[0337] Table 2: Results of blue fluorescent OLED components

[0338]

[0339] b) Phosphorescent OLED components

[0340] The compounds of the present invention can be used as a matrix material (host material) M in a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL) and / or in an emitting layer (EML) (see Table 5). For this purpose, all materials are applied by thermal vapor deposition in a vacuum chamber. The emitting layer is always composed of at least one or more matrix materials M and a phosphorescent dopant Ir added to one or more matrix materials in a specific volume ratio by co-evaporation. Details given in the form of M1:M2:Ir (55%:35%:10%) mean that the material M1 is present in the layer at a volume ratio of 55%, M2 is present in the layer at a volume ratio of 35%, and Ir is present in the layer at a volume ratio of 10%. Similarly, the electron transport layer can also be composed of a mixture of two materials. The exact structure of the OLED can be found in Table 3. The materials used to manufacture the OLED are shown in Table 5.

[0341] The OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in percentage) were determined and calculated from the current-voltage-luminous density characteristic (IUL characteristic) as a function of the luminous density assuming Lambertian emission. The values ​​at 1000 cd / m 2 EQE (%) and voltage (V) at luminous density.

[0342] OLEDs have the following layer structure:

[0343] base

[0344] Hole injection layer (HIL), composed of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0345] Hole transport layer (HTL), see Table 3

[0346] Electron blocking layer (EBL), see Table 3

[0347] Emission layer (EML), see Table 3

[0348] Hole blocking layer (HBL), see Table 3

[0349] Electron transport layer (ETL), composed of ETM1:ETM2 (50%:50%), 30 nm

[0350] Electron injection layer (EIL), composed of ETM2, 1 nm

[0351] Aluminum cathode, 100 nm

[0352] Table 3: Structure of phosphorescent OLED components

[0353]

[0354]

[0355]

[0356] Table 4: Results of phosphorescent OLED components

[0357]

[0358]

[0359] Table 5: Structural formulas of the materials used

[0360]

[0361]

[0362]

Claims

1. A compound comprising a substructure of formula (1), The symbols used are as follows: M is Si, Ge, Sn, Ti, Zr or Hf; W is identical or different in each case and is CR or N, wherein not more than one W in each ring is N; or two W together form a group of formula (2), wherein one of the two dashed bonds represents a bond to N, and the other dashed bond represents a bond to Z; Z is identical or different in each case and is a single bond, BR, CR2, C=O, SiR2, GeR2, NR, P(=O)R, O, S or SO2; Y is identical or different in each case and is NR, O or S; or Y together with the explicitly indicated carbon atom and the adjacent X forms a radical of the formula (3) or (4), wherein W, Z and X have the definitions given above, the dashed bond marked with * represents the bond to M, and the other two dashed bonds represent the connection of this structure within formula (1); X is identical or different in each case and is CR or N, wherein not more than two X in each ring are N, or two adjacent X in formula (2) together represent CR2, NR, O or S; R is identical or different in each case and is 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 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by Si(R 1 )2、C=O、NR 1 , O, S, or CONR 1 or having 5 to 40 aromatic ring atoms and may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group; at the same time, the two R groups together can also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; Ar is identical or different in each case and is an aromatic ring having 5 to 40 atoms and may be replaced by one or more R 1 group-substituted aromatic or heteroaromatic ring systems; R 1 are identical or different in each case and are 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 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group can be replaced by one or more R 2 group, wherein one or more non-adjacent CH2 groups may be replaced by Si(R 2 )2、C=O、NR 2 , O, S, or CONR 2 and wherein one or more hydrogen atoms in the alkyl, alkenyl or alkynyl group may be replaced by D, F, Cl, Br, I or CN, or have 5 to 40 aromatic ring atoms and in each case by one or more R 2 An aromatic or heteroaromatic ring system substituted with a group; at the same time, two or more R 1 The groups together may also form an aliphatic, aromatic or heteroaromatic ring system; R 2 are in each case identical or different and are H, D, F, CN, or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in particular a hydrocarbon radical, in which one or more hydrogen atoms may also be replaced by F.

2. The compound according to claim 1, wherein the compound is selected from the compounds of formula (5) and formula (6), The symbols used therein have the definitions given in claim 1, and: R M are the same or different in each case and are F, CN, OR 1 ,OAr,N(R 1 )2,NAr2,Si(R 1 )3, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl or alkoxy group may be replaced by one or more R 1 group and one or more non-adjacent CH2 groups may be replaced by Si(R 1 )2、C=O、NR 1 , O, S, or CONR 1 or having 5 to 40 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group; at the same time, two R M The groups together may also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system, wherein the two R M The group may be connected by a single bond or by a 1 )2, O, S, NR 1 and BR groups; in addition, one or more R M It may be linked to one or more R to form a ring system.

3. The compound according to claim 1 or 2, characterized in that Y is in each case identical or different and is NR, or is characterized in that Y together with the explicitly indicated carbon atom and the adjacent X forms a group of the formula (3).

4. Compound according to one or more of claims 1 to 3, characterized in that The substructure of formula (1) is selected from the structures of formula (7) and formula (8), The symbols used therein have the definitions given in claim 1, and Y in formula (8) is NR, O or S.

5. The compound according to one or more of claims 1 and 4, selected from the group consisting of compounds of formula (9), formula (10), formula (11) and formula (12), The symbols used therein have the definitions given in claims 1 and 2, and Y in formula (10) and formula (12) is NR, O or S.

6. Compound according to one or more of claims 1 to 5, characterized in that Z is in each case identical or different and is a single bond, CR2, BR or O.

7. Compound according to one or more of claims 1 to 6, characterized in that The two W groups together are a group of formula (2a), ， or characterized in that Z is a single bond and one of the two W groups in the same ring is CR and the other of the two W groups is N.

8. Compound according to one or more of claims 1 to 7, characterized in that The substructure of formula (1) is selected from the structures of formula (7a), formula (7b), formula (8a) and formula (8b), The symbols used therein have the definitions given in claim 1, Y in formula (8a) and formula (8b) is NR, O or S, and Z in formula (7a) and formula (8a) is preferably a single bond.

9. The compound according to one or more of claims 1 to 8, selected from the group consisting of compounds of formula (9a), formula (9b), formula (10a), formula (10b), formula (11a), formula (11b), formula (12a) and formula (12b), The symbols used therein have the definitions given in claims 1 and 2, Y in formula (10a), formula (10b), formula (12a) and formula (12b) is NR, O or S, and Z in formula (9a), formula (10a), formula (11a) and formula (12a) is preferably a single bond.

10. Compounds according to one or more of claims 1 to 9, selected from the group consisting of compounds of formula (9a-1), formula (10a-1), formula (11a-1) and formula (12a-1), wherein the symbols have the definitions given in claims 1 and 2, Y in formula (10a-1) and formula (12a-1) is NR, O or S, and Z is preferably a single bond.

11. Compound according to one or more of claims 1 and 10, characterized in that M is Si or Ge, preferably Si.

12. Compound according to one or more of claims 1 to 11, characterized in that The compounds have not more than four substituents R other than H and D bonded to a carbon atom.

13. Compound according to one or more of claims 1 to 12, characterized in that R M are identical or different in each case and are selected from straight-chain alkyl radicals having 1 to 6 carbon atoms or branched or cyclic alkyl radicals having 3 to 6 carbon atoms, in which one or more hydrogen atoms may also each be replaced by D, or have 6 to 13 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group; at the same time, two R M The groups can also form a ring system together; or two R M The groups together are a group of formula (13), where the dotted bond represents the bond to M, and R 1 As defined in claim 1.

14. A preparation 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 electronic devices.

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

17. The electronic device according to claim 16, wherein the electronic device is an organic electroluminescent device, characterized in that The compound according to one or more of claims 1 to 13 is used as a matrix material for a phosphorescent emitter or an emitter exhibiting TADF (thermally activated delayed fluorescence) in an emitting layer, or as a hole transport material or electron blocking material in a hole transport layer or electron blocking layer, or as an electron transport material in an electron transport layer or 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 of formula (eTMM1), formula (eTMM2), formula (eTMM3), formula (eTMM4) or formula (eTMM5), Formula (eTMM1), Formula (eTMM2), Formula (eTMM3), Formula (eTMM4), Formula (eTMM5), The symbols and notations used are as follows: L 2 are identical or different in each case and are a single bond or have 5 to 24 ring atoms and may be replaced by one or more R 7 group-substituted aromatic or heteroaromatic ring systems; R# is identical or different in each case and is D, F, CN or has 6 to 24 ring atoms and may be replaced by one or more R 6 group-substituted aromatic ring systems; Y is the same or different in each instance and is N or CR 7 , which excludes the possibility that two adjacent Ys are both N; V 2 O or S; R 6 are identical or different in each case and are H, D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may be replaced by one or more R 7 group and one or more non-adjacent CH2 groups may be replaced by Si(R 7 )2、C=O、NR 7 , O, S, or CONR 7 or having 5 to 60 ring atoms and in each case being replaced by one or more R 7 Aromatic or heteroaromatic ring system substituted with a group; wherein the two R 6 The groups may also be taken together to form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar 5 are identical or different in each case and have 5 to 40 ring atoms and may be replaced by one or more R 7 group-substituted aromatic or heteroaromatic ring systems; R 7 are identical or different in each case and are H, D, F, Cl, Br, I, N(R 8 )2,CN,NO2,OR 8 , SR 8 ,Si(R 8 )3,B(OR 8 )2,C(=O)R 8 ,P(=O)(R 8 )2,S(=O)R 8 , S(=O)2R 8 , OSO2R 8 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 8 group and one or more non-adjacent CH2 groups may be replaced by Si(R 8 )2、C=O、NR 8 , O, S, or CONR 8 or having 5 to 40 ring atoms and in each case being replaced by one or more R 8 An aromatic or heteroaromatic ring system substituted with a group; at the same time, two or more R 7 The groups together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R 8 are in each case identical or different and are H, D, F, or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in particular a hydrocarbon radical, in which one or more hydrogen 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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