Polycyclic compounds for organic electroluminescent devices

Abstract

The present invention relates to compounds suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, comprising said compounds.

Description

Detailed Description of the Invention

[0001] The present invention relates to polycyclic compounds for use in electronic devices, particularly organic electroluminescent devices, and to electronic devices, particularly organic electroluminescent devices, comprising these polycyclic compounds.

[0002] The emitting materials used in organic electroluminescent devices are often phosphorescent organometallic complexes or fluorescent compounds.In general, there is still a need for improvements in electroluminescent devices.

[0003] WO2019 / 004248A1, WO2019 / 035268A1, WO2019 / 074093A1, WO2019 / 088799A1 and WO2019 / 102936A1 disclose polycyclic compounds that can be used in organic electroluminescent devices, but do not disclose the compounds according to the present invention.

[0004] In general, there is still a need for improvements in these polycyclic compounds, for example for use as emitters, in particular as fluorescent emitters, in particular with regard to lifetime and color purity, with regard to device efficiency and operating voltage.

[0005] It is therefore an object of the present invention to provide compounds which are suitable for use in organic electronic devices, in particular organic electroluminescent devices, and which, when used in such devices, result in good device properties, and to provide corresponding electronic devices.

[0006] More particularly, the problem addressed by the present invention is to provide compounds that provide long life, good efficiency and low operating voltage.

[0007] Furthermore, the compounds should have good processability and in particular they should exhibit good solubility.

[0008] A further problem addressed by the present invention can be seen as providing compounds suitable in particular for use as emitters in phosphorescent and fluorescent electroluminescent devices. More particularly, the problem addressed by the present invention is to provide emitters suitable for blue electroluminescent devices.

[0009] Furthermore, the compounds, especially when used as emitters in organic electroluminescent devices, should result in devices with excellent color purity.

[0010] A further challenge is to provide electronic components having excellent performance at very low cost and with consistent quality.

[0011] Furthermore, the electronic device must be capable of being used or adapted for many purposes. More particularly, the performance of the electronic device must be maintained over a wide temperature range.

[0012] Surprisingly, it has been found that certain compounds, described in detail below, solve this problem, are suitable for use in electroluminescent devices, and provide improvements in organic electroluminescent devices, in particular with regard to lifetime, color purity, efficiency and operating voltage.The present invention therefore provides those compounds, and electronic devices, in particular organic electroluminescent devices, comprising those compounds.

[0013] The present invention provides compounds comprising at least one structure of formula (I), preferably compounds of formula (I). [ka] where the symbols and subscripts used are as follows: Z is N, P, B, Al, P(=O), P(=S) or Ga, preferably N, P(=O), B or Al, more preferably N or B; Y 1 , Y 2 , Y 3is a bond, N(Ar), N(R), P(Ar), P(R), P(=O)Ar, P(=O)R, P(=S)Ar, P(=S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, C(R) 2 , Si(R) 2 , C=NR, C=NAr, C=C(R) 2 , O, S, Se, S=O or SO 2 and preferably a bond, N(Ar), N(R), B(Ar), B(R), P(R), P(=O)Ar, C=O, C(R) 2 , O, S, S=O or SO 2 and more preferably a bond, C(R) 2 , O, S, N(Ar) or B(Ar); p 2 , p 3 are the same or different and are 0 or 1; X is N, CR or Y 1 , Y 2 Or Y 3 is C when the group is attached thereto, with the proviso that not more than two X groups in any one ring are N; R is the same or different at each occurrence and is H, D, OH, F, Cl, Br, I, CN, NO 2 , N(Ar) 2 , N(R 1 ) 2 , C(=O)N(Ar) 2 , C(=O)N(R 1 ) 2 , C(Ar) 3 , C(R 1 ) 3 , Si(Ar) 3 , Si(R 1 ) 3 , B(Ar) 2 , B(R 1 ) 2 , C(=O)Ar, C(=O)R 1 , P(=O)(Ar) 2 , P(=O)(R 1 ) 2 , P(Ar) 2 , P(R 1 ) 2 , S(=O)Ar, S(=O)R1 , S(=O) 2 Ar, S(=O) 2 R 1 , O.S.O. 2 Ar, O.S.O. 2 R 1 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is in each case composed of one or more R 1 radical, wherein one or more non-adjacent CH 2 The group is R 1 C=CR 1 , C≡C, Si(R 1 ) 2 , C=O, C=S, C=Se, C=NR 1 , -C(=O)O-, -C(=O)NR 1 -, NR 1 , P(=O)(R 1 ), -O-, -S-, SO or SO 2 or 5 to 60 aromatic ring atoms, in each case having one or more R 1 an aromatic or heteroaromatic ring system or a ring system having 5 to 60 aromatic ring atoms, optionally substituted by a radical, and one or more R 1 an aryloxy or heteroaryloxy group, optionally substituted by a radical; at the same time, two R radicals may together form a ring system; Ar may be the same or different in each occurrence and has 5 to 60 aromatic ring atoms and one or more R 1 at the same time, two Ar radicals bonded to the same carbon, silicon, nitrogen, phosphorus or boron atom are bridged by a single bond or by a B(R 1 ), C(R 1 ) 2 , Si(R 1 )2 , C=O, C=NR 1 , C=C(R 1 ) 2 , O, S, S=O, SO 2 , N(R 1 ), P(R 1 ) and P(=O)R 1 may also be coupled together via a bridge selected from: R 1 are the same or different for each occurrence and are H, D, F, Cl, Br, I, CN, NO 2 , N(Ar') 2 , N(R 2 ) 2 , C(=O)Ar', C(=O)R 2 , P(=O)(Ar') 2 , P(Ar') 2 , B(Ar') 2 , B(R 2 ) 2 , C(Ar') 3 , C(R 2 ) 3 , Si(Ar') 3 , Si(R 2 ) 3 a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms (each of which may be selected from the group consisting of one or more R 2 radical, wherein one or more non-adjacent CH 2 The group is -R 2 C=CR 2 -, -C≡C-, Si(R 2 ) 2 , C=O, C=S, C=Se, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 2 ), -O-, -S-, SO or SO 2 and where one or more hydrogen atoms are replaced by D, F, Cl, Br, I, CN or NO 2or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be replaced by one or more R 2 or having 5 to 60 aromatic ring atoms and one or more R 2 an aryloxy or heteroaryloxy group, optionally substituted by a radical, or a aryloxy group having 5 to 60 aromatic ring atoms and one or more R 2 aralkyl or heteroaralkyl groups, or combinations of these systems, optionally substituted by radicals; at the same time, two or more, preferably adjacent R 1 The radicals may together form a ring system; at the same time, one or more R 1 The radical may form a ring system with further moieties of said compound; Ar' may be the same or different in each occurrence and has 5 to 30 aromatic ring atoms and one or more R 2 at the same time, two Ar′ radicals bonded to the same carbon, silicon, nitrogen, phosphorus or boron atom are bridged by a single bond or by B(R 2 ), C(R 2 ) 2 , Si(R 2 ) 2 , C=O, C=NR 2 , C=C(R 2 ) 2 , O, S, S=O, SO 2 , N(R 2 ), P(R 2 ) and P(=O)R 2 may also be coupled together via a bridge selected from: R 2are identical or different at each occurrence and are selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and which may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms; at the same time, two or more, preferably adjacent, substituents R 2 may together form a ring system; however, When Z is selected from N and P, at least one Y 1 , Y 2 , Y 3 The groups are P(=O)Ar, P(=O)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, S=O or SO 2 and preferably B(Ar), B(R), P(=O)Ar, P(=O)R, C=O, S=O or SO 2 and more preferably B(R) or B(Ar), or When Z is selected from B, Al, P(=O), P(=S) and Ga, at least one Y 1 , Y 2 , Y 3 The groups are N(Ar), N(R), P(Ar), P(R), O, S or Se, preferably N(Ar), N(R), O or S, more preferably N(Ar); wherein at least two R radicals, together with the further group to which they are bonded, form a condensed ring, and the two R radicals form at least one structure of formula (RA-1) to (RA-12). [ka] Here, R 1 has the meaning given above, the dotted line indicates the site of attachment to the atom of the group to which the two R radicals are bonded, and the further symbols have the following meanings: Y 4 are the same or different for each occurrence, and C(R1 ) 2 , (R 1 ) 2 CC(R 1 ) 2 , (R 1 )C=C(R 1 ), N.R. 1 , NAr, O or S, preferably C(R 1 ) 2 , (R 1 ) 2 CC(R 1 ) 2 , (R 1 )C=C(R 1 ), O or S; R a are identical or different at each occurrence and are represented by F, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is, in each case, represented by one or more R 2 radical, wherein one or more non-adjacent CH 2 The group is R 2 C=CR 2 , C≡C, Si(R 2 ) 2 , C=O, C=S, C=Se, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 1 ), -O-, -S-, SO or SO 2 and optionally substituted by, 5 to 60 aromatic ring atoms, in each case one or more R 2 an aromatic or heteroaromatic ring system or a ring system having 5 to 60 aromatic ring atoms, optionally substituted by a radical, and one or more R 2 an aryloxy or heteroaryloxy group, optionally substituted by a radical; aIt is also possible for the radicals to form a ring system together; s is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2; t is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2; v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2.

[0014] An aryl group, in the sense of the present invention, contains 6 to 40 carbon atoms; a heteroaryl group, in the sense of the present invention, 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. An aryl or heteroaryl group is understood here to mean a single aromatic ring, i.e. benzene, or a single heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatic systems which are linked together by a single bond (for example biphenyl), in contrast, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

[0015] In the sense of the present invention, electron-deficient heteroaryl group is a heteroaryl group that has at least one heteroaromatic 6-membered ring with at least one nitrogen atom.An additional aromatic or heteroaromatic 5- or 6-membered ring may be condensed to this 6-membered ring.Examples of electron-deficient heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline or quinoxaline.

[0016] In the sense of the present invention, an aromatic ring system has 6 to 60 carbon atoms in the ring system. In the sense of the present invention, a heteroaromatic ring system contains 2 to 60 carbon atoms and at least one heteroatom in the ring system, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and / or S. In the sense of the present invention, an aromatic or heteroaromatic ring system is to be understood as meaning a system which does not necessarily contain only aryl or heteroaryl groups, but in which two or more aryl or heteroaryl groups can also be linked by non-aromatic units, such as carbon, nitrogen or oxygen atoms. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, stilbenes, etc., are also considered as aromatic ring systems in the sense of the present invention, as are systems in which two or more aryl groups are linked, for example by short alkyl groups. Preferably, the aromatic ring system is selected from fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene or a group in which two or more aryl and / or heteroaryl groups are linked together by a single bond.

[0017] In the sense of the present invention, it has 1 to 20 carbon atoms and each hydrogen atom or CH 2An aliphatic hydrocarbyl radical or an alkyl group or an alkenyl or alkynyl group, which radicals may be substituted by the abovementioned radicals, is preferably understood to mean the methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, 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, pentynyl, hexynyl or octynyl radical. An alkoxy group having 1 to 40 carbon atoms is preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. A thioalkyl group having 1 to 40 carbon atoms is understood to mean, in particular, 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, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.In general, an alkyl, alkoxy or thioalkyl group according to the present invention may be linear, branched or cyclic, wherein there is one or more adjacent CH. 2 groups may be replaced by the groups described above; furthermore, one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN, or NO 2 , preferably by F, Cl or CN, more preferably by F or CN, particularly preferably by CN.

[0018] Aromatic or heteroaromatic ring systems having 5 to 60 or 5 to 40 aromatic ring atoms, which in each case may be substituted by the abovementioned radicals and which may be bonded to the aromatic or heteroaromatic system in any desired position, are in particular benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, triphenylene, terphenylene, 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, quinoxalimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, Pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazapyrylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,It is understood to mean radicals derived from 5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole, or radicals derived from combinations of these systems.

[0019] In the sense of the present invention, the term that two or more radicals may together form a ring is understood to mean, inter alia, that two radicals are linked to each other by a chemical bond, with the formal removal of two hydrogen atoms, as illustrated by the following scheme: [ka]

[0020] In addition, however, the above terms are also understood to mean that when one of the two radicals is hydrogen, the second radical is bonded to the bonded position of the hydrogen atom to form a ring, which is exemplified by the following scheme: [ka]

[0021] In a preferred form, the compound of the invention may comprise a structure of formula (IIa), (IIb), (IIc) and / or (IId); more preferably, the compound of the invention is selected from compounds of formula (IIa), (IIb), (IIc) and / or (IId). [ka] Here, p 2 , p 3 , Y 1 , Y 2 , Y 3, X, Z and R have the meanings given above, in particular in formula (I), the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the index n is 0, 1, 2 or 3, preferably 0, 1 or 2, where the sum of the indexes m and n is preferably 0, 1, 2, 3 or 4.

[0022] Preferably, in formulae (I), (IIa), (IIb), (IIc) and (IId), not more than 4, preferably not more than 2, X groups are N, more preferably it may be the case that all X groups are CR.

[0023] In a further preferred embodiment, the compound of the present invention comprises the structure of formula (IIIa), (IIIb) and (IIIc), where the compound of the present invention is more preferably selected from the compounds of formula (IIIa), (IIIb) and (IIIc). [ka] Here, Y 1 , Y 2 , Y 3 , X, Z and R have the meanings given above, in particular for formula (I), the index l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, the index n is 0, 1, 2 or 3, preferably 0, 1 or 2, where the sum of the indexes l, m and n is preferably 2, 3, 4, 5, 6, 7 or 8, preferably the structures of the formulae (IIIa) and (IIIb), particularly preferably the structure of the formula (IIIa).

[0024] The sum of the indices m, n and l in the compounds of formulae (IIIa), (IIIb) and (IIIc) is 10 or less, particularly preferably 8 or less, more preferably 6 or less.

[0025] Furthermore, there may be cases where at least two R radicals forming a fused ring forming the structure of formulae (RA-1) to (RA-12) are R radicals from adjacent X groups.

[0026] In a preferred embodiment of the invention, at least two R radicals together with the further group to which they are attached form a fused ring, where the two R radicals preferably form at least one of the structures of formulae (RA-1a) to (RA-4f). Here, the symbol R a and R 1 and the indices s and t have the meanings given above, especially in formula (I), and the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2. [ka]

[0027] More preferably, the compound comprises at least one of the structures of formulae (IVa) to (IVu); more preferably, the compound is selected from the compounds of formulae (IVa) to (IVu). [ka] [ka] [ka] Here, Y 1 , Y 2 , Y 3, X, Z and R have the meanings given above, in particular in formula (I), the symbol o denotes at least one connection site of the structures of formulae (RA-1) to (RA-12), the index l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, the index n is 0, 1, 2 or 3, preferably 0, 1 or 2, the index j is 0, 1 or 2, preferably 0 or 1, the index k is 0 or 1, preferably 0, where the sum of the indexes k, j, l, m and n is preferably 0, 1, 2, 3, 4, 5 or 6. Preference is given to structures / compounds of formulae (IVa) to (IVk), particularly preferred are structures / compounds of formulae (IVa) to (IVc).

[0028] Preferably, the compound of the present invention comprises at least one structure of formulae (IVa-1) to (IVb-4); more preferably, the compound of the present invention is selected from the compounds of formulae (IVa-1) to (IVb-4). [ka] where the subscripts s and v and the symbol Y 1 , Y 2 , Y 3 , Y 4 , X, Z, R, R a and R 1 has the meaning given above, in particular in formula (I), wherein the index n is 0, 1, 2 or 3, preferably 0, 1 or 2, and the index k is 0 or 1, preferably 0, where the sum of the indexes k and n is preferably 0, 1, 2, 3, 4, 5 or 6, more preferably 2, 3, 4 or 5.

[0029] Preferably, the compound of the present invention comprises at least one structure of formulae (IVe-1) to (IVh-4); more preferably, the compound of the present invention is selected from the compounds of formulae (IVe-1) to (IVh-4). [ka] [ka] where the subscripts s and v, Y 1 , Y 2 , Y 4 , X, Z, R, R a And R 1 has the meaning given above, in particular in formula (I), the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, the index n is 0, 1, 2 or 3, preferably 0, 1 or 2, the index j is 0, 1 or 2, preferably 0 or 1 and the index k is 0 or 1, preferably 0, where the sum of the indices k, j, l, m and n is 0, 1, 2, 3, 4, 5, 6, 7 or 8, more preferably 2, 3, 4, 5 or 6.

[0030] Furthermore, Y 2 and / or Y 3 In the above equation, where Y 1 is a bond and Y 2 and / or Y 3 is, N(Ar), N(R), P(Ar), P(R), P(=O)Ar, P(=O)R, P(=S)Ar, P(=S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, C(R) 2 , Si(R) 2 , C=NR, C=C(R) 2 , O, S, Se, S=O, or SO 2 , preferably N(Ar), N(R), B(Ar), B(R), P(R), P(=O)Ar, C=O, C(R) 2 , O, S, S=O, or SO 2 , more preferably C(R) 2 , O, S, N(Ar) or B(Ar).

[0031] Furthermore, Y 2 and / or Y 3 In the above equation, where Y 2 indicates a bond, and Y 1 and / or Y 3is, N(Ar), N(R), P(Ar), P(R), P(=O)Ar, P(=O)R, P(=S)Ar, P(=S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, C(R) 2 , Si(R) 2 , C=NR, C=C(R) 2 , O, S, Se, S=O, or SO 2 , preferably N(Ar), N(R), B(Ar), B(R), P(R), P(=O)Ar, C=O, C(R) 2 , O, S, S=O, or SO 2 , more preferably C(R) 2 , O, S, N(Ar) or B(Ar).

[0032] In a further preferred form, at least two R radicals form a fused ring with the additional group to which the two R radicals are attached, where the two R radicals form a structure of formula (RB). [ka] Here, R 1 has the meaning given above, in particular in formula (I), the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y 5 is C(R 1 ) 2 , N.R. 1 , NAr, O or S, preferably C(R 1 ) 2 , NAr or O.

[0033] wherein at least two R radicals forming a structure of formula (RB) and forming a fused ring are R radicals from adjacent X groups.

[0034] Preferably, this may be the case where the compound has at least two fused rings, where at least one fused ring is formed from a structure of formula (RA-1) to (RA-12) and a further ring is formed from a structure of formula (RA-1) to (RA-12) or (RB), where the compound comprises at least one of the structures of formula (Va) to (Vz), preferably the compound is selected from the compounds of formula (Va) to (Vz). [ka] [ka] [ka] Here, Y 1 , Y 2 , Y 3 , X, Z and R have the meanings described above, in particular in formula (I), the symbol o denotes at least one connection site of the structures of formulae (RA-1) to (RA-12) or of the structure of formula (RB), the index l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, the index n is 0, 1, 2 or 3, preferably 0, 1 or 2, the index j is 0, 1 or 2, preferably 0 or 1, the index k is 0 or 1, preferably 0, where the sum of the indexes k, j, l, m and n is preferably 0, 1, 2, 3 or 4, more preferably 2, 3 or 4. Preference is given to structures / compounds of formulae (Va) to (Vp), particularly preferably to structures / compounds of formulae (Va) to (Vd). Preferably, the sum of the indices k, j, l, m and n is 0, 1, 2 or 3, preferably 1 or 2.

[0035] Here, it may be the case that formulae (Va) to (Vz) have at least two fused rings, where the fused rings are identical and the moiety formed by the two R radicals can be represented by at least one of the structures of formulae (RA-1) to (RA-12).

[0036] Furthermore, it may be the case that formulae (Va) to (Vz) have at least two fused rings, where the fused rings are different and the moiety formed by the two R radicals can in each case be represented by at least one of the structures of formulae (RA-1) to (RA-12).

[0037] Furthermore, it may be the case that formulae (Va) to (Vz) have at least two fused rings, where the fused rings are different and the moiety formed by the two R radicals is represented by at least one of the structures of formulae (RA-1) to (RA-12), and one of the two fused rings has a moiety formed by two R radicals represented by one of the structures of formula (RB).

[0038] In a further aspect, the compound of the present invention preferably comprises at least one structure of formula (Va-1) to (Va-18); more preferably, the compound of the present invention is selected from the compounds of formula (Va-1) to (Va-18). [ka] [ka] where the subscripts s and v and the symbol Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , X, Z, R, R a and R 1 has the meaning given above, in particular in formula (I) or in formula (RB), the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, the index n is 0, 1, 2 or 3, preferably 0, 1 or 2 and the index k is 0 or 1, preferably 0, where the sum of the indices k, m and n is preferably 0, 1, 2, 3, 4, 5, 6, 7 or 8, more preferably 0, 1, 2, 3 or 4.

[0039] In a further aspect, the compound of the present invention preferably comprises at least one structure of formula (Vc-1) to (Vc-18); more preferably, the compound of the present invention is selected from the compounds of formula (Vc-1) to (Vc-18). [ka] [ka] where the subscripts s and v and the symbol Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , X, Z, R, R a and R 1 has the meaning given above, in particular in formula (I) or in formula (RB), the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, the index n is 0, 1, 2 or 3, preferably 0, 1 or 2 and the index k is 0 or 1, preferably 0, where the sum of the indices k, m and n is preferably 0, 1, 2, 3, 4, 5, 6, 7 or 8, more preferably 0, 1, 2, 3 or 4.

[0040] In the formulae (Va-1) to (Va-18) and / or (Vc-1) to (Vc-18), preferably, Y 1 indicates a bond, and Y 2 and / or Y 3 is, N(Ar), N(R), P(Ar), P(R), P(=O)Ar, P(=O)R, P(=S)Ar, P(=S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, C(R) 2 , Si(R) 2 , C=NR, C=C(R) 2 , O, S, Se, S=O or SO 2 , preferably N(Ar), N(R), B(Ar), B(R), P(R), P(=O)Ar, C=O, C(R) 2 , O, S, S=O or SO 2 , more preferably C(R) 2, O, S, N(Ar) or B(Ar).

[0041] Preferably, in formulas (Va-1) to (Va-18) and / or (Vc-1) to (Vc-18), Y 2 indicates a bond, and Y 1 and / or Y 3 is, N(Ar), N(R), P(Ar), P(R), P(=O)Ar, P(=O)R, P(=S)Ar, P(=S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, C(R) 2 , Si(R) 2 , C=NR, C=C(R) 2 , O, S, Se, S=O or SO 2 , preferably N(Ar), N(R), B(Ar), B(R), P(R), P(=O)Ar, C=O, C(R) 2 , O, S, S=O or SO 2 , more preferably C(R) 2 , O, S, N(Ar) or B(Ar).

[0042] Furthermore, in formulas (I), (IIa), and (IIb), the subscript p 2 and p 3 The sum of is 2, and Y 1 , Y 2 , Y 3 At least one of the groups is a bond and Y 1 , Y 2 , Y 3 At least one, preferably at least two of the groups are B(Ar) or B(R), Z is N, and / or in (IIIa), (IVa) to (IVc), (Va) to (Vd), (Va-1) to (Va-18) or (Vc-1) to (Vc-18), Y 1 , Y 2 , Y 3 At least one of the groups is a bond, and Y 1 , Y 2 , Y 3 This may be the case when at least one, preferably at least two of the groups is B(Ar) or B(R) and Z is N.

[0043] In addition, in formulas (I), (IIa), and (IIb), the subscript p 2 and p 3 The sum of is 2, and Y 1 , Y 2 , Y 3 At least two of the groups, preferably Y 1 , Y 2 , Y 3 all of the groups are B(Ar) or B(R), Z is N, and / or in formula (IIIa), (IVa) to (IVc), (Va) to (Vd), (Va-1) to (Va-18) or (Vc-1) to (Vc-18), Y 1 , Y 2 , Y 3 At least two of the groups, preferably Y 1 , Y 2 , Y 3 It may be the case that all of the groups are B(Ar) or B(R) and Z is N.

[0044] Furthermore, in formulas (I), (IIa), and (IIb), the subscript p 2 and p 3 The sum of is 2, and Y 1 , Y 2 , Y 3 At least one of the groups is a bond, preferably Y 1 , Y 2 , Y 3 At least one, preferably at least two of the groups are N(Ar) or N(R), Z is B, and / or in formula (IIIa), (IVa) to (IVc), (Va) to (Vd), (Va-1) to (Va-18) or (Vc-1) to (Vc-18), Y 1 , Y 2 , Y 3 At least one of the groups is a bond, and Y 1 , Y 2 , Y 3 This may be the case when at least one, preferably at least two, of the groups is N(Ar) or N(R) and Z is B.

[0045] Furthermore, in formulas (I), (IIa), and (IIb), the subscript p 2 and p 3 The sum of is 2, and Y 1 , Y 2 , Y 3 At least two of the groups, preferably Y 1 , Y 2 , Y 3 all of the groups are N(Ar) or N(R), Z is B, and / or in formula (IIIa), (IVa) to (IVc), (Va) to (Vd), (Va-1) to (Va-18) or (Vc-1) to (Vc-18), Y 1 , Y 2 , Y 3 At least two of the groups, preferably Y 1 , Y 2 , Y 3 It may also be the case that all of the groups are N(Ar) or N(R) and Z is B.

[0046] In a further aspect, the compound of the present invention preferably comprises at least one structure of formula (Ve-1) to (Ve-18); more preferably, the compound of the present invention is selected from the compounds of formula (Ve-1) to (Ve-18). [ka] [ka] [ka] where the subscripts s and v and the symbol Y 1 , Y 2 , Y 4 , Y 5 , X, Z, R, R a and R 1has the meaning given above, in particular in formula (I) or in formula (RB), the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, the index j is 0, 1 or 2, preferably 0 or 1 and the index k is 0 or 1, preferably 0, where the sum of the indices j, k and m is preferably 0, 1, 2, 3, 4, 5, 6, 7 or 8, more preferably 0, 1, 2, 3 or 4.

[0047] In a further aspect, the compound of the present invention preferably comprises at least one structure of formula (Vl-1) to (Vl-18); more preferably, the compound of the present invention is selected from the compounds of formula (Vl-1) to (Vl-18). [ka] [ka] [ka] where the subscripts s and v and the symbol Y 1 , Y 2 , Y 4 , Y 5 , X, Z, R, R a and R 1 has the meaning given above, in particular in formula (I) or in formula (RB), the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, the index n is 0, 1, 2 or 3, preferably 0, 1 or 2 and the index j is 0, 1 or 2, preferably 0 or 1, where the sum of the indices j, m and n is preferably 0, 1, 2, 3, 4, 5, 6, 7 or 8, more preferably 0, 1, 2, 3 or 4.

[0048] In addition, in formulas (I) and (IIa) to (IId), the subscript p 2 and p 3 The sum of is 1 or the subscript p 2 is 1 and Y 1 , Y 2 , Y3 At least one of the groups, preferably Y 1 , Y 2 , Y 3 two of the groups are B(Ar) or B(R), Z is N, and / or in formula (IIIb), (IVd) to (IVm), (Ve) to (Vp), (Ve-1) to (Ve-18) or (Vl-1) to (Vl-18), Y 1 , Y 2 At least one of the groups, preferably Y 1 , Y 2 This may be the case when both groups are B(Ar) or B(R) and Z is N.

[0049] Furthermore, in formulas (I) and (IIa) to (IId), the subscript p 2 and p 3 The sum of is 1 or the subscript p 2 is 1 and Y 1 , Y 2 , Y 3 At least one of the groups, preferably Y 1 , Y 2 , Y 3 two of the groups are N(Ar) or N(R), Z is B, and / or in (IIIb), (IVd) to (IVm), (Ve) to (Vp), (Ve-1) to (Ve-18) or (Vl-1) to (Vl-18), Y 1 , Y 2 At least one of the groups, preferably Y 1 , Y 2 This may be the case when both of the groups are N(Ar) or N(R) and Z is B.

[0050] The substituents R and R of the above formula a , R 1 and R 2 But R and R a , R 1 and R 2 This may be the case where R, R together with the ring atoms of the ring system to which they are attached do not form a fused aromatic or heteroaromatic ring system. a and R 1 Possible substituents R which may be attached to the radical 1and R 2 together to form a fused aromatic or heteroaromatic ring system.

[0051] Especially R, R a , R 1 and / or R 2 When two radicals, which may be selected from, together form a ring system, this ring system may be monocyclic or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic. In this case, the radicals which together form a ring system may be adjacent, that is, they may be bonded to the same carbon atom or to carbon atoms which are directly bonded to each other, or they may be further removed from each other. Furthermore, the substituents R, R a , R 1 and / or R 2 The ring systems provided in may be linked to each other by single bonds, which may result in ring closure. In this case, the respective corresponding binding sites are preferably R, R a , R 1 and / or R 2 Available in.

[0052] In a preferred form, the compounds of the present invention may be represented by at least one of the structures of formulae (I), (IIa)-(IId), (IIIa)-(IIIc), (IVa)-(IVu), (IVa-1)-(IVb-4), (IVe-1)-(IVh-4), (Va)-(Vz), (Va-1)-(Va-18), (Vc-1)-(Vc-18), (Ve-1)-(Ve-18) and / or (Vl-1)-(Vl-18). Preferably, the compounds of the present invention comprising the structures of formulae (I), (IIa) to (IId), (IIIa) to (IIIc), (IVa) to (IVu), (IVa-1) to (IVb-4), (IVe-1) to (IVh-4), (Va) to (Vz), (Va-1) to (Va-18), (Vc-1) to (Vc-18), (Ve-1) to (Ve-18) and / or (Vl-1) to (Vl-18) have a molecular weight of 5000 g / mol or less, preferably 4000 g / mol or less, particularly preferably 3000 g / mol or less, especially preferably 2000 g / mol or less, most preferably 1200 g / mol or less.

[0053] A further feature of the preferred compounds of the invention is that they are sublimable. These compounds generally have a molar mass of less than about 1200 g / mol.

[0054] Preferred aromatic or heteroaromatic ring systems R, R aand / or Ar is selected from the group consisting of phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta- or para-terphenyl or branched terphenyl, quaterphenyl, in particular ortho-, meta- or para-quaterphenyl or branched quaterphenyl, fluorene which may be bonded via the 1, 2, 3 or 4 positions, spirobifluorene which may be bonded via the 1, 2, 3 or 4 positions, naphthalene, in particular 1- or 2-bonded naphthalene, indole, benzofuran, benzothiophene, carbazole which may be bonded via the 1, 2, 3 or 4 positions, dibenzofuran which may be bonded via the 1, 2, 3 or 4 positions, dibenzothiophene which may be bonded via the 1, 2, 3 or 4 positions, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which may be selected from the group consisting of one or more R 1 and optionally substituted by a radical.

[0055] Preferably, at least one substituent R is identical or different at each occurrence and is selected from the group consisting of H, D, or an aromatic or heteroaromatic ring system selected from the groups of formulae Ar-1 to Ar-75 below, where the substituent R preferably forms a ring according to the structure of formulae (RA-1) to (RA-12) or (RB), or the substituent R is identical or different at each occurrence and is selected from an aromatic or heteroaromatic ring system selected from the groups of formulae Ar-1 to Ar-75 below, and / or the Ar group is identical or different at each occurrence and is selected from the groups of formulae Ar-1 to Ar-75 below. [ka] [ka] [ka] [ka] Here, R 1 is as described above, with the dotted lines indicating connection sites, and further: Ar 1 are identical or different at each occurrence and have 6 to 18 aromatic ring atoms, and in each case, one or more R 1 a divalent aromatic or heteroaromatic ring system, optionally substituted by radicals; A is the same or different for each occurrence, and C(R 1 ) 2 , N.R. 1 , O or S; p is 0 or 1, where p=0 is Ar 1 means that the group is absent and the corresponding aromatic or heteroaromatic group is directly bonded to HetAr; q is 0 or 1, where q=0 means that there is no A group attached at this position and R 1 It means that the radical is instead bonded to the corresponding carbon atom.

[0056] The above groups for Ar may have two or more A groups, and these possible options include all combinations of the definitions of A. A preferred embodiment in this case is where one A group is NR 1 and the other A group is C(R 1 ) 2 or both A groups are NR 1 or both A groups are O.

[0057] A is NR 1 When the substituent R 1 preferably has 5 to 24 aromatic ring atoms and one or more R 2 In a particularly preferred embodiment, R is an aromatic or heteroaromatic group, optionally substituted by a radical. 1The substituents, which may be the same or different at each occurrence, are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, in particular 6 to 18 aromatic ring atoms, which do not have fused aryl groups and which do not have fused heteroaryl groups, in which two or more aromatic or heteroaromatic 6-membered ring groups are bonded to each other, in each case one or more R 2 The preferred are phenyl, biphenyl, terphenyl and quaterphenyl having the bonding patterns shown in Ar-1 to Ar-11 above, and these structures are R 1 In addition, R of 1 or more 2 It may be substituted by a radical, and is preferably unsubstituted. More preferred are triazines, pyrimidines and quinazolines as shown above in Ar-47 to Ar-50, Ar-57 and Ar-58, the structures of which are represented by R 1 In addition, R of 1 or more 2 It may be substituted by a radical.

[0058] Preferred substituents R and R a The following describes this.

[0059] In a preferred embodiment of the invention, R is identical or different at each occurrence and is selected from the group consisting of H, D, F, CN, NO 2 , Si(R 1 ) 3 , B(OR 1 ) 2 , a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl group is in each case one or more R 1 or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, in each case one or more R 1 The aromatic or heteroaromatic group is optionally substituted by a radical.

[0060] In a further preferred embodiment of the invention, R is identical or different at each occurrence and is selected from the group consisting of H, D, F, a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl group is in each case selected from one or more R 1 or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, in each case one or more R 1 is selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by radicals.

[0061] In addition, at least one substituent R may be the same or different at each occurrence and may be H, D, 6 to 30 aromatic ring atoms, and one or more R 1 Aromatic or heteroaromatic ring systems, optionally substituted by radicals, and N(Ar) 2 In a further preferred embodiment of the invention, the substituents R form a ring according to the structure of formula (RA-1) to (RA-12) or (RB), or R is identical or different at each occurrence and has H, D, 6 to 30 aromatic ring atoms and one or more R 1 Aromatic or heteroaromatic ring systems, optionally substituted by radicals, and N(Ar) 2 More preferably, R is the same or different at each occurrence and is H or has 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, and in each case, one or more R 1 is selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by radicals.

[0062] In a preferred embodiment of the invention, R a are identical or different at each occurrence and are linear alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, where the alkyl group is, in each case, one or more R 1radicals), and having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, in each case one or more R 1 is selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by radicals.

[0063] In a further preferred embodiment of the invention, R a are identical or different at each occurrence and are linear alkyl groups having 1 to 10 carbon atoms or branched or cyclic alkyl groups having 3 to 10 carbon atoms, where the alkyl group is, in each case, one or more R 1 substituted with an aromatic ring atom, 6 to 30 aromatic ring atoms, and one or more R 1 More preferably, R is selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by radicals. a are identical or different at each occurrence and are linear alkyl groups having 1 to 5 carbon atoms or branched or cyclic alkyl groups having 3 to 5 carbon atoms, where the alkyl group is, in each case, one or more R 1 or 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, in each case one or more R 1 is selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by radicals.

[0064] In a preferred embodiment of the invention, R a are identical or different at each occurrence and are linear alkyl groups having 1 to 6 carbon atoms or cyclic alkyl groups having 3 to 6 carbon atoms, where the alkyl group is, in each case, one or more R 1 or 6 to 24 aromatic ring atoms, in each case one or more of R 1 and at the same time, two Ra The radicals may together form a ring system. More preferably, R a are identical or different at each occurrence and are linear alkyl groups having 1, 2, 3 or 4 carbon atoms or branched or cyclic alkyl groups having 3 to 6 carbon atoms, where the alkyl group is, in each case, one or more R 1 or having 6 to 12 aromatic ring atoms, in particular 6 aromatic ring atoms, in each case one or more preferably non-aromatic, R 1 and at the same time, two R a The radicals may together form a ring system. Most preferably, R a are the same or different at each occurrence and are selected from the group consisting of straight chain alkyl groups having 1, 2, 3 or 4 carbon atoms or branched alkyl groups having 3 to 6 carbon atoms. Most preferably, R a is a methyl group or a phenyl group, where two phenyl groups may together form a ring system, and is preferably a methyl group rather than a phenyl group.

[0065] Preferred aromatic or heteroaromatic ring systems R, R aor Ar is phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta- or para-terphenyl or branched terphenyl, quaterphenyl, in particular ortho-, meta- or para-quaterphenyl or branched quaterphenyl, fluorene which may be bonded via the 1, 2, 3 or 4 positions, spirobifluorene which may be bonded via the 1, 2, 3 or 4 positions, naphthalene, in particular 1- or 2-bonded naphthalene, indole, benzofuran, benzothiophene, carbazole which may be bonded via the 1, 2, 3 or 4 positions, dibenzofuran which may be bonded via the 1, 2, 3 or 4 positions, dibenzothiophene which may be bonded via the 1, 2, 3 or 4 positions, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which may be selected from the group consisting of one or more R 1 The structures Ar-1 to Ar-75 shown above are particularly preferred, and the structures of the formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), and (Ar-75) are preferred, and the structures of the formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16) are particularly preferred.

[0066] Further preferred R groups are of the formula -Ar 4 -N(Ar 2 )(Ar 3 ), where Ar 2 , Ar 3 and Ar 4 are identical or different at each occurrence and have 5 to 24 aromatic ring atoms, and in each case, one or more R 1 Ar is an aromatic or heteroaromatic ring system, optionally substituted by radicals. 2 , Ar 3 and Ar4 The total number of aromatic ring atoms in is 60 or less, preferably 40 or less.

[0067] In this case, Ar 4 and Ar 2 may be bonded to each other, and / or Ar 2 and Ar 3 is a single bond, C(R 1 ) 2 , N.R. 1 , O and S. Preferably, Ar 4 and Ar 2 to each other, or Ar 2 and Ar 3 to each other are in each case ortho to the position of the bond to the nitrogen atom, e.g., preferably a carbazole is formed. 2 , Ar 3 and Ar 4 None of the groups are bonded to each other.

[0068] Preferably, Ar 4 has 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms, and in each case, one or more R 1 More preferably, Ar is an aromatic or heteroaromatic ring system, optionally substituted by a radical. 4 is ortho-, meta-, or para-phenylene or ortho-, meta-, or para-biphenyl (each of which may be one or more R 1 Preferably, the alkyl group is selected from the group consisting of: 4 is an unsubstituted phenylene group.

[0069] Preferably, Ar 2 and Ar 3 are identical or different at each occurrence and have 6 to 24 aromatic ring atoms, and in each case, one or more R 1Ar is an aromatic or heteroaromatic ring system, optionally substituted by radicals. Particularly preferred is Ar 2 and Ar 3 The groups may be the same or different at each occurrence and include benzene, ortho-, meta- or para-biphenyl, ortho-, meta- or para-terphenyl or branched terphenyl, ortho-, meta- or para-quaterphenyl or branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene, 1-, 2-, 3- or 4-carbazole, 1-, 2-, 3- or 4-dibenzofuran, 1-, 2-, 3- or 4-dibenzothiophene, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2-, 4- or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene or triphenylene, each of which may be selected from the group consisting of one or more R 1 Most preferably, Ar is selected from the group consisting of 2 and Ar 3 are identical or different at each occurrence and are selected from the group consisting of benzene, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta- or para-terphenyl or branched terphenyl, quaterphenyl, in particular ortho-, meta- or para-quaterphenyl or branched quaterphenyl, fluorene, in particular 1-, 2-, 3- or 4-fluorene, or spirobifluorene, in particular 1-, 2-, 3- or 4-spirobifluorene.

[0070] In a further preferred embodiment of the invention, R 1 are identical or different at each occurrence and are H, D, F, CN, a linear alkyl group which may have 1 to 10 carbon atoms or a branched or cyclic alkyl group which may have 3 to 10 carbon atoms, where the alkyl group may in each case be one or more R 2or 6 to 24 aromatic ring atoms, in each case one or more of R 2 In a particularly preferred embodiment of the invention, R is selected from the group consisting of aromatic or heteroaromatic ring systems, optionally substituted by radicals. 1 are identical or different at each occurrence and are H, a linear alkyl group having 1 to 6 carbon atoms, in particular 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, where the alkyl group is one or more R 5 radicals, but preferably unsubstituted), or 6 to 13 aromatic ring atoms, in each case one or more R 5 The radical is selected from the group consisting of an aromatic or heteroaromatic ring system which may be substituted, but is preferably unsubstituted.

[0071] In a further preferred embodiment of the invention, R 2 is the same or different at each occurrence and is H, 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).

[0072] At the same time, in compounds of the invention processed by vacuum deposition, the alkyl groups preferably have 5 or fewer carbon atoms, more preferably 4 or fewer carbon atoms, and most preferably 1 or fewer carbon atoms. For compounds processed from solution, preferred compounds are those substituted with alkyl groups having up to 10 carbon atoms, especially branched alkyl groups, or oligoarylene groups, such as ortho-, meta- or para-terphenyl or branched terphenyl or quaterphenyl groups.

[0073] Furthermore, it may be a compound comprising exactly two or exactly three structures of formula (I), (IIa) to (IId), (IIIa) to (IIIc), (IVa) to (IVu), (IVa-1) to (IVb-4), (IVe-1) to (IVh-4), (Va) to (Vz), (Va-1) to (Va-18), (Vc-1) to (Vc-18), (Ve-1) to (Ve-18) and / or (Vl-1) to (Vl-18), wherein preferably Y 1 , Y 2 , Y 3 One of the groups, or Y 1 , Y 2 , Y 3 One of the aromatic or heteroaromatic ring systems to which at least one of the groups is attached is shared by both structures.

[0074] In a preferred embodiment, the compound comprises at least one of the structures of formulae (D-1) to (D-4), where the compound more preferably conforms to formulae (D-1) to (D-4). [ka] [ka] Here, Y 2a is C or Si, and L 1 The group represents a linking group, preferably a bond or a group having 5 to 40, preferably 5 to 30, aromatic ring atoms and one or more R 1 an aromatic or heteroaromatic ring system, optionally substituted by radicals, the further symbols and indices used having the meanings given above, in particular in formula (I).

[0075] In a further preferred embodiment of the invention, L 1 is a bond or an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having 6 to 12 carbon atoms, which may be one or more R 1 It may be substituted by a radical, but is preferably unsubstituted, where R 1may have the meaning given above, especially in formula (I). More preferably, L 1 is an aromatic ring system having 6 to 10 aromatic ring atoms, or an aromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which may be represented by one or more R 2 It may be substituted by a radical, but is preferably unsubstituted, where R 2 may have the meaning given above, especially in formula (I).

[0076] More preferably, the symbol L shown in the formula (D4) 1 is identical or different on each occurrence and is a bond or an aryl or heteroaryl radical having 5 to 24 ring atoms, preferably 6 to 13 ring atoms and more preferably 6 to 10 ring atoms, in which the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is bonded directly, i.e. via an atom of the aromatic or heteroaromatic group, to the respective atom of the further group.

[0077] Furthermore, L shown in formula (D4) 1 The group may be the case of comprising an aromatic ring system having up to two fused aromatic and / or heteroaromatic 6-membered rings, preferably without fused aromatic or heteroaromatic ring systems. Thus, naphthyl structures are preferred over anthracene structures. Furthermore, fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structures are preferred over naphthyl structures.

[0078] Particularly preferred are non-fused structures, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0079] Suitable aromatic or heteroaromatic ring systems L 1Examples of are selected from the group consisting of ortho-, meta- or para-phenylene, ortho-, meta- or para-biphenylene, terphenylene, particularly branched terphenylene, quaternary phenylene, particularly branched quaternary phenylene, fluorenylene, spirobifluorenylene, dibenzofuranylene, dibenzothienylene, and carbazolylene, each of which may be selected from the group consisting of one or more R 1 The radicals may be substituted, but are preferably unsubstituted.

[0080] The above preferred aspects may optionally be combined with one another, subject to the limitations of claim 1. In a particularly preferred embodiment of the invention, the above preferred aspects occur simultaneously.

[0081] Examples of preferred compounds according to the above aspects are those shown in the table below. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0082] Preferred forms of the compounds of the invention are specifically illustrated in the Examples, and these compounds can be used alone or in combination with further compounds for all purposes of the invention.

[0083] The preferred embodiments described above can be combined with one another if desired, provided that the conditions specified in claim 1 are met. In a particularly preferred embodiment of the invention, the preferred embodiments described above are applied simultaneously.

[0084] The compounds of the invention can in principle be prepared in a variety of ways, however the methods described below have been found to be particularly suitable.

[0085] Thus, the present invention relates to a method for preparing a base skeleton having a Z group or a precursor of a Z group, which is then reacted with Y 1 , Y 2 , Y3 is introduced by a nucleophilic aromatic substitution reaction or a coupling reaction.

[0086] Suitable compounds comprising at least one heterocyclic structure are often commercially available, whereby the starting compounds detailed in the examples can be obtained by known methods, as referenced therein.

[0087] These compounds can be reacted with further compounds comprising at least one aromatic or heteroaromatic group in known coupling reactions, the conditions necessary for this purpose are well known to those skilled in the art and the detailed descriptions in the examples will assist those skilled in the art in carrying out these reactions.

[0088] Particularly suitable and preferred coupling reactions resulting in CC bond formation and / or CN bond formation are those according to Buchwald, Suzuki, Yamamoto, Stille, Heck, Negishi, Sonogashira and Hiyama. These reactions are well known and the examples provide further guidance to the skilled artisan.

[0089] The basics of the preparation methods detailed above are in principle known from the literature for analogous compounds and can be readily adapted by those skilled in the art to the preparation of the compounds of the invention. Further information can be found in the Examples.

[0090] By these methods, optionally followed by purification, such as recrystallization or sublimation, the compounds of the present invention can be obtained in high purity, preferably greater than 99% ( 1 H-NMR and / or HPLC).

[0091] The compounds of the present invention can also be mixed with polymers. It is also possible to covalently incorporate these compounds into polymers. This is especially possible for compounds substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic ester, or with reactive polymerizable groups such as olefins or oxetanes. They find use as monomers for producing the corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization is preferably carried out via halogen or boronic acid functional groups, or via polymerizable groups. It is possible to further crosslink the polymer via such groups. The compounds and polymers of the present invention can be used in the form of crosslinked or non-crosslinked layers.

[0092] The present invention further provides polymers, oligomers or dendrimers comprising one or more of the structures of formula (I) and preferred forms of this formula or compounds of the present invention as detailed above, in which there are one or more bonds to the compounds of the present invention or to the structures of formula (I) and preferred forms of this formula, in the polymer, oligomer or dendrimer. By linking the structures of (I) and preferred forms of this formula or compounds, they therefore form side chains of the polymer or oligomer or are linked within the main chain. The polymers, oligomers or dendrimers may be conjugated, partially conjugated or not conjugated. The oligomers or polymers may be linear, branched or dendritic. For the repeat units of the compounds of the present invention in the oligomers, dendrimers and polymers, the same preferred forms apply as described above.

[0093] To prepare oligomers or polymers, the monomers of the invention are homopolymerized or copolymerized with further monomers. The units of formula (I) or the preferred forms described above and below are preferably present in the range of 0.01 to 99.9 mol %, preferably 5 to 90 mol %, more preferably 20 to 80 mol %. Suitable and preferred comonomers forming the polymer backbone are fluorenes (for example according to EP 842208 or WO 2000 / 022026), spirobifluorenes (for example according to EP 707020, EP 894107 or WO 2006 / 061181), paraphenylenes (for example according to WO 92 / 18552), carbazoles (for example according to WO 2004 / 070772 or WO 2004 / 113468), thiophenes ( For example, according to EP1028136), dihydrophenanthrenes (for example, according to WO2005 / 014689), cis- and trans-indenofluorenes (for example, according to WO2004 / 041901 or WO2004 / 113412), ketones (for example, according to WO2005 / 040302), phenanthrenes (for example, according to WO2005 / 104264 or WO2007 / 017066), or a plurality of these units. The polymers, oligomers and dendrimers may also contain further units, for example hole transport units, in particular those based on triarylamines, and / or electron transport units.

[0094] Furthermore, of particular interest are compounds of the invention characterized by a high glass transition temperature.In this connection, preferred are compounds of the invention comprising the structure of formula (I) or the preferred forms described above and below, which have a glass transition temperature (measured according to DIN 51005 (2005-08 edition)) of at least 70°C, more preferably at least 110°C, even more preferably at least 125°C, particularly preferably at least 150°C.

[0095] To process the compounds of the invention in liquid phase, for example by spin-coating or printing methods, a formulation of the compounds of the invention is required. These formulations can be, for example, solutions, dispersions or emulsions. For this purpose, it is preferable to use a mixture of two or more solvents. 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, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene. , phenetole, 1,4-diisopropylbenzene, dibenzyl 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.

[0096] Therefore, the present invention further relates to a formulation or composition comprising at least one compound of the present invention and at least one further compound. The further compound is, for example, a solvent, in particular one of the above-mentioned solvents, or a mixture of these solvents. If the further compound comprises a solvent, then this mixture is referred to as a formulation. Alternatively, the further compound can be at least one further organic or inorganic compound also used in electronic devices, for example, a light emitter and / or a matrix material, where these compounds are different from the compound of the present invention. Suitable light emitters and matrix materials are described below in the context of organic electroluminescent devices. This further compound can also be a polymer, optionally with groups for further crosslinking.

[0097] Therefore, the present invention further provides a composition comprising the compound of the present invention and at least one additional organic functional material.The functional material is generally an organic or inorganic material that is introduced between anode and cathode.Preferably, the organic functional material is selected from the group consisting of fluorescent emitter, phosphorescent emitter, emitter that shows TADF (thermally activated delayed fluorescence), host material, electron transport material, electron injection material, hole conducting material, hole injection material, electron blocking material, hole blocking material, wide gap material and n-dopant.

[0098] The present invention further provides the use of the compounds of the present invention in electronic devices, particularly organic electroluminescent devices, preferably as emitters, more preferably as blue emitters.In this case, the compounds of the present invention preferably exhibit fluorescent properties, thus providing selective fluorescent emitters.Furthermore, the compounds of the present invention may be used for the conversion of light in color converters.

[0099] The present invention further provides an electronic device comprising at least one compound according to the invention.In the sense of the present invention, an electronic device is a device comprising at least one layer comprising at least one organic compound.This component may also comprise other layers made of inorganic materials or entirely of inorganic materials.

[0100] The electronic device is preferably selected from the group consisting of, more preferably selected from the group consisting of organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), preferably organic light emitting diodes (OLEDs), small molecule based organic light emitting diodes (sOLED), polymer based organic light emitting diodes (PLED), light emitting electrochemical cells (LEC), organic laser diodes (O-laser), organic plasma light emitting devices (DM Koller et al., Nature Photonics 2008, 1-4), 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), organic photodetectors, organic photoreceptors, organic field quenchers (O-FQDs), organic electronic sensors, preferably organic electroluminescent devices (OLEDs, sOLEDs, PLEDs, LECs, etc.), more preferably organic light emitting diodes (OLEDs), small molecule based organic light emitting diodes (sOLEDs), polymer based organic light emitting diodes (PLEDs), and in particular phosphorescent OLEDs.

[0101] The organic electroluminescent device comprises a cathode, an anode, and at least one light-emitting layer. Besides these layers, it may also comprise further 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 generating layers. For example, an intermediate layer with exciton blocking functionality may be introduced between two light-emitting layers as well. Similarly, an intermediate layer with exciton blocking functionality, for example, introduced between two light-emitting layers, is also possible. However, it should be pointed out that each of these layers does not necessarily have to be present. In this case, it is possible for the organic electroluminescent device to comprise a light-emitting layer, or multiple light-emitting layers. If multiple light-emitting layers are present, they preferably have multiple emission maxima in the range from 380 nm to 750 nm as a whole, resulting in a white light emission as a whole, i.e., various light-emitting compounds capable of emitting fluorescence or phosphorescence are used in the light-emitting layers. Particularly preferred is a system having three light-emitting layers, the three layers exhibiting blue, green and orange or red emission.The organic electroluminescent device according to the invention may be a series OLED, in particular for white emission.

[0102] The compounds of the invention may be used in different layers depending on the exact structure.Preferably, an organic electroluminescent device comprises a compound of formula (I) or the preferred forms described above as emitter, preferably as blue emitter, in the light-emitting layer.

[0103] When the compounds according to the invention are used as emitters in a light-emitting layer, known suitable matrix materials are preferably used.

[0104] A preferred mixture of the compound of the invention and the matrix material comprises 99% to 1% by volume, preferably 98% to 10% by volume, more preferably 97% to 60% by volume, in particular 95% to 80% by volume of the matrix material, based on the entire mixture of the phosphor and the matrix material. Correspondingly, the mixture comprises 1% to 99% by volume, preferably 2% to 90% by volume, more preferably 3% to 40% by volume, in particular 5% to 20% by volume of the phosphor, based on the entire mixture of the phosphor and the matrix material.

[0105] Suitable matrix materials which may be used in combination with the compounds of the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g. according to WO2004 / 013080, WO2004 / 093207, WO2006 / 005627 or WO2010 / 006680, triarylamines, carbazole derivatives, e.g. CBP (N,N-biscarbazolylbiphenyl) or compounds according to WO2005 / 039246, US2005 / 0069729, JP2004 / 288381, EP1205527, WO2008 / carbazole derivatives as disclosed in 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, JP 2005 / 347160, bipolar matrix materials, for example according to WO 07 / 137725, silanes, e.g. according to WO 2005 / 111172, azaboroles or boronic 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, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, diazasilol or tetraazasilol derivatives, e.g. according to WO 2010 / 05 4729, diazaphosphole derivatives, for example according to WO2010 / 054730, bridged carbazole derivatives, for example according to WO2011 / 042107, WO2011 / 060867, WO2011 / 088877 and WO2012 / 143080, triphenylene derivatives, for example according to WO2012 / 048781, dibenzofuran derivatives, for example according to WO2015 / 169412, WO2016 / 015810, WO2016 / 023608, WO2017 / 148564 or WO2017 / 148565, and also bizcarbazoles,For example according to JP 3139321 B2. Further preferred matrix or host materials are anthracenes. Particularly preferred anthracenes are disclosed in WO 2014 / 106523 A1, very particularly preferably of formula (II). Further particularly preferred anthracenes are disclosed in WO 2007 / 065547 A1, very particularly preferably of formula (2) and (3), in particular of formula (A1) to (A64). Further particularly preferred anthracenes are disclosed in WO 2007 / 065548 A1, very particularly preferably of formula (1), in particular of formula H1 to H20.

[0106] Furthermore, the co-host used may be a compound that does not participate to a significant extent, if at all, in charge transport, as disclosed, for example, in WO2010 / 108579. Particularly suitable for combination with the compounds of the present invention as co-matrix materials are compounds that have a large band gap and do not participate to a significant extent, if at all, in charge transport of the light-emitting layer. Such materials are preferably purely hydrocarbons. Examples of such materials can be found, for example, in WO2009 / 124627 or WO2010 / 006680.

[0107] In a preferred embodiment, the compounds of the invention used as emitters are preferably used in combination with one or more phosphorescent emitters (triplet emitters) and / or compounds which are TADF (thermally activated delayed fluorescence) host materials, preferably forming hyperfluorescent and / or hyperphosphorescent systems.

[0108] WO2015 / 091716A1 and WO2016 / 193243A1 disclose OLEDs that contain both phosphorescent compounds and fluorescent emitters in the emitting layer, and energy is transferred from the phosphorescent compound to the fluorescent emitter (hyperphosphorescence).In this sense, the phosphorescent compound therefore acts as a host material.As those skilled in the art know, in order to allow the energy from the host material to be transferred to the emitter with maximum efficiency, the host material has higher singlet and triplet energy compared to the emitter.The systems disclosed in the prior art have just such an energy relationship.

[0109] In the sense of the present invention, phosphorescence is understood to mean luminescence from excited states, in particular excited triplet states, having a higher spin multiplicity, i.e. a spin state > 1. In the sense of the present application, all luminescent complexes containing transition metals or lanthanides, in particular all iridium, platinum and copper complexes, are to be considered as phosphorescent compounds.

[0110] Suitable phosphorescent compounds (=triplet emitters) are in particular compounds which emit light when appropriately excited, preferably in the visible range, and which furthermore comprise at least one atom, in particular a metal with 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 which comprise copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds which comprise iridium or platinum.

[0111] Examples of such luminophores are described in applications WO00 / 70655, WO2001 / 41512, WO2002 / 02714, WO2002 / 15645, EP1191613, EP1191612, EP1191614, WO05 / 033244, WO05 / 019373, US2005 / 0258742, WO2009 / 146770, WO2010 / 015307, WO 2010 / 031485, WO2010 / 054731, WO2010 / 054728, WO2010 / 086089, WO2010 / 099852, WO2010 / 102709 , WO2011 / 032626, WO2011 / 066898, WO2011 / 157339, WO2012 / 007086, WO2014 / 008982, WO2014 / 023 377, WO2014 / 094961, WO2014 / 094960, WO2015 / 036074, WO2015 / 104045, WO2015 / 117718, WO2016 / 015815, WO2016 / 124304, WO2017 / 032439, WO2018 / 011186, WO2018019687, WO2018019688, WO2018 041769, WO2018054798, WO2018069196, WO2018069197, WO2018069273, WO2018134392, WO2018178001, WO2018177981, WO2019020538, WO2019115423, WO2019158453 and WO2019179909. In general, all phosphorescent complexes as used in the prior art in the field of phosphorescent electroluminescent devices and known to a person skilled in the art in the field of organic electroluminescent devices are suitable, and a person skilled in the art can use further phosphorescent complexes without inventive ingenuity.

[0112] The compounds of the present invention may preferably be used in combination with the TADF host materials and / or TADF emitters described above.

[0113] The process for thermally activated delayed fluorescence (TADF) is disclosed, for example, in BHUoyama et al., Nature 2012, Vol. 492, 234. To enable this process, for example, -1 Relatively low singlet-triplet separation ΔE(S 1 -T 1 ) is required for the emitter. In principle, the spin-forbidden T 1 →S 1 To broaden the transition, the matrix can be provided with further compounds with spin-orbit coupling, as well as the emitter, whereby the intersystem separation is achieved by spatial proximity or possible interactions between the molecules, or the spin-orbit coupling occurs via metal atoms present in the emitter.

[0114] In a further embodiment of the present invention, the organic electroluminescent device of the present invention does not include a hole injection layer and / or a hole transport layer and / or a hole blocking layer and / or an electron transport layer, which means that the light emitting layer is directly adjacent to the hole injection layer or the anode, and / or the light emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO2005 / 053051.Furthermore, the same or similar metal complex as the metal complex in the light emitting layer can also be used as a hole transport or hole injection material directly adjacent to the light emitting layer, as described, for example, in WO2009 / 030981.

[0115] In the further layer of the organic electroluminescent device of the present invention, any material as is usually used according to the prior art can be used.Therefore, those skilled in the art can use any material known for organic electroluminescent devices in combination with the compound of the present invention according to formula (I) or the above preferred form without inventive ingenuity.

[0116] More preferably, it is an organic electroluminescent device in which one or more layers are coated by a sublimation process. In this case, the material is -5Less than mbar, preferably less than 10 -6 It is applied by deposition in a vacuum sublimation system at an initial pressure of less than 10 mbar. The initial pressure may be lower, for example 10 -7 It may be less than mbar.

[0117] Also preferred are organic electroluminescent devices, characterized in that one or more layers are deposited by using the OVPD (organic vapor phase deposition) method or by means of carrier gas sublimation. In this case, the material is preferably 10 -5 It is applied at pressures of mbar to 1 bar. A special method of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and thus structured. See for example MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301.

[0118] Furthermore, organic electroluminescent devices are preferred, 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 or nozzle printing, particularly preferably by LITI (Light Induced Thermal Imaging, Thermal Transfer Printing) or inkjet printing. For this purpose, soluble compounds are required, which can be obtained, for example, via suitable substitution.

[0119] The formulations in which the compounds of formula (I) or the preferred forms thereof as described above are applied are novel.Thus, the present invention further provides a formulation comprising at least one solvent and a compound of formula (I) or the preferred forms thereof as described above.

[0120] Furthermore, hybrid methods are also possible, where, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.

[0121] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices comprising the compounds of the invention without the need for inventive skill.

[0122] The compounds of the present invention and the organic electroluminescent device of the present invention have the special feature of improved lifetime compared to the prior art.At the same time, the further electronic properties of electroluminescent device, such as efficiency or operating voltage, remain at least as good.In a further variant, the compounds of the present invention and the organic electroluminescent device of the present invention are characterized by improved efficiency and / or operating voltage and longer lifetime, in particular, compared to the prior art.

[0123] The electronic devices, in particular organic electroluminescent devices, of the present invention are notable for one or more of the following surprising advantages over the prior art: 1. Electronic devices, in particular organic electroluminescent devices, comprising the formula (I) or the preferred forms described above and below as emitters have a very low emission band with low FWHM (Full Width Half Maximum) values ​​and in particular produce pure color emission, recognizable by low CIEy values. 2. The electronic device, particularly the organic electroluminescent device, comprising (I) or the preferred forms described above and below as emitters has excellent efficiency.In this sense, the compound of the present invention (I) or the preferred forms described above and below provides low operating voltage when used in electronic devices. 3. Using the compounds of formula (I) or the preferred forms described above and below, the formation of light loss channels can be avoided in electronic devices, particularly organic electroluminescent devices.As a result, these devices are characterized by high PL efficiency and high EL efficiency of the emitter and excellent energy transfer to the dopant of the material. 4. Compounds of formula (I) or the preferred forms described above and below have excellent glass film formation. 5. Compounds of formula (I) or the preferred forms described above and below form very good films from solution and exhibit excellent solubility.

[0124] The above advantages are not accompanied by excessively high degradation of further electronic properties.

[0125] It should be noted that the variations of the embodiments described in the present invention are included within the scope of the present invention. Each feature disclosed in the present invention may be replaced with an alternative feature that fulfills the same purpose or an equivalent or similar purpose, unless this is explicitly excluded. Therefore, each feature disclosed in the present invention should be considered as an example of a general series, or an equivalent or similar feature, unless otherwise specified.

[0126] All features of the present invention can be combined with one another in any way, unless the particular features and / or steps are mutually exclusive. This is particularly true for the preferred features of the present invention. Similarly, features of non-essential combinations can be used separately (and not in combination).

[0127] It should be noted that many features, particularly those of the preferred forms of the invention, should be considered inventive in their own right and not merely as part of the forms of the invention, and that independent protection may be sought for these features in addition to or as an alternative to the invention presently claimed.

[0128] The technical teachings disclosed with the present invention may be abstracted and combined with other embodiments.

[0129] The present invention is described in more detail in the following examples, but is not limited thereby. Using the details described, a person skilled in the art will be able to prepare further compounds according to the present invention, use them in electronic devices, and thereby practice the present invention throughout the scope of the claims, without the need for inventive ingenuity.

[0130] Working Example: The following syntheses are carried out in dry solvents under protective gas atmosphere unless otherwise stated. Metal complexes are further handled in the dark or under yellow light. Solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. Each number in brackets or the number shown for the individual compounds refers to the CAS number of the literature-known compound. When a compound has multiple enantiomeric, diastereomeric or tautomeric forms, one form is shown in a representative manner.

[0131] Synthesis of synthon S: Example S1: [ka] 27.2 g (100 mmol) of 2-bromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-97-4], 32.4 g (100 mmol) of 2-(6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononen-2-yl)-4,4,5,5-tetrahydro-4,4,5,5-tetramethyl-2,5-diphenyl-1,2-dioxane [1801624-97-4] A well-stirred mixture of methyl-1,3,2-dioxaborolane [1801624-63-4], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 350 ml of toluene, 80 ml of dioxane and 300 ml of water is heated under reflux for 16 hours. After cooling, the organic phase is separated from the aqueous phase, washed once with 300 ml of water, once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The desiccant is filtered using a silica gel bed in the form of a toluene slurry and the filtrate is concentrated to dryness. The glassy residue is recrystallized in isopropanol. Yield: 30.8 g (78 mmol) 78%. Purity: 1 Approximately 97% by H NMR.

[0132] The following compounds may be prepared similarly: [ka] [ka]

[0133] Example S50: [ka] To a well-stirred solution of 39.5 g (100 mmol) of S1 in 500 ml of dichloromethane, 100 mg of iron powder is added, followed by dropwise addition of a mixture of 6.4 ml (240 mmol) of bromine and 100 ml of dichloromethane in the dark over a period of 3 hours. After the addition is complete, the mixture is stirred under reflux for 4 hours and at room temperature for 8 hours. 200 ml of saturated sodium sulfite solution is added to remove excess bromine, the organic phase is separated, washed with 500 ml of water and 300 ml of saturated sodium bicarbonate solution, and dried over magnesium sulfate. The drying agent is filtered off, the filtrate is concentrated to dryness, and the red viscous residue is recrystallized in about 500 ml of isopropanol. Yield: 33.7 g (61 mmol) 61%; purity: about 97% 1 By H NMR.

[0134] The following compounds may be prepared similarly: [ka]

[0135] Example S100: [ka] Similar procedure to K. Nozaki et al., Angew. Chem., IE, 42(18), 2051-2053, 2003. To a well-stirred mixture of 55.2 g (100 mmol) of S50, 16.4 g (110 mmol) of 4-tert-butylaniline [769-92-6], 24.1 g (250 mmol) of sodium tert-butoxide in 1000 ml of toluene, 405 mg (2 mmol) of tri-tert-butylphosphine [131274-22-1], and 404 mg (1.8 mmol) of palladium(II) acetate are added, and the mixture is stirred at 80° C. for 24 hours. After cooling, the reaction mixture is washed three times with 500 ml of water each. The organic phase is dried over magnesium sulfate, which is filtered off from them through a bed of silica gel in the form of a toluene slurry, and the filtrate is concentrated to dryness under reduced pressure. The residue is subjected to flash chromatography, silica gel, n-heptane / ethyl acetate, A. Semarau's Torrent automated column system. Yield: 36.3 g (67 mmol) 67%; purity: about 97% 1 By H NMR.

[0136] The following compounds may be prepared similarly: [ka] [ka]

[0137] Example S150: [ka] To a well-stirred mixture of 36.8 g (100 mmol) of 1,2,3,5-tetrahydro-1,1,2,2,3,3-hexamethyl-8-phenylcyclopenta[b]carbazole [2082697-87-6], 16.4 g (110 mmol) of 4-tert-butylaniline [769-92-6], 12.1 g (125 mmol) of sodium tert-butoxide in 1000 ml of toluene, 405 mg (2 mmol) of tri-tert-butylphosphine [131274-22-1], and 404 mg (1.8 mmol) of palladium(II) acetate are added, and the mixture is stirred for 16 hours at 100° C. After cooling, the reaction mixture is washed three times with 500 ml of water each. The organic phase is dried over magnesium sulfate, which is filtered off from them through a bed of silica gel in the form of a toluene slurry, and the filtrate is concentrated to dryness under reduced pressure. The residue is subjected to flash chromatography, silica gel, n-heptane / ethyl acetate, A. Semarau's Torrent automated column system. Yield: 43.9 g (88 mmol) 88%; purity: about 97% 1 By H NMR.

[0138] The following compounds may be prepared similarly: [ka] [ka]

[0139] Example S200: [ka] To a well-stirred mixture of 54.0 g (100 mmol) of S100, 1000 ml of glacial acetic acid and 1000 ml of dichloromethane (DCM) is added dropwise a mixture of 10.8 ml (210 mmol) of bromine and 200 ml of DCM in the dark at room temperature, and the mixture is stirred for another 24 h. 200 ml of saturated sodium sulfite solution and 500 ml of water are added, the organic phase is separated and washed three times with 500 ml each of water and once with saturated sodium chloride solution. 500 ml of methanol is added and the DCM is distilled off under reduced pressure while the product crystallizes. The crystals are suction filtered, washed three times with 100 ml each of methanol and dried under reduced pressure. Recrystallization from toluene or acetonitrile with the addition of DCM. T~180°C, p~10 -3 Drying at mbar. Yield: 62.8 g (90 mmol) 90%; Purity: approx. 97% 1 By H NMR.

[0140] The following compounds may be prepared similarly: [ka] [ka] [ka]

[0141] Example S250: [ka] To a well-stirred mixture of 27.2 g (100 mmol) of 2-bromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-97-4], 5.3 g (50 mmol) of 4-methylaniline [106-49-0], 24.2 g (250 mmol) of sodium tert-butoxide in 600 ml of toluene, 405 mg (2 mmol) of tri-tert-butylphosphine [131274-22-1], and 404 mg (1.8 mmol) of palladium(II) acetate are added, and the mixture is stirred for 16 hours at 110° C. After cooling, the reaction mixture is washed three times with 500 ml of water each. The organic phase is dried over magnesium sulfate, which is filtered off from them through a bed of silica gel in the form of a toluene slurry, and the filtrate is concentrated to dryness under reduced pressure. The residue is subjected to flash chromatography, silica gel, n-heptane / ethyl acetate, A. Semarau's Trent automated column system. Yield: 20.0 g (41 mmol) 82%; purity: about 97% 1 By H NMR.

[0142] The following compounds may be prepared similarly: [ka] [ka]

[0143] Example S300: [ka] To a well-stirred mixture of 50.0 g (100 mmol) of S250 in 500 ml of THF, in the dark at +5°C, 35.6 g (200 mmol) of N-bromosuccinimide are added in portions and the mixture is stirred for another 4 h. THF is mostly removed under reduced pressure, 300 ml of methanol are added, the mixture is stirred for another 30 min, the crude product is suction filtered, washed three times with 50 ml of methanol each and dried under reduced pressure. Purification is performed by recrystallization from acetonitrile with the addition of DCM or by flash chromatography, silica gel, n-heptane / ethyl acetate, A. Semrau's Trent automated column system. T~160°C, p~10 -3 Drying at mbar. Yield: 48.0 g (73 mmol) 73%; Purity: approx. 95% 1 By H NMR.

[0144] The following compounds may be prepared similarly: [ka] [ka]

[0145] Example S400: [ka] To a well-stirred mixture of 13.6 g (50 mmol) of 2-bromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-97-4], 13.9 g (50 mmol) of 2-amino-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-97-4], 5.8 g (60 mmol) of sodium tert-butoxide in 300 ml of toluene, 732 mg (1 mmol) of bis(diphenylphosphino)ferrocenepalladium(II) chloride [72287-62-4] is added, and the mixture is stirred at 110° C. for 16 hours. After cooling, the reaction mixture is washed three times with 500 ml of water each time. The organic phase is dried over magnesium sulfate, which is filtered off from them through a bed of silica gel in the form of a toluene slurry, and the filtrate is concentrated to dryness under reduced pressure. The residue is subjected to flash chromatography, silica gel, n-heptane / ethyl acetate, A. Semarau's Trent automated column system. Yield: 18.4 g (45 mmol) 90%; purity: about 97% 1 By H NMR.

[0146] The following compounds may be prepared similarly: [ka] [ka] [ka] [ka]

[0147] Example S450: [ka] 45.1 g (110 mmol) of S400, 11.3 g (50 mmol) of 1-bromo-2,3-dichlorobenzene [56961-77-4], 12.5 g (130 mmol) of sodium tert-butoxide [865-48-5], 354 mg (0.5 mmol) of amphos 2 PdCl 2 A mixture of [887919-35-9] and 200 ml of o-xylene is stirred at 80 ° C for 3 hours and at 130 ° C for 6 hours. After cooling, the reaction mixture is mixed with 500 ml of ethyl acetate and 500 ml of water, the organic phase is removed, washed once with 500 ml of water and three times with 300 ml each of saturated sodium chloride solution and dried over magnesium sulfate. The mixture is filtered through a silica gel bed in the form of an ethyl acetate slurry, the filtrate is concentrated to dryness, the residue is boiled with 300 ml of ethanol, the solids are filtered off, they are washed twice with 50 ml of ethanol and dried under reduced pressure. Yield: 29.3 g (31.5 mmol) 63%; purity: about 95% 1 By H NMR.

[0148] The following compounds may be prepared similarly: [ka] [ka] [ka] [ka] [ka] [ka]

[0149] Example dopant D1: The following sequence is carried out as a three-stage one-pot reaction. Step 1: Lithiation of S200 [ka] A baked out, argon inerted four-neck flask equipped with a magnetic stir bar, dropping funnel, water separator, reflux condenser and argon blanket is charged with 34.9 g (50 mmol) of S200 in 1700 ml of tert-butylbenzene. The reaction mixture is cooled to -40°C and 110.5 ml (210 mmol) of tert-butyllithium, 1.9 M in n-pentane, is added dropwise. The mixture is stirred at -40°C for a further 30 minutes, allowed to return to room temperature and heated to 70°C while n-pentane is distilled off on the water separator over about 1 hour.

[0150] Step 2: Transmetallation and cyclization [ka] The reaction mixture is cooled to -40°C. 10.4 ml (110 mmol) of boron tribromide are added dropwise over about 10 minutes. After the addition is complete, the reaction mixture is stirred at room temperature for 1 hour. The reaction mixture is cooled to 0°C and 19.2 ml (110 mmol) of diisopropylethylamine are added dropwise over about 30 minutes. The reaction mixture is stirred at 160°C for 16 hours. After cooling, the diisopropylethylammonium hydrobromide is suction filtered using a double-ended frit and the filtrate is cooled to -78°C.

[0151] Step 3: Arylation to D1 [ka] A twice baked out argon inerted Schrenko flask equipped with a magnetic stir bar is charged with 27.8 g (150 mmol) of 2-bromo-1,3-dimethylbenzene [576-22-7] in 1000 ml of diethyl ether and cooled to -78 °C. 60.0 ml (150 mmol) of n-butyllithium, 2.5 M in n-hexane, is added dropwise to it over about 20 minutes; and the mixture is stirred for another 30 minutes. The reaction mixture is warmed to room temperature and the solvent is completely removed under reduced pressure. The lithium organyl is suspended in 300 ml of toluene and transferred to the cold reaction mixture from step 2. The mixture is stirred for another hour, and the reaction mixture is allowed to warm to room temperature overnight. 15 ml of acetone is carefully added to the reaction mixture and concentrated to dryness. The oily residue is taken up in DCM on ISOLUTE™ and hot filtered through a bed of silica gel with a n-pentane-DCM mixture (10:1). The filtrate is concentrated to dryness. The residue is subjected to two flash chromatography steps: silica gel, n-heptane / ethyl acetate, A. Semarau's Trent automated column system. Further purification is performed by repeated hot extraction with acetonitrile and final fractional sublimation or thermal treatment under reduced pressure. Yield: 16.1 g (21 mmol) 42%; purity: about 99.9% 1 By H NMR.

[0152] The following compounds may be prepared similarly: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0153] Example dopant D100: Step 1: Lithiation of S450 [ka] A baked out, argon inerted four-neck flask equipped with a magnetic stir bar, dropping funnel, water separator, reflux condenser and argon blanket is charged with 46.4 g (50 mmol) of S450 and 200 ml of tert-butylbenzene and cooled to -40° C. 64.7 ml (110 mmol) of tert-butyllithium, 1.7 M in n-pentane, is added dropwise to the mixture over 10 minutes. The reaction mixture is allowed to warm to room temperature and stirred at 60° C. for a further 3 hours, during which time n-pentane is distilled off on a water separator over about 1 hour.

[0154] Step 2: Transmetallation and cyclization [ka] The reaction mixture is cooled to -40°C. 5.7 ml (60 mmol) of boron tribromide are added dropwise over about 10 minutes. After the addition is complete, the reaction mixture is stirred at room temperature for 1 hour. The reaction mixture is cooled to 0°C and 21.0 ml (120 mmol) of diisopropylethylamine are added dropwise over about 30 minutes. The reaction mixture is stirred at 130°C for 5 hours. After cooling, the mixture is diluted with 500 ml of toluene, hydrolyzed by adding 300 ml of 10% by weight aqueous potassium acetate solution, the organic phase is removed under reduced pressure and concentrated to dryness. The oily residue is taken up in DCM on ISOLUTE™ and hot filtered through a silica gel bed with a n-pentane-DCM mixture (10:1). The filtrate is concentrated to dryness. The residue is subjected to flash chromatography twice: silica gel, n-heptane / ethyl acetate, A. Semarau's Trent automated column system. Further purification is achieved by repeated hot extraction with acetonitrile and final fractional sublimation or heat treatment under reduced pressure. Yield: 18.5 g (20.5 mmol) 41%; Purity: approx. 99.9% 1 By H NMR.

[0155] The following compounds may be prepared similarly: [ka] [ka] [ka] [ka] [ka]

[0156] 1) Vacuum processed elements: The OLEDs according to the invention and according to the prior art are produced by the general method described in WO2004 / 058911 adapted to the circumstances described therein (layer thickness range, materials used).

[0157] In the following examples, various OLED results are shown. Glass plates coated with 50 nm structured ITO (indium tin oxide) (cleaned in a Miele laboratory glass washer, Extran detergent from Merck) are pretreated with UV ozone for 25 min (PR-100 UV ozone generator from UVP) and within 30 min, for process improvement, coated with 20 nm PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS® P VP AI 4083 from Heraeus Precious Metals GmbH, Germany, spin-coated from an aqueous solution) and baked at 180° C. for 10 min. These coated glass plates form the substrates on which the OLEDs are applied. The OLED basically has the following layer structure: substrate / hole injection layer 1 (HL1) made of Ref-HTM1 doped with 5% NDP-9 (available from Novaled), hole transport layer 1 (HTL1) made of 20nm / 160nm HTL1 / emissive layer (EML), 20nm / hole blocking layer (HBL), 10nm / electron transport layer (ETL), electron injection layer (EIL) made of 20nm / 1nm ETM2 / and finally the cathode. The cathode is formed by a 100nm thick layer of aluminium.

[0158] First, vacuum processed OLEDs are described. For this purpose, all materials are applied by thermal evaporation in a vacuum chamber. In this case, the emitting layer always consists of at least one matrix material (host material) and a light-emitting dopant (emitter) that is mixed into the matrix material in a certain volume ratio by co-evaporation. A specification given in the form SMB1:D1 (95:5%) means here that the material SMB1 is present in the layer in a volume ratio of 95% and D1 in a proportion of 5%. Similarly, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLED can be seen in Table 1. The materials used in the manufacture of the OLED are given in Table 3.

[0159] OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, current efficiency (measured in cd / A), power efficiency (measured in lm / W) and external quantum efficiency (EQE, measured in percent) are calculated as a function of luminous flux density, calculated from the current-voltage-luminance characteristic (IUL characteristic), assuming Lambertian emission characteristics. The electroluminescence spectrum is calculated for a luminous flux density of 1000 cd / m 2 and these are used to calculate the CIE 1931y color coordinates.

[0160] Use of the compounds of the present invention as materials in OLEDs One use of the compounds of the present invention is as dopants in the light-emitting layer of an OLED. Compounds from Table 3 are used as prior art comparisons. OLED results are summarized in Table 2. [Table 1-1] [Table 1-2] [Table 2-1] [Table 2-2] [Table 3]

[0161] The compounds of the present invention show narrower electroluminescence spectrum, as specified by smaller FWHM value (Full Width Half Maximum-width of emission spectrum at half peak height (nm)) compared to reference. This leads to smaller CIEy color coordinate, which corresponds to improved color purity. Moreover, in some cases, they have higher efficiency and operating voltage, which leads to further improvement of power efficiency.

Claims

1. A compound of formula (IIIa). 【Chemistry 1】 (where the symbols and subscripts used are as follows: Z is N; Y １ , Y ２ , Y ３ is a bond, and Y １ , Y ２ , Y ３ Two of the are B(Ar) or B(R), or Y １ , Y ２ , Y ３ all of are B(Ar) or B(R); R is the same or different for each occurrence and is H, D, F, CN, NO ２ , Si(R １ ) ３ , B(OR １ ) ２ , a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl group is in each case one or more R １ radicals), or 5 to 40 aromatic ring atoms, in each case one or more R １ an aromatic or heteroaromatic ring system, optionally substituted by a radical; at the same time, two R radicals may together form a ring system; Ar is the same or different in each occurrence and has 5 to 60 aromatic ring atoms and one or more R １ an aromatic or heteroaromatic ring system, optionally substituted by radicals; At the same time, two Ar radicals bonded to the same carbon, silicon, nitrogen, phosphorus or boron atom can be bridged by a single bond, or by B(R １ ), C(R １ ) ２ , Si(R １ ) ２ , C=O, C=NR １ , C=C(R １ ) ２ ,O,S,S=O,SO ２ , N(R １ ), P(R １ ) and P(=O)R １ may also be coupled together via a bridge selected from: R １ are the same or different at each occurrence and are H, D, F, CN, a straight chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be one or more R ２ radicals), or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which may be substituted by one or more R ２ optionally replaced by a radical; R ２ are the same or different at each occurrence and are selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and which may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms; wherein at least two R radicals, together with the further group to which they are bonded, form a condensed ring, and the two R radicals form at least one structure of formula (RA-1) to (RA-12): 【Chemistry 2】 Here, R １ has the meaning given above, the dotted line indicates the site of attachment to the atom of the group to which the two R radicals are bonded, and further symbols have the following meanings: Y ４ are the same or different for each occurrence, and C(R １ ) ２ , (R １ ) ２ C-C(R １ ) ２ , (R １ ) C=C(R １ ), N.R. １ , NAr, O or S; R ａ are identical or different at each occurrence and are selected from the group consisting of F, a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the alkyl group is, in each case, one or more of R ２ or 6 to 30 aromatic ring atoms, in each case one or more R ２ an aromatic or heteroaromatic ring system, optionally substituted by radicals; n is 0, 1, 2 or 3; s is 0, 1, 2, 3, 4, 5 or 6; t is 0, 1, 2, 3, 4, 5, 6, 7 or 8; v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

2. The compound according to claim 1, characterized in that at least two R radicals forming a fused ring and forming a structure of formulae (RA-1) to (RA-12) are R radicals from adjacent C atoms.

3. 3. The compound according to claim 1 or 2, characterized in that at least two R radicals, together with the further group to which they are attached, form a fused ring, wherein said two R radicals form at least one of the structures of formulae (RA-1a) to (RA-4f). 【Chemistry 3】 (wherein the symbol R ａ and R １ and the subscripts have the meanings given in claim 1, and the subscript m is 0, 1, 2, 3 or 4.

4. The compound according to any one of claims 1 to 3, selected from the compounds of formulae (IVa) to (IVc): 【Chemistry 4】 (Here, Y １ , Y ２ , Y ３ , Z and R have the meanings according to claim 1, the symbol o denotes at least one attachment site of the structures (RA-1) to (RA-12), the index n is 0, 1, 2 or 3 and the index k is 0 or 1).

5. The compound according to any one of claims 1 to 4, selected from the compounds of formulae (IVa-1) to (IVb-4): 【Chemistry 5】 (where the subscripts s and v and the symbol Y １ , Y ２ , Y ３ , Y ４ , Z., R., R. ａ and R １ has the meaning according to claim 1, the index n is 0, 1, 2 or 3 and the index k is 0 or 1.

6. 6. The compound according to any one of claims 1 to 5, wherein at least two R radicals, together with a further group to which the two R radicals are attached, form a fused ring, where the two R radicals form a structure of formula (RB). 【Chemistry 6】 (Here, R １ has the meaning according to claim 1, the index m is 0, 1, 2, 3 or 4, Y ５ is C(R １ ) ２ , N.R. １ , NAr, O or S)

7. The compound according to any one of claims 1 to 6, wherein the compound has at least two fused rings, where at least one fused ring is formed by a structure of formulae (RA-1) to (RA-12) and a further ring is formed from a structure of formulae (RA-1) to (RA-12) or (RB), and is selected from the compounds of formulae (Va) to (Vd). 【Chemistry 7】 (Here, Y １ , Y ２ , Y ３ , Z and R have the meanings according to claim 1, the symbol o denotes at least one attachment site of the structures of the formulae (RA-1) to (RA-12) or of the structure of the formula (RB), the subscript n is 0, 1, 2 or 3, and the subscript k is 0 or 1.

8. The compound according to any one of claims 1 to 7, selected from the compounds of formulae (Va-1) to (Va-18): 【Chemistry 8-1】 【Chemistry 8-2】 (where s and v, Y １ , Y ２ , Y ３ , Y ４ , Y ５ , Z., R., R. ａ And R １ has the meaning according to claim 1 or 6, the index m is 0, 1, 2, 3 or 4, the index n is 0, 1, 2 or 3 and the index k is 0 or 1.

9. In the formula (IIIa), (IVa) to (IVc), (Va) to (Vd) or (Va-1) to (Va-18), Y １ , Y ２ , Y ３ At least one of the groups is a bond; Y １ , Y ２ , Y ３ A compound according to any one of claims 1 to 8, characterised in that at least two of the groups are B(Ar) or B(R) and Z is N.

10. In (IIIa), (IVa) to (IVc), (Va) to (Vd) or (Va-1) to (Va-18), Y １ , Y ２ , Y ３ Compounds according to any one of claims 1 to 8, characterised in that all of the radicals are B(Ar) or B(R) and Z is N.

11. A compound selected from the group consisting of: 【Chemistry 9-1】 【Chemistry 9-2】 【Chemistry 9-3】

12. 12. An oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 11, wherein apart from hydrogen atoms or substituents there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

13. A formulation comprising at least one compound according to any one of claims 1 to 11, or an oligomer, polymer or dendrimer according to claim 12, and at least one further compound.

14. A composition comprising at least one compound according to any one of claims 1 to 11, or an oligomer, polymer or dendrimer according to claim 12, and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF, host materials, electron transport materials, electron injection materials, hole conducting materials, hole injection materials, electron blocking materials and hole blocking materials.

15. A base skeleton having a Z group or a precursor of the Z group is synthesized, １ , Y ２ , Y ３ A process for the preparation of a compound according to any one of claims 1 to 11, characterized in that at least one of the groups is introduced by an aromatic nucleophilic or coupling reaction.

16. Use of a compound according to any one of claims 1 to 11, or an oligomer, polymer or dendrimer according to claim 12 in an electronic device.

17. An electronic device comprising a compound according to any one of claims 1 to 11, or an oligomer, polymer or dendrimer according to claim 12.

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