Aromatic hetreocycles for organic electroluminescent devices

Abstract

The present invention relates to aromatic heterocycles that are suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing these compounds.

Description

[0001] Aromatic heterocycles for organic electroluminescent devices

[0002] The present invention relates to aromatic heterocycles for use in electronic devices, in particular in organic electroluminescent devices, and to electronic devices, in particular organic electroluminescent devices, containing these heterocyclic compounds.

[0003] In organic electroluminescent devices, phosphorescent organometallic complexes or fluorescent compounds are often used as emitting materials. In general, there is still room for improvement in electroluminescent devices.

[0004] Polycyclic compounds that can be used in organic electroluminescent devices are known from US 2010 / 0051928, WO 2010 / 104047 A1, WO 2017 / 175690, WO 2019 / 132506 A1, WO 2019 / 111971 A1, and WO 2020 / 064666 A1. Compounds according to the present invention are not disclosed.

[0005] In WO 2019 / 111971 A1, compounds are particularly preferred which are present at position R 5 and R 14 in formulas (3-11) are substituted by a diarylamino group and have no further substituents on the respective aromatic group to which the diarylamino group is bound (cf. WO 2019 / 111971 A1, formula (3-13).

[0006] Furthermore, compounds containing anthracene groups that can be used as matrix materials are known from publication CN 109761981. The use of this compound as an emitter is not described and is not practical. Similar compounds are also described in John B. Henry et al., J. Phys. Chem. A 2011, 115, 5435-5442.

[0007] In general, there is still room for improvement in the use of these heterocyclic compounds, for example for use as emitters, especially as fluorescent emitters, particularly with regard to lifetime, color purity, but also with regard to efficiency and operating voltage of the device.

[0008] The object of the present invention is therefore to provide compounds which are suitable for use in an organic electronic device, in particular in an organic electroluminescent device, and which, when used in this device, lead to good device properties, as well as to provide the corresponding electronic device.

[0009] In particular, it is the object of the present invention to provide connections that result in a long service life, good efficiency and low operating voltage.

[0010] Furthermore, the compounds should have excellent processability, with the compounds particularly showing good solubility.

[0011] A further object of the present invention can be seen in providing compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, in particular as emitters. In particular, it is an object of the present invention to provide emitters suitable for red, green, or blue electroluminescent devices, preferably for blue electroluminescent devices.

[0012] Furthermore, the compounds should lead to devices with excellent color purity, particularly when used as emitters in organic electroluminescent devices.

[0013] Another objective is to provide electronic devices with excellent performance at the lowest possible cost and with consistent quality. Furthermore, the electronic devices should be able to be used or adapted for a variety of purposes. In particular, the performance of the electronic devices should be maintained over a wide temperature range.

[0014] Surprisingly, it has been found that certain compounds, described in more detail below, achieve this objective, are highly suitable for use in electroluminescent devices, and lead to organic electroluminescent devices that exhibit very good properties, particularly with regard to lifetime, color purity, efficiency, and operating voltage. These compounds, as well as electronic devices, in particular organic electroluminescent devices, containing such compounds, are therefore the subject of the present invention.

[0015] The present invention relates to a compound comprising at least one structure of formula (I), preferably a compound according to formula (I),

[0016] Formula (I) where A at each occurrence, identically or differently, represents a partial structure of formula (A1) or (A2), preferably of formula (A1),

[0017] Formula (A1 ) Formula (A2) to which two partial structures B are condensed, and the symbols o and * represent the two condensation sites of the respective partial structure B, wherein a partial structure B is condensed to A via the positions marked with o and a partial structure B is condensed to A via the positions marked with * and at least one of the partial structures B is selected from a partial structure of the formula (B1 ) and another of the partial structures B is selected from a partial structure of the formula (B1) set out above or a partial structure of the formula (B2) where the dashed bonds represent the condensation sites of substructure B to A, the ring C cat each occurrence, identically or differently, represents a condensed aliphatic or heteroaliphatic ring having 5 to 60 ring atoms, which may be substituted by one or more radicals R, preferably represents an aliphatic or heteroaliphatic ring having 5 to 20, particularly preferably 5 to 18, very particularly preferably 5 to 12 ring atoms, which may be substituted by one or more radicals R, the ring C b at each occurrence, identically or differently, represents a condensed aliphatic or heteroaliphatic ring having 5 to 60 ring atoms, which may be substituted by one or more radicals R, preferably an aliphatic or heteroaliphatic ring having 5 to 20, particularly preferably 5 to 18, very particularly preferably 5 to 12 ring atoms, which may be substituted by one or more radicals R, and the following applies to the other symbols:

[0018] Z stands for N, C-CN or CR, the same or different at each occurrenceC , preferably N or C-CN and particularly preferably C-CN;

[0019] Y is the same or different at each occurrence CO, P(=O)R C , SO, SO2, C(O)O, C(S)O, C(O)S, C(=O)NR C , C(=O)NAr', preferably CO, P(=O)R C , SO, SO2, particularly preferably CO;

[0020] W 1 , W 2 represents, identically or differently at each occurrence, C(R)2, O, S, Si(R)2, preferably C(R)2;

[0021] X represents, identically or differently at each occurrence, N or CR, preferably CR, with the proviso that no more than two of the groups X, X b stand for N in a cycle;

[0022] X a represents N or CR, the same or different at each occurrence a preferably for CR a ;

[0023] X b represents N or CR, the same or different at each occurrence b , preferably for CR bprovided that no more than two of the groups X, X b stand for N in a cycle;

[0024] X c represents N or CR, the same or different at each occurrence C , preferably for CR C ;

[0025] R is the same or different at each occurrence and is H, D, OH, F, CI, Br, I, CN, NO2, N(Ar)2, N(R d )2, C(=O)N(Ar)2, C(=O)N(R d )2, C(Ar)3, C(R d )3, Si(Ar)3, Si(R d )3, B(Ar)2, B(R d )2, C(=O)Ar, C(=O)R d , P(=O)(Ar)2, P(=O)( R d )2, P(Ar)2, P(R d )2, S(=O)Ar, S(=O)R d , S(=O)2Ar, S(=O)2R d , OSChAr, OSO2R d, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R d may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R d C=CR d , C^C, Si(R d )2, C=O, C=S, C=Se, C=NR d , -C(=O)O-, -C(=O)NR d -, NR d , P(=O)( R d ), -O-, -S-, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R d may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R dmay be substituted, or an arylthio or heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R d may be substituted, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R d may be substituted, or an arylalkyl or heteroarylalkyl group having 5 to 60 aromatic ring atoms and 1 to 10 C atoms in the alkyl radical, which may be substituted by one or more radicals R d may be substituted; a radical R may be substituted with another group, preferably R or R b form a ring system;

[0026] Ar is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is substituted by one or more radicals R dmay be substituted, whereby two radicals Ar which bind to the same C atom, Si atom, N atom, P atom or B atom may also be connected by a single bond or a bridge selected from B(R d ), C(R d )2, Si(R d )2, C=O, C=NR d , C=C(R d )2, O, S, S=O, SO2, N(R d ), P(R d ) and P(=O)R d , be bridged together;

[0027] R a , R b , R c , R d is, at each occurrence, the same or different: H, D, OH, F, CI, Br, I, CN, NO2, 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)R 1 , S(=O)2Ar', S(=O)2R 1 , OSO2Ar', OSO2R 1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 1 may be substituted, where one or more non-adjacent CH2 groups are substituted by e, C=NR 1 , -C(=O)O-, - or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 can be substituted; two radicals R a , R b , R c , R dalso form a ring system with each other or with another group, preferably R;

[0028] Ar' is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is substituted with one or more radicals R 1 may be substituted, whereby two radicals Ar' which bind to the same C-atom, Si-atom, N-atom, P-atom or B-atom may also be connected by a single bond or a bridge selected from 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, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 , be bridged together;

[0029] R 1 is, at each occurrence, the same or different: H, D, F, CI, Br, I, CN, NO2, 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 straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or an alkenyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, with one or more non-adjacent CH2 groups being replaced by -R 2 C =NR 2 , -C(=O)O-, or SO2 and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2 may be substituted, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms which may be substituted with one or more radicals R2 may be substituted, or a combination of these systems; two or more, preferably adjacent, radicals R 1 form a ring system, whereby one or more residues R 1 form a ring system with another part of the compound;

[0030] Ar” is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is substituted by one or more radicals R 2 may be substituted, whereby two radicals Ar” which bind to the same C-atom, Si-atom, N-atom, P-atom or B-atom may also be linked by a single bond or a bridge selected from B(R 2 ), C(R 2 )2, Si(R 2 )2, C=O, C=NR 2 , C=C(R 2 )2, 0, S, S=O, SO2, N(R 2 ), P(R 2 ) and P(=O)R 2 , be bridged together;

[0031] R 2is selected, identically or differently at each occurrence, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, CI, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, where two or more, preferably adjacent, substituents R 2 together form a ring system. Preferred structures / compounds of formula (I) are those in which both partial structures B are selected from a partial structure of formula (B1).

[0032] In a preferred embodiment, the compounds according to the invention can comprise a structure of the formulas (I-1) to (I-4), particularly preferably the compounds according to the invention can be selected from the compounds of the formulas (I-1) to (I-4),

[0033] Formula (I-2)

[0034] Formula (I-4) where the symbols C b , C c , Y, W 1 , W 2 , Z, X, X a , X b and X c have the meanings given above, in particular for formula (I).

[0035] Structures of formulas (I-1) and / or (I-3) are preferred and structures of formula (I-1) are particularly preferred.

[0036] Preferably, it can be provided that at least one, preferably at least two of the radicals R, R a , R b , R c , R dare not equal to H, preferably not equal to H, D, OH, NO2, F, CI, Br, I. Accordingly, the radical R, which is preferably adjacent to a group X b or R b is preferably selected from CN, N(Ar)2, N(R d )2, C(=O)N(Ar)2, C(=O)N(R d )2, C(Ar)3, C(R d )3, Si(Ar)3, Si(R d )3, B(Ar)2, B(R d )2, C(=O)Ar, C(=O)R d , P(=O)(Ar)2, P(=O)(R d )2, P(Ar)2, P(R d )2, S(=O)Ar, S(=O)R d , S(=O)2Ar, S(=O)2R d , OSC Ar, OSO2R d , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R d may be substituted, wherein one or more non-adjacent CH2 groups are substituted by Rd C=CR d , C=C, Si(R d )2, C=O, C=S, C=Se, C=NR d , -C(=O)O-, -C(=O)NR d -, NR d , P(=O)( R d ), -O-, -S-, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R d may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R d may be substituted, or an arylthio or heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R d may be substituted, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R dmay be substituted, or an arylalkyl or heteroarylalkyl group having 5 to 60 aromatic ring atoms and 1 to 10 C atoms in the alkyl radical, which may be substituted by one or more radicals R d may be substituted; a radical R may be substituted with another group, preferably R or R b form a ring system; and / or at least one of the radicals R a , R b , R c , R d is preferably selected, identically or differently at each occurrence, from CN, 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)R 1 , S(=O)2Ar', S(=O)2R 1 , OSChAr', OSO2R 1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 1 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by 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 SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1can be substituted; two radicals R a , R b , R c , R d also form a ring system with each other or with another group. Here, residues N(Ar)2, N(R d )2, less preferred than the other groups mentioned.

[0037] An aryl group within the meaning of this invention contains 6 to 40 C atoms; a heteroaryl group within the meaning of this invention contains 2 to 40 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e. benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc., or a condensed (fused) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatics linked to one another by a single bond, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as an aromatic ring system.

[0038] An electron-poor heteroaryl group within the meaning of the present invention is a heteroaryl group that has at least one heteroaromatic six-membered ring containing at least one nitrogen atom. Further aromatic or heteroaromatic five-membered rings or six-membered rings can be fused to this six-membered ring. Examples of electron-poor heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, or quinoxaline.

[0039] An aromatic ring system within the meaning of this invention contains 6 to 60 C atoms in the ring system, preferably 6 to 40 C atoms in the ring system. A heteroaromatic ring system within the meaning of this invention contains 2 to 60 C atoms, preferably 3 to 40 C atoms, and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system within the meaning of this invention is to be understood as a system which does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be connected by a non-aromatic unit, such as a C, N or O atom. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc.are understood as aromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are linked, for example, by a short alkyl group. The aromatic ring system is preferably selected from fluorene, 9,9'-spirobifluorene, 9,9-diarylamine, or groups in which two or more aryl and / or heteroaryl groups are linked by single bonds.

[0040] In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which may contain 1 to 20 C atoms and in which individual H atoms or CH2 groups may be substituted by the above-mentioned groups, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neo-pentyl, cyclopentyl, n-hexyl, neo-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, Cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentinyl, hexynyl, heptynyl or octynyl.Unter einer Alkoxygruppe mit 1 bis 40 C-Atomen werden bevorzugt Methoxy, Trifluormethoxy, Ethoxy, n-Propoxy, i-Propoxy, n-Butoxy, i-Butoxy, s-Butoxy, t-Butoxy, n-Pentoxy, s-Pentoxy, 2-Methylbutoxy, n- Hexoxy, Cyclohexyloxy, n-Heptoxy, Cycloheptyloxy, n-Octyloxy, Cyclo- octyloxy, 2-Ethylhexyloxy, Pentafluorethoxy und 2,2,2-Trifluorethoxy verstanden. Unter einer Thioalkylgruppe mit 1 bis 40 C-Atomen werden insbesondere Methylthio, Ethylthio, n-Propylthio, i-Propylthio, n-Butylthio,.

[0041] 1-Butylthio, s-Butylthio, t-Butylthio, n-Pentylthio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclooctylthio,

[0042] 2-Ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio, or octynylthio. In general, alkyl, alkoxy, or thioalkyl groups according to the present invention can be straight-chain, branched, or cyclic, wherein one or more non-adjacent CH2 groups can be replaced by the above-mentioned groups; Furthermore, one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, preferably F, Cl or CN, more preferably F or CN, particularly preferably CN.

[0043] An aromatic or heteroaromatic ring system with 5 - 60 or 5 to 40 aromatic ring atoms, which may also be substituted with the above-mentioned radicals and which may be linked to the aromatic or heteroaromatic ring via any position, is understood to mean, in particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, 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,Phenothiazin, Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1 ,2-Thiazol, 1 ,3-Thiazol, Benzo- thiazol, Pyridazin, Hexaazatriphenylen, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1 ,5-Diazaanthracen, 2,7-Diazapyren, 2,3-Diaza- pyren, 1 ,6-Diazapyren, 1 ,8-Diazapyren, 4,5-Diazapyren, 4,5,9, 10-Tetra- azaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1 ,2,3-Triazol, 1 ,2,4-Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1 ,2,4-Oxadiazol, 1 ,2,5-Oxa- diazol, 1 ,3,4-Oxadiazol, 1 ,2,3-Thiadiazol, 1 ,2,4-Thiadiazol, 1 ,2,5-Thiadi- azol, 1 ,3,4-Thiadiazol, 1 ,3,5-Triazin, 1 ,2,4-Triazin, 1 ,2,3-Triazin, Tetrazol, 1 ,2,4,5-Tetrazin, 1 ,2,3,4-Tetrazin, 1 ,2,3,5-Tetrazin, Purin, Pteridin, Indolizin und Benzothiadiazol oder Gruppen,which are derived from combinations of these systems.,

[0044] For the purposes of this description, the phrase "two or more residues can form a ring" is understood to mean, among other things, that the two residues are linked by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme.

[0045] In education

[0046] Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring. This is illustrated by the following scheme:

[0047] Preferably, it can be provided that at least one of the radicals R, R dis / are not equal to H, preferably at least one of the radicals R, R d is / are not equal to H, D, F, CI, Br, I.

[0048] Preferably, it can further be provided that at least one of the radicals R c , preferably both residues R c is / are equal to H or D.

[0049] In a preferred embodiment, it can be provided that a radical R, preferably the radical R, which belongs to a group X b or a residue R b adjacent, is an aromatic or heteroaromatic ring system with 5 to 13 aromatic ring atoms, which is substituted with one or more radicals R d can be substituted.

[0050] Furthermore, it can be particularly preferably provided that the residue bonded to the group Y in the vicinity of the group Y does not have an acidic proton, preferably a keto-enol tautomerism is excluded in the case of Y being C=O. An acidic proton in this sense is a proton which has a high pKa value, wherein the pKa value of a proton is preferably at least 21, preferably at least 22, and particularly preferably at least 25.

[0051] In a further preferred embodiment, it can be provided that a compound according to the invention comprises at least one partial structure of the

[0052] Formula (B1-5) Formula (B1-6)

[0053] Formula (B1-15) Formula (B1-16)

[0054] Formula (B1 -29) Formula (B1 -30) where the symbols C c , W 1 , Y, R, R b , R c and R dhave the meanings given above, in particular for formula (I), the dashed bonds represent the condensation sites of the partial structure at A and the following applies to the symbols and indices used:

[0055] X 1 represents N or CR, the same or different at each occurrence d , preferably for CR d provided that no more than two of the groups X 1 stand for N in a cycle;

[0056] Y 1 is the same or different at each occurrence C(R d )2, (R d )2C-C(R d )2, (R d )C=C(R d ), NR d , NAr', 0, S, SO, SO2, Se, P(O)R d , BR d or Si(R d )2, preferably C(R d )2, (R d )2C-C(R d )2, (R d )C=C(R d ), 0 or S, particularly preferably C(R d)2; k is 0 or 1; n is 0, 1, 2 or 3, preferably 0, 1 or 2; m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0057] I is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2.

[0058] Structures of the formulas (B1-1) to (B1-18) are preferred, structures of the formulas (B1-1) to (B1-3) are particularly preferred, and structures of the formulas (B1-2) and (B1-3) are particularly preferred.

[0059] In a further preferred embodiment, if the compound comprises a partial structure (B2), the partial structure (B2) is selected from structures of the formulas (B2-1) to (B2-30),

[0060] Formula (B2-29) Formula (B2-30) where the symbols C b , W 1 , W 2 , Z, R, R b , R c and R d have the meanings given above, in particular for formula (I), the symbols X 1 , Y1 and the indices k, n, m and I have the meanings given above, in particular for formulas (B1-1) to (B1-30), the dashed bonds represent the condensation sites of the partial structure at A.

[0061] Structures of the formulas (B2-1) to (B2-18) are preferred, structures of the formulas (B2-1) to (B2-3) are particularly preferred, and structures of the formulas (B2-2) and (B2-3) are particularly specifically preferred.

[0062] In a preferred embodiment, the compounds according to the invention can comprise a structure of the formulas (11-1) to (11-21), particularly preferably the compounds according to the invention can be selected from the compounds of the formulas (11-1) to (11-21),

[0063] Formula (11-21 ) where the symbols C b , C c , Y, W 1 , W 2 , Z, R, R a , R b , R c and R dhave the meanings given above, in particular for formula (I), the symbol Y 1 has the meaning given above, in particular for formulas (B1-1) to (B1-30) and the following applies to the other indices used: m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0064] I is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2.

[0065] Structures / compounds of the formulas (II-1) to (II-7) are preferred, structures / compounds of the formulas (II-1) and (II-2) are particularly preferred and structures / compounds of the formula (II-1) are very particularly preferred.

[0066] Furthermore, it can be provided that the condensed ring C c is selected from a structure of the formulas (CCY-1 ) to (CCY-10),

[0067] Formula (CCY-1) Formula (CCY-2) Formula (CCY-3) Formula (CCY-4) where R has the meaning given above, in particular for formula (I), the dashed bonds represent the bonding sites of the condensed ring to the other groups and furthermore:

[0068] Z 1 , Z 4 is the same or different at each occurrence C(R 3 )2, 0, S or Si(R 3 )2, preferably C(R 3 )2;

[0069] Z 2 is C(R)2, O, S, NR or C(=O), where two adjacent groups Z 2 may represent -CR=CR- or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms, which may be substituted by one or more radicals R;

[0070] G is an alkylene group having 1, 2 or 3 C atoms, which may be substituted by one or more radicals R, -CR=CR- or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms, which may be substituted by one or more radicals R;

[0071] R 3 is the same or different at each occurrence: H, D, F, CI, Br, I, CN, NO2, N(Ar')2, N(R d )2, C(=O)Ar', C(=O)R d , P(=O)(Ar')2, P(Ar')2, B(Ar')2, B(R d )2, C(Ar')3, C(R d )s, Si(Ar')s, Si(R d )s, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or an alkenyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R d may be substituted, with one or more non-adjacent CH2 groups being substituted by Se, C=NR d , -C(=O)O- or SO2 and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each substituted by one or more radicals R d may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R d may be substituted, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms which may be substituted with one or more radicals R d may be substituted, or a combination of these systems; two radicals R 3 which are bonded to the same carbon atom, form an aliphatic or aromatic ring system and thus span a spiro system; furthermore, R 3 with one, preferably adjacent, radical R, R a , R c or R 3form an aliphatic ring system, where Ar' and R d have the meanings given in claim 1; with the proviso that in these groups no two heteroatoms are directly bonded to one another and no two C=O groups are directly bonded to one another.

[0072] In a preferred embodiment of the invention, R 3 not equal to H and / or D.

[0073] In a preferred embodiment of the structure according to formula (CCy-1) to (CCy-10), a maximum of one of the groups Z 1 , Z 2 and Z 4 represents a heteroatom, in particular O or NR, and the other groups represent C(R 3 )2 or C(R)2 or Z 1 and Z 4 are the same or different at each occurrence for O and Z 2 stands for C(R)2. In a particularly preferred embodiment of the invention, Z 1 and Z 4 the same or different at each occurrence for C(R 3 )2 and Z2 stands for C(R)2 and particularly preferably for C(R 3 )2 or CH2.

[0074] In a preferred embodiment of the present invention, it can be provided that the condensed ring C c is selected from a structure of the formulas (CRA-1) to (CRA-13) Formula CRA-7

[0075] Formula CRA-13 where R has the meaning given above, in particular for formula (I), the dashed bonds represent the attachment points of the condensed ring to the other groups and the other symbols have the following meaning:

[0076] Y 2 is at each occurrence, identically or differently, C(R)2, (R)2C-C(R)2, (R)C=C(R), NR, NAr', O or S, preferably C(R)2, (R)2C-C(R)2, (R)C=C(R), O or S;

[0077] R fis, identically or differently at each occurrence, F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R d may be substituted, where one or more non-adjacent CH2 groups are substituted by e, C=NR d , -C(=O)O-, - or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R d may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R d can be substituted; two radicals R f also with each other or a residue R fform a ring system with a radical R or with another group, where R d has the meaning given in claim 1;; r is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, particularly preferably 0 or 1; s is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2; t is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3 or 4, particularly 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, particularly preferably 0, 1 or 2,

[0078] Structures of the formulas CRA-1 to CRA-5 are preferred and structures of the formulas CRA-3 and CRA-4 are particularly preferred.

[0079] Particularly preferably, it can be provided that the condensed ring C c is selected from a structure of the formulas (CRA-1a) to (CRA-4f),

[0080] Formula CRA-1 a Formula CRA-1 b Formula CRA-1 c where the dashed bonds represent the attachment points of the condensed ring to the other groups, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2 and the symbols R, R d , R f and the indices s, t and v have the meanings set out above, in particular for formula (I) and / or formulas (CRA-1) to (CRA-13).

[0081] Structures of the formulas CRA-3b and CRA-4f are preferred.

[0082] In a preferred embodiment, it can be provided that the ring C described above and below c by substitutes R d instead of R. In this preferred embodiment, for example, the substituents R and R d of the groups Z set out above and below 1 to Z 4 , G, Y 2 , R 3 and R f by R d or R 1This applies in particular to the formulas (CCy-1 ) to (CCy-10), (CRA-1 to CRA-13) and (CRA-1 a) to (CRA-4f) in which, for example, the substituents R and R d by R d or R 1 are to be replaced.

[0083] In a further preferred embodiment, it can be provided that the ring C set out above and below b by substitutes R 1 instead of R. In this preferred embodiment, for example, the substituents R and R d of the groups Z set out above and below 1 to Z 4 , G, Y 2 , R 3 and R f by R 1 or R 2 to be replaced, whereby these definitions apply to the groups Z set out below 5 to Z 7 , G 1 , Y 4 and R gare set out by way of example and apply accordingly. This applies in particular to the formulas (CCy-1 ) to (CCy-10), (CRA-1 to CRA-13) and (CRA-1 a) to (CRA-4f) in which, for example, the substituents R and R d by R 1 or R 2 are to be replaced.

[0084] The Ring C c includes a group W 1 , whereby this group causes aromatic or heteroaromatic substituents R, which may originate from this group, to form no continuous conjugation with the basic structure of the partial structure B, in particular with the ring which contains two groups X c has.

[0085] Furthermore, it can be provided that the condensed ring C b is selected from a structure of the formulas (BCY-1) to (BCY-10),

[0086] Formula (BCy-9) Formula (BCy-10) where R has the meaning given above, in particular for formula (I), the symbols G, Z 1 and Z2 have the meanings given above, in particular for formulas (CCy-1) to (CCy-10), the dashed bonds represent the attachment points of the condensed ring to the other groups and furthermore:

[0087] Z 3 is the same or different at each occurrence C(R 3 )2, 0, S or Si(R 3 )2, preferably C(R 3 )2, where R 3 has the meaning given above, in particular for formulas (CCy-1) to (CCy-10); with the proviso that in these groups no two heteroatoms are directly bonded to one another and no two C=0 groups are directly bonded to one another. In a preferred embodiment of the invention, R 3 not equal to H and / or D.

[0088] If adjacent radicals in the structures according to the invention form an aliphatic ring system, it is preferred if this does not contain any acidic benzylic protons. Benzylic protons are understood to be protons that bond to an alkyl carbon atom that is directly bonded to an aryl or heteroaryl group. This can be achieved by fully substituting the carbon atoms of the aliphatic ring system that bond directly to an aryl or heteroaryl group and do not contain any bonded hydrogen atoms. Thus, the absence of acidic benzylic protons in the formulas (CCy-1) to (CCy-3) and / or (BCy-1) to (BCy-3) is achieved by Z 1 and Z 4 or Z 1 and Z 3 , if these are for C(R 3 )2 are defined so that R 3is not hydrogen. This can also be achieved by the carbon atoms of the aliphatic ring system that bind directly to an aryl or heteroaryl group being the bridgeheads of a bi- or polycyclic structure. Due to the spatial structure of the bi- or polycyclic system, the protons bound to bridgehead carbon atoms are significantly less acidic than benzylic protons on carbon atoms that are not bound in a bi- or polycyclic structure, and are considered non-acidic protons for the purposes of the present invention. Thus, the absence of acidic benzylic protons in formulas (CCy-1) to (CCy-3) and / or (BCy-1) to (BCy-3) is achieved by the bicyclic structure, whereby R 1 , when it stands for H, is significantly less acidic than benzylic protons, since the corresponding anion of the bicyclic structure is not mesomeric stabilized. Even if R 1in formulas (CCy-1 ) to (CCy-3) and / or (BCy-1 ) to (BCy-3) represents H, this is therefore a non-acidic proton within the meaning of the present application.

[0089] Preferably, it can be provided that, in particular in formulas (CCy-1 ) to (CCy-3) and / or (BCy-1 ) to (BCy-3), the following applies: R 3 is the same or different at each occurrence: F, CI, Br, I, CN, NO2, N(Ar')2, N(R d )2, C(=O)Ar', C(=O)R d , P(=O)(Ar')2, P(Ar')2, B(Ar')2, B(R d )2, C(Ar')3, C(R d )3, Si(Ar')s, Si(R d )s, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or an alkenyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R d may be substituted, with one or more non-adjacent CH2 groups being substituted by - C=NR d or SO2 and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R d may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R d may be substituted, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms which may be substituted with one or more radicals R d may be substituted, or a combination of these systems; two radicals R 3 which are bonded to the same carbon atom, form an aliphatic or aromatic ring system and thus span a spiro system; furthermore, R 3 with one, preferably adjacent, radical R, R a , R c or R 3form an aliphatic ring system, where Ar' and R d have the meanings given above, in particular for formula (I).

[0090] Preferably, it can be provided that in particular in formulas (CCy-1 ) to (CCy-3) and / or (BCy-1 ) to (BCy-3) the following applies:

[0091] R 3 is, at each occurrence, identically or differently, F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or an alkenyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R d may be substituted, with one or more non-adjacent CH2 groups being substituted by - C=NR d or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R dmay be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R d can be substituted; two radicals R 3 also with each other or a residue R 3 with a remainder R, R a , R c or form a ring system with another group, preferably an aliphatic ring system.

[0092] In a preferred embodiment of the structure according to formula (BCy-1) to (BCy-10), a maximum of one of the groups Z 1 , Z 2 and Z 3 represents a heteroatom, in particular O or NR, and the other groups represent C(R 3 )2or C(R)2or Z 1 and Z 3 are the same or different at each occurrence for O and Z 2 stands for C(R)2. In a particularly preferred embodiment of the invention, Z 1 and Z 3 the same or different at each occurrence for C(R 3)2and Z 2 stands for C(R)2 and particularly preferably for C(R 3 )2or CH2.

[0093] In a preferred embodiment of the invention, the radical R which is bonded to the bridgehead atom, preferably to the bridgehead atom according to formulas (CCy-4) to (CCy-10) or (BCy-4) to (BCy-10), is selected, identically or differently on each occurrence, from the group consisting of H, D, F, a straight-chain alkyl group having 1 to 10 C atoms which is reacted with one or more radicals R 1 may be substituted, but is preferably unsubstituted, a branched or cyclic alkyl group having 3 to 10 C atoms, which with one or more radicals R 1 may be substituted, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 5 to 12 aromatic ring atoms, each substituted by one or more radicals R 1may be substituted. Particularly preferably, the radical R which is bonded to the bridgehead atom according to formula (CCy-4) or (BCy-4) is selected, identically or differently on each occurrence, from the group consisting of H, F, a straight-chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 or 4 C atoms or a phenyl group which may be substituted by an alkyl group having 1 to 4 C atoms, but is preferably unsubstituted. Very particularly preferably, the radical R is selected, identically or differently on each occurrence, from the group consisting of H, methyl or tert-butyl.

[0094] In a preferred embodiment of the present invention, it can be provided that the condensed ring C b is selected from a structure of the formulas (BRA-1) to (BRA-12)

[0095] Formula BRA-4 Formula BRA-5 Formula BRA-6

[0096]

[0097] Formula BRA-10 Formula BRA-11 Formula BRA-12 where R has the meaning given above, in particular for formula (I), the symbols Y 2 and R f and the indices r, s, t and v have the meanings given above, in particular for formulas (CRA-1) to (CRA-13), the dashed bonds represent the attachment points of the condensed ring to the other groups.

[0098] Structures of the formulas BRA-1 to RBA-4 are preferred and structures of the formulas BRA-3 and BRA-4 are particularly preferred.

[0099] Particularly preferably, it can be provided that the condensed ring C b is selected from a structure of the formulas (BRA-1a) to (BRA-3f)

[0100] Formula BRA-1 a Formula BRA-1 b Formula BRA-1 c

[0101] Formula BRA-3d Formula BRA-3e Formula BRA-3f where the dashed bonds represent the attachment points of the condensed ring to the other groups, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2 and the symbols R, R d , R f and the indices s, t and v have the meanings set out above, in particular for formula (I) and / or formulas (CRA-1) to (CRA-13).

[0102] Structures of the formulas BRA-3f are preferred.

[0103] In a preferred embodiment, it can be provided that the ring C described above and below b by substitutes R d instead of R. In this preferred embodiment, for example, the substituents R and R d of the groups W set out above and below 1 , W 2 , Z 1 to Z 3 , G, Y 2 , R 3 and R f by R d or R 1This applies in particular to the formulas (BCy-1 ) to (BCy-10), (BRA-1 to BRA-12) and (BRA-1 a) to (BRA-3f) in which, for example, the substituents R and R d by R d or R 1 In a further preferred embodiment, it can be provided that the ring C described above and below b by substitutes R 1 instead of R. In this preferred embodiment, for example, the substituents R and R d of the groups W set out above and below 1 , W 2 , Z 1 to Z 3 , G, Y 2 , R 3 and R f by R 1 or R 2 to be replaced, whereby these definitions apply to the groups Z set out below 5 to Z 7 , G 1 , Y 4 and R gare set out by way of example and apply accordingly. This applies in particular to the formulas (BCy-1 ) to (BCy-10), (BRA-1 to BRA-12) and (BRA-1 a) to (BRA-3f) in which, for example, the substituents R and R d by R 1 or R 2 are to be replaced.

[0104] The Ring C b includes groups W 1 , W 2 , whereby these groups cause that aromatic or heteroaromatic substituents R, which may originate from these groups, cannot form a continuous conjugation with the basic structure of the partial structure B, in particular with the ring which contains the group Z or X c has.

[0105] In a preferred embodiment of the present invention, it can be provided that at least two radicals R, R a , R b , R c , R d with the other groups to which the two residues R, R a , R b , R c , R dbind, forming a condensed ring, where the two residues R, R a , R b , R c , R d form at least one structure of the following formulas (Cy-1) to (Cy-10),

[0106] Formula (Cy-1) Formula (Cy-2) Formula (Cy-3) Formula (Cy-4)

[0107] Formula (Cy-5) Formula (Cy-6) Formula (Cy-7) Formula (Cy-8)

[0108] Formula (Cy-9) Formula (Cy-10) where R 1 has the meaning previously explained, in particular for formula (I), the dashed bonds represent the attachment points to the atoms of the groups to which the two radicals R, R a , R b , R c , R d bind, represent and still applies:

[0109] Z 5 , Z 7 is the same or different at each occurrence C(R 4 )2, 0, S, NR 4 or C(=O);

[0110] Z 6 is C(R 1 )2, 0, S, NR 1or C(=0), where two adjacent groups Z 2 for -CR 1 =CR 1 - or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms, which is substituted by one or more radicals R 1 can be substituted, can stand;

[0111] G 1 is an alkylene group with 1, 2 or 3 C atoms, which with one or more radicals R 1 can be substituted, -CR 1 =CR 1 - or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms, which is substituted by one or more radicals R 1 can be substituted;

[0112] R 4 is, at each occurrence, the same or different: H, D, F, CI, Br, I, CN, NO2, 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 straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or an alkenyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, with one or more non-adjacent CH2 groups being substituted by -

[0113] C=NR 2 or SO2 and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2 may be substituted, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms which may be substituted with one or more radicals R2 may be substituted, or a combination of these systems; two radicals R 4 which are bonded to the same carbon atom, form an aliphatic or aromatic ring system and thus span a spiro system; furthermore, R 4 with one, preferably adjacent, radical R, R a , R b , R c , R d or R 1 form an aliphatic ring system, the symbols R 1 , R 2 and Ar" have the meanings given above, in particular for formula (I); with the proviso that in these groups no two heteroatoms are directly bonded to one another and no two C=O groups are directly bonded to one another.

[0114] In a preferred embodiment of the invention, R 4 not equal to H and / or D.

[0115] The absence of acidic benzylic protons in the formulas (Cy-1) to (Cy-3) is preferably achieved by Z5 and Z 7 , if these are for C(R 4 )2 are defined such that R 4 is not hydrogen. This can also be achieved by the carbon atoms of the aliphatic ring system that bind directly to an aryl or heteroaryl group being the bridgeheads of a bi- or polycyclic structure. Due to the spatial structure of the bi- or polycyclic system, the protons bound to bridgehead carbon atoms are significantly less acidic than benzylic protons on carbon atoms that are not bound in a bi- or polycyclic structure, and are considered non-acidic protons for the purposes of the present invention. Thus, the absence of acidic benzylic protons in formulas (Cy-4) to (Cy-10) is preferably achieved by the bicyclic structure, whereby R 1, when it stands for H, is significantly less acidic than benzylic protons, since the corresponding anion of the bicyclic structure is not mesomeric stabilized. Even if R 1 in formulas (Cy-4) to (Cy-10) stands for H, it is therefore a non-acidic proton within the meaning of the present application.

[0116] Preferably, it can be provided that in particular in formulas (Cy-1) to (Cy-3) the following applies:

[0117] R 4 is the same or different at each occurrence: F, CI, Br, I, CN, NO2, 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 straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or an alkenyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R 2may be substituted, with one or more non-adjacent CH2 groups being substituted by - C=NR 2 or SO2 and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2 may be substituted, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms which may be substituted with one or more radicals R 2 may be substituted, or a combination of these systems; two radicals R 4 which are bonded to the same carbon atom, form an aliphatic or aromatic ring system and thus span a spiro system; furthermore, R 4with a preferably adjacent radical R, R a , R c , R d , R 1 or form a ring system with another group, preferably an aliphatic ring system.

[0118] Preferably, it can be provided that in particular in formulas (Cy-1) to (Cy-3) the following applies:

[0119] R 4 is, identically or differently at each occurrence, F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 2 may be substituted, where one or more non-adjacent CH2 groups are substituted by e, C=NR 2 , -C(=O)O-, - or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2 can be substituted; two radicals R 4 also with each other or a residue R 4 with a remainder R, R a , R c , R d , R 1 or form a ring system with another group, preferably an aliphatic ring system.

[0120] In a preferred embodiment of the structure according to formula (Cy-1) to (Cy-10), a maximum of one of the groups Z 5 , Z 6 and Z 7 for a heteroatom, in particular for O or NR 4 , or for O or NR 1 , and the other groups represent C(R 4 )2or C(R 1 )2or Z5 and Z 7 are the same or different at each occurrence and represent O or NR 4 and Z 6 stands for C(R 1 )2. In a particularly preferred embodiment of the invention, Z 5 and Z 7 the same or different at each occurrence for C(R 4 )2and Z 6 stands for C(R 1 )2 and particularly preferably for C(R 4 )2 or CH2.

[0121] In a preferred embodiment of the invention, the radical R 1 which is bonded to the bridgehead atom, preferably to the bridgehead atom according to formulas (Cy-4) to (Cy-10), identically or differently on each occurrence selected from the group consisting of H, D, F, a straight-chain alkyl group having 1 to 10 C atoms, which with one or more radicals R 2 may be substituted, but is preferably unsubstituted, a branched or cyclic alkyl group having 3 to 10 C atoms, which with one or more radicals R2 may be substituted, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 5 to 12 aromatic ring atoms, each substituted by one or more radicals R 2 may be substituted. Particularly preferred is the radical R 1 which is bonded to the bridgehead atom according to formula (CY-4), is selected, identically or differently on each occurrence, from the group consisting of H, F, a straight-chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 or 4 C atoms, or a phenyl group which may be substituted by an alkyl group having 1 to 4 C atoms, but is preferably unsubstituted. Most preferably, the radical R 1 at each occurrence, the same or different, selected from the group consisting of H, methyl or tert-butyl.

[0122] In a preferred embodiment of the present invention, it can be provided that at least two radicals R, R a , Rb , R c , R d with the other groups to which the two residues R, R a , R b , R c , R d bind, forming a condensed ring, where the two residues R, R a , R b , R c , R d form at least one structure of the formulas (RA-1) to (RA-13)

[0123] Formula RA-1 Formula RA-2 Formula RA-3 where R 1 has the meaning explained above, the dashed bonds are the attachment points to the atoms of the groups to which the two radicals R, R a , R b , R c , R d bind, represent, and the other symbols have the following meaning:

[0124] Y 4 is the same or different at each occurrence C(R 1 )2, (R 1 )2C-C(R 1 )2, (R 1 )C=C(R 1 ), NR 1 , NAr', 0 or S, preferably C(R 1 )2, (R 1)2C-C(R 1 )2, (R 1 )C=C(R 1 ), 0 or S; R g is, identically or differently at each occurrence, F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 2 may be substituted, where one or more non-adjacent CH2 groups are substituted by e, C=NR 2 , -C(=O)O-, - or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2can be substituted; two radicals R g also with each other or a residue R g with a remainder R 1 or form a ring system with another group, where R 2 has the meaning given in claim 1; r is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, particularly preferably 0 or 1; s is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2; t is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3 or 4, particularly 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, particularly preferably 0, 1 or 2.

[0125] Structures of the formulas RA-1, RA-3, RA-4 and RA-5 are preferred, and structures of the formulas RA-4 and RA-5 are particularly preferred. In a preferred embodiment of the invention, at least two radicals R, R a , R b , R c , R dwith the other groups to which the two residues R, R a , R b , R c , R d bind, forming a condensed ring, where the two residues R, R a , R b , R c , R d Form structures of formulas (RA-1 a) to (RA-4f)

[0126] Formula RA-3a Formula RA-3b

[0127] Formula RA-4f where the dashed bonds represent the bonding sites through which the two radicals R, R a , R b , R c , R d bind, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2 and the symbols R 1 , R 2 , R g and the indices s and t have the meaning set out above, in particular for formula (I) and / or formulas (RA-1) to (RA-13).

[0128] Structures of the formula RA-4f are preferred.

[0129] Furthermore, it can be provided that a residue R b and a remainder Rd the structures of formulas (Cy-1 ) to (Cy-10), (RA-1 ) to (RA-13) and / or (RA-1 a) to (RA-4f) and form a condensed ring, wherein the radical R b and the rest R d are preferably adjacent.

[0130] Furthermore, it can be provided that two residues R d the structures of the formulas (Cy-1 ) to (Cy-10), (RA-1 ) to (RA-13) and / or (RA-1 a) to (RA-4f) and form a condensed ring, wherein the radicals R d are preferably adjacent. Furthermore, the two radicals R d also come from different rings.

[0131] In a further embodiment, it can be provided that a residue R b with a residue R or R d form the structures of the formulas (Cy-1 ) to (Cy-10), (RA-1 ) to (RA-13) and / or (RA-1 a) to (RA-4f) and form a condensed ring.

[0132] In a further preferred embodiment, at least two radicals R, R a , R b , R c , R d , preferably at least two radicals R, R b , R d with the other groups to which the two residues R, R a , R b , R c , R d or the two residues R, R b , R d bind, forming a condensed ring, where the two residues R, R a , R b , R c , R d , preferably the two radicals R, R b , R d Form structures of the formula (RB)

[0133] Formula RB where R 1 has the meaning given above, in particular for formula (I), the dashed bonds represent the attachment points via which the two radicals R, R a , R b , R c , R d or the two residues R, R b , R dbind, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y 5 C(R 1 )2, NR 1 , NAr', BR 1 , BAr', O or S, preferably C(R 1 )2, NAr' or O, particularly preferably C(R 1 )2 or O, where Ar' has the meaning given above, in particular for formula (I).

[0134] It can be provided that a residue R b with a residue R or R d form the structures of formula (RB) and form a condensed ring. Furthermore, it can be provided that two radicals R d form the structures of formula (RB) and form a condensed ring, where the radicals R d are preferably adjacent. Furthermore, it can be provided that a radical R b and a remainder R d form the structures of formula (RB) and form a condensed ring, where the radicals R b and remainder R d are preferably adjacent.

[0135] In particular, it can be provided that in preferred structures / compounds the sum of the indices r, s, t, v, m and n is preferably 0, 1, 2 or 3, particularly preferably 1 or 2.

[0136] Particularly preferably, the compounds comprise at least one structure of the structure of the formulas (III-1) to (III-20), particularly preferably the compounds are selected from compounds of the formulas (III-1) to (III-20), wherein the compounds comprise at least one condensed ring

[0137] Formula (111-1 ) Formula (III-2) where the symbols C b , C c , Y, W 1 , W 2 , Z, R a , R b , R c and R dhave the meanings given above, in particular for formula (I), the symbol o stands for the condensation sites of the at least one condensed ring and the further indices have the following meaning: m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0138] I is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2.

[0139] Preferably, the compounds can have at least two condensed rings, wherein at least one condensed ring is formed by structures of the formulas (RA-1) to (RA-13) and / or (RA-1 a) to (RA-4f) and a further ring is formed by structures of the formulas (RA-1) to (RA-13), (RA-1 a) to (RA-4f) or (RB).

[0140] The compounds particularly preferably comprise at least one structure of the formulas (IV-1) to (IV-3), particularly preferably the compounds are selected from compounds of the formulas (IV-1) to (IV-3), wherein the compounds have at least two condensed rings

[0141] Formula (IV-3) where the symbols C c , W 1 , Y, R a , R b and R c have the meanings given above, in particular for formula (I), the symbol o stands for the condensation sites of the at least two condensed rings.

[0142] Preferably, at least one of the condensed rings, particularly preferably both of the condensed rings, in particular in formulas (IV-1) to (IV-3), are represented by at least two radicals R, R a , R b , R c , R d and the other groups to which the two residues R, R a , R b , R c , R dbind, wherein the at least two radicals R, R a , R b , R c , R d Form structures of formulas (RA-1) to (RA-12) and / or formula (RB), preferably structures of formulas (RA-1) to (RA-12).

[0143] Furthermore, it can be provided that the substituents R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 and R 4 according to the above formulas with the ring atoms of the ring system to which the substituents R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 and R 4 bind, do not form a fused aromatic or heteroaromatic ring system. This excludes the formation of a fused aromatic or heteroaromatic ring system with possible substituents R d , R 1 and R 2which are bound to the substituents R, R a , R b , R c , R d , R f , R g , R 1 , R 3 and R 4 may be bound.

[0144] When the compound according to the invention is substituted with aromatic or heteroaromatic groups R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 or R 4is substituted, it is preferred if these do not contain any aryl or heteroaryl groups with more than two directly fused aromatic six-membered rings. Particularly preferably, the substituents do not contain any aryl or heteroaryl groups with directly fused six-membered rings. This preference is due to the low triplet energy of such structures. Condensed aryl groups with more than two directly fused aromatic six-membered rings that are nevertheless also suitable according to the invention are phenanthrene and triphenylene, since these also have a high triplet level.

[0145] Preferably, it can therefore be provided that the radical R does not comprise a continuously conjugated anthracene group, preferably none of the radicals R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 and R 4a continuously conjugated anthracene group.

[0146] A continuous conjugation of the anthracene group is formed as soon as direct bonds are formed between the anthracene group, the basic structure according to the invention, which is shown in formula (I), and an optional aromatic or heteroaromatic linking group. A further linkage between the aforementioned conjugated groups, which occurs, for example, via an S, N, or O atom or a carbonyl group, does not harm the conjugation. In a fluorene system, the two aromatic rings are directly bonded, with the sp 3 hybridized carbon atom in position 9 prevents condensation of these rings, but conjugation can occur, since this sp 3hybridized carbon atom in position 9 does not necessarily lie between the groups connected via a connecting group. In contrast, in a spirobifluorene structure, continuous conjugation can be formed if the connection between the groups connected via the spirobifluorene group is made via the same phenyl group of the spirobifluorene structure or via phenyl groups of the spirobifluorene structure that are directly bonded to each other and lie in one plane. If the connection between the groups connected via a spirobifluorene group is made via different phenyl groups of the second spirobifluorene structure that are connected via the sp 3 hybridized carbon atom in position 9, the conjugation is interrupted.

[0147] Particularly preferably, it can further be provided that the radical R does not comprise an anthracene group, preferably none of the radicals R, R a , R b, R c and R d , particularly preferably none of the radicals R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 and R 4 an anthracene group.

[0148] It can also be provided, very particularly preferably, that the radicals R do not comprise an aromatic or heteroaromatic ring system which has three linearly condensed aromatic 6 rings, wherein preferably none of the radicals R, R a , R b , R c and R d , particularly preferably none of the radicals R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 and R 4 an aromatic or heteroaromatic ring system which has three linearly condensed aromatic 6 rings.

[0149] Furthermore, it can be provided that none of the residues R, Ra , R b , R c and R d , particularly preferably none of the radicals R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 and R 4 comprises or forms a fluorenone group. This includes substituents attached to the radicals R, R a , R b , R c , R d , etc. A fluorenone comprises a 5-membered ring with a CO group to which two aromatic 6-membered rings are fused.

[0150] When two residues, which can be selected in particular from R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 and R 4, together form a ring system, this can be mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic. The radicals forming a ring system can be adjacent, ie these radicals are bonded to the same carbon atom or to carbon atoms that are directly bonded to each other, or they can be further apart. Furthermore, the radicals bonded to the substituents R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 and / or R 4 The ring systems provided with the ring can also be connected to one another via a bond, so that a ring closure can be effected. In this case, each of the corresponding bonding sites is preferably provided with a substituent R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 and / or R4 provided.

[0151] Preferably, it can be provided that the structure / connection is symmetrical with respect to the substructures B.

[0152] Symmetrical with respect to the substructures B means in particular that the corresponding residues R, R a , R b , R c , R d , R f , R g , R 1 , R 2 , R 3 and R 4 are the same and do not differ.

[0153] Structures / compounds in which the substructures B are symmetrical are characterized by a surprisingly high color purity, which is particularly reflected in a narrow emission spectrum.

[0154] In a further embodiment, the structure / connection may be asymmetrical with respect to the connection with respect to the substructures B.

[0155] Furthermore, it can be provided that a radical R, preferably the radical R, which belongs to a group X b or a residue R b adjacent, at least one group selected from C(Ar)s, C(R d )s, Si(Ar)s, Si(R d )s, B(R d )2, preferably selected from C(Ar)s, C(R d )s, Si(Ar)s, Si(R d )s, particularly preferably a fluorene group which is reacted with one or more radicals R d may be substituted, comprises, represents or is substituted with a radical R b forms.

[0156] Furthermore, it can be provided that the remainder R b and / or R d at least one group selected from C(Ar')s, C(R 1 )3, Si(Ar')s, Si(R 1 )s, B(R 1 )2, preferably selected from C(Ar')s, C(R 1 )3, Si(Ar')s, Si(R 1 )s, preferably a fluorene group which is reacted with one or more radicals R 1may be substituted, comprises, represents or is substituted with a radical R b or R d Structures / compounds with one of the aforementioned groups selected from C(Ar)s, C(R d )s, Si(Ar)s, Si(R d )s, B(R d )2 or C(Ar')3, C(R 1 )3, Si(Ar')3, Si(R 1 )s, B(R 1 )2, particularly preferably a fluorene group, are characterized by a surprisingly high efficiency.

[0157] According to a preferred embodiment, a compound according to the invention can be prepared by at least one of the structures according to formulas (I) and / or (I-1) to (I-4). Compounds according to the invention, preferably comprising structures according to formulas (I) and / or (I-1) to (I-4), preferably have a molecular weight of less than or equal to 5000 g / mol, preferably less than or equal to 4000 g / mol, particularly preferably less than or equal to 3000 g / mol, especially preferably less than or equal to 2000 g / mol, and most preferably less than or equal to 1200 g / mol.

[0158] Furthermore, preferred compounds according to the invention are characterized by their sublimability. These compounds generally have a molecular weight of less than approximately 1200 g / mol.

[0159] Preferred aromatic or heteroaromatic ring systems Ar, R, R a , R b , R c , R d , R f , R g , R 3 , R4 and / or Ar' are selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which may be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which may be linked via the 1-, 2-, 3- or 4-position, naphthalene, in particular 1- or linked naphthalene, indole, benzofuran, benzothiophene, carbazole, which may be linked via the 1-, 2-, 3-, 4- or 9-position, dibenzofuran, which may be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, which may be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, Indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which is substituted with one or more radicals R d , R 1 or R2 Preferably, at least one substituent R, R a , R b , R c , R d is selected, identically or differently on each occurrence, from the group consisting of H, D, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms or an aromatic or heteroaromatic ring system selected from the groups of the following formulas Ar-1 to Ar-75, preferably the substituents R, R a , R b , R c , R d either form a condensed ring, preferably according to the structures of formulas (RA-1) to (RA-13) or (RB) or the substituent R, R a , R b , R c , R dis selected, identically or differently on each occurrence, from the group consisting of H, D or an aromatic or heteroaromatic ring system selected from the groups of the following formulas Ar-1 to Ar-75, and / or the group Ar' is selected, identically or differently on each occurrence, from the groups of the following formulas Ar-1 to Ar-75,

[0160]

[0161] Ar-67 Ar-68 where R 1 has the meanings mentioned above, the dashed bond represents the attachment point to the corresponding group and furthermore:

[0162] Ar 1 is at each occurrence, identically or differently, a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, each of which is substituted by one or more radicals R 1 can be substituted;

[0163] A is the same or different at each occurrence C(R 1 )2, NR 1 , 0 or S; p is 0 or 1 , where p = 0 means that the group Ar 1 is not present and that the corresponding aromatic or heteroaromatic group is directly bonded to the corresponding radical; q is 0 or 1 , where q = 0 means that no group A is bonded to this position and the corresponding carbon atoms are bonded instead to radicals R 1 are bound.

[0164] The structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-40), (Ar-41), (Ar-42), (Ar-43), (Ar-44), (Ar-45), (Ar-46), (Ar-69), (Ar-70), (Ar-75) are preferred and structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16) are particularly preferred.

[0165] If the above-mentioned groups have several groups A for Ar, all combinations from the definition of A are possible. Preferred embodiments are then those in which one group A for NR 1 and the other group A for C(R 1 )2 or in which both groups A for NR 1 or in which both groups A stand for 0.

[0166] If A for NR 1 the substituent R 1 which is bonded to the nitrogen atom, preferably represents an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 2 In a particularly preferred embodiment, this substituent R 1identically or differently on each occurrence, represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 18 aromatic ring atoms, which does not contain any condensed aryl groups and which does not contain any condensed heteroaryl groups in which two or more aromatic or heteroaromatic 6-ring groups are directly fused to one another, and which in each case is also substituted by one or more radicals R 2 may be substituted. Preferred are phenyl, biphenyl, terphenyl and quaterphenyl with linkage patterns as listed above for Ar-1 to Ar-11, where these structures are substituted by R 1 by one or more residues R 2 may be substituted, but are preferably unsubstituted. Preference is also given to triazine, pyrimidine and quinazoline, as listed above for Ar-47 to Ar-50, Ar-57 and Ar-58, where these structures are substituted by R 1 by one or more residues R 2can be substituted.

[0167] In the following, preferred substituents R, R a , R b , R c , R d , R f and R 9 described.

[0168] In a preferred embodiment of the invention, R, R a , R b , R c , R d identically or differently at each occurrence selected from the group consisting of H, D, F, CN, NO2, Si(R 1 )s, B(OR 1 )2, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted.

[0169] In a further preferred embodiment of the invention, substituent R, R a , R b , R c , R d identically or differently on each occurrence selected from the group consisting of H, D, F, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted.

[0170] Furthermore, it can be provided that at least one substituent R, R a , R b , R c , R dis selected, identically or differently at each occurrence, from the group consisting of H, D, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which is reacted with one or more radicals R 1 may be substituted. In a further preferred embodiment of the invention, the substituents R, R a , R b , R c , R d either a ring according to the structures of the formulas (RA-1 ) to (RA-13), (RA-1 a) to (RA-4f) or (RB) or R, R a , R b , R c , R d is selected, identically or differently at each occurrence, from the group consisting of H, D, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which is reacted with one or more radicals R 1 may be substituted. Particularly preferred is substituent R, R a , R b , R c , R didentically or differently on each occurrence selected from the group consisting of H or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, particularly preferably having 6 to 13 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted. In a preferred embodiment of the invention, R f or R 9 identically or differently on each occurrence selected from the group consisting of a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl group is in each case substituted with one or more radicals R d or R 2 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each substituted by one or more radicals Rd or R 2 can be substituted.

[0171] In a further preferred embodiment of the invention, R f or R 9 identically or differently on each occurrence selected from the group consisting of a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl group is in each case substituted with one or more radicals R d or R 2 may be substituted, an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, which is substituted with one or more radicals R d or R 2 can be substituted.

[0172] Particularly preferred is the radical R, which preferably corresponds to a group X b or R b is adjacent, or R didentically or differently on each occurrence selected from the group consisting of a straight-chain alkyl group having 1 to 5 C atoms or a branched or cyclic alkyl group having 3 to 5 C atoms, where the alkyl group is in each case substituted with one or more radicals R d or R 1 may be substituted or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, particularly preferably having 6 to 13 aromatic ring atoms, each of which is substituted by one or more radicals R d or R 1 can be substituted.

[0173] In a preferred embodiment of the invention, R f or R 9at each occurrence, identically or differently selected from the group consisting of a straight-chain alkyl group having 1 to 6 C atoms or a cyclic alkyl group having 3 to 6 C atoms, where the alkyl group is in each case substituted with one or more radicals R d or R 2 may be substituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R d or R 2 can be substituted; two radicals R f or R 9 also form a ring system with each other. R is particularly preferably f or R 9 at each occurrence, identically or differently selected from the group consisting of a straight-chain alkyl group having 1, 2, 3 or 4 C atoms or a branched or cyclic alkyl group having 3 to 6 C atoms, where the alkyl group is in each case substituted with one or more radicals R dor R 2 may be substituted, but is preferably unsubstituted, or an aromatic ring system having 6 to 12 aromatic ring atoms, in particular having 6 aromatic ring atoms, each substituted by one or more, preferably non-aromatic, radicals R d or R 2 may be substituted, but is preferably unsubstituted; two radicals R f or R 9 form a ring system with each other. R is particularly preferably f or R 9 at each occurrence, identically or differently selected from the group consisting of a straight-chain alkyl group having 1, 2, 3 or 4 C atoms, or a branched alkyl group having 3 to 6 C atoms. R is most preferably f or R 9for a methyl group or for a phenyl group, where two phenyl groups together can form a ring system, with a methyl group being preferred over a phenyl group.

[0174] Preferred aromatic or heteroaromatic ring systems for which the substituents R, R 3 , R a , R b , R c , R d , R f , R 9or Ar, Ar' or Ar" are selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which may be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which may be linked via the 1-, 2-, 3- or 4-position, naphthalene, in particular 1- or 2-linked naphthalene, indole, benzofuran, benzothiophene, carbazole, which may be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which may be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, which may be linked via the 1-, 2-, 3- or 4-position, Indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which is substituted with one or more radicals R d , R 1or R 2 may be substituted. The structures Ar-1 to Ar-75 listed above are particularly preferred, with structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-40), (Ar-41), (Ar-42), (Ar-43), (Ar-44), (Ar-45), (Ar-46), (Ar-69), (Ar-70), (Ar-75) being preferred and structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16) being particularly preferred. With regard to the structures Ar-1 to Ar-75, it should be noted that these can be substituted with a substituent R 1 In the case of the ring system R, R 3 , R f or Ar, these substituents are R 1 by R d and in the case of Ar“, R 9 these substituents R 1 by R 2 to replace.

[0175] Other suitable groups R, R a , R b , R c , R d are groups of the formula -Ar 4 -N(Ar 2 )(Ar 3), where Ar 2 , Ar 3 and Ar 4 identically or differently on each occurrence represent an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which is substituted by one or more radicals R 1 The total number of aromatic ring atoms of Ar 2 , Ar 3 and Ar 4 maximum 60 and preferably maximum 40. These groups of the formula -Ar 4 -N(Ar 2 )(Ar 3 ) are not preferred.

[0176] Ar 4 and Ar 2 with each other and / or Ar 2 and Ar 3 with each other also by a group selected from C(R 1 )2, NR 1 , O or S. Preferably, the linking of Ar 4 and Ar 2 with each other or from Ar 2 and Ar 3are ortho to the position of the linkage to the nitrogen atom. In a further embodiment of the invention, none of the groups Ar 2 , Ar 3 or Ar 4 connected to each other.

[0177] Ar is preferred 4 an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted. Particularly preferred is Ar 4 selected from the group consisting of ortho-, meta- or para-phenylene or ortho-, meta- or para-biphenyl, each of which is substituted by one or more radicals R 1 may be substituted, but are preferably unsubstituted. Ar is particularly preferred 4 an unsubstituted phenylene group.

[0178] Preference is given to Ar 2 and Ar 3identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 1 Particularly preferred groups Ar 2 or Ar 3 are, identically or differently at each occurrence, selected from the group consisting of benzene, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spiro-bifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene, 1-, 2-

[0179] 3- or 4-carbazole, 1-, 2-, 3- or 4-dibenzofuran, 1-, 2-, 3- or 4-di-benzothiophene, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2-,

[0180] 4- or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene or triphenylene, each of which is substituted by one or more radicals R 1may be substituted. Particularly preferred are Ar 2 and Ar 3 identically or differently on each occurrence selected from the group consisting of benzene, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, in particular 1-, 2-, 3- or 4-fluorene, or spirobifluorene, in particular 1-, 2-, 3- or 4-spirobifluorene.

[0181] In a further preferred embodiment of the invention, R 1 identically or differently on each occurrence selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl group is in each case substituted with one or more radicals R 2may be substituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 2 may be substituted. In a particularly preferred embodiment of the invention, R 1 identically or differently on each occurrence selected from the group consisting of H, a straight-chain alkyl group having 1 to 6 C atoms, in particular having 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group having 3 to 6 C atoms, where the alkyl group is substituted with one or more radicals R 2 may be substituted, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, each substituted by one or more radicals R 2 can be substituted, but is preferably unsubstituted.

[0182] In a further preferred embodiment of the invention, R 2identical or different on each occurrence H, an alkyl group having 1 to 4 C atoms or an aryl group having 6 to 10 C atoms, which may be substituted by an alkyl group having 1 to 4 C atoms, but is preferably unsubstituted.

[0183] In compounds according to the invention that are processed by vacuum evaporation, the alkyl groups preferably have no more than five carbon atoms, more preferably no more than four carbon atoms, and most preferably no more than one carbon atom. For compounds that are processed from solution, compounds substituted by alkyl groups, especially branched alkyl groups, with up to 10 carbon atoms, or substituted by oligoarylene groups, for example ortho-, meta-, para-, or branched terphenyl or quaterphenyl groups, are also suitable.

[0184] Furthermore, it can be provided that the compound comprises exactly two or exactly three structures according to formula (I), (I-1) to (I-4) and / or (II-1) to (II-21), wherein preferably one of the aromatic or heteroaromatic ring systems which are represented by at least one of the groups R, R b , R d can be represented or to which the groups R, R b , R d bind, is shared by both structures.

[0185] In a preferred embodiment, the compounds are selected from compounds according to formula (D-1), (D2) or (D-3),

[0186] Formula (D-3) where the group L 1represents a connecting group, preferably a bond or an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R, and the other symbols used have the meanings given above, in particular for formula (I).

[0187] In a further preferred embodiment of the invention, L 1 represents 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 substituted by one or more radicals R, but is preferably unsubstituted, where R may have the meaning given above, in particular for formula (I). L is particularly preferably 1represents an aromatic ring system with 6 to 10 aromatic ring atoms or a heteroaromatic ring system with 6 to 13 heteroaromatic ring atoms, each represented by one or more radicals R 1 may be substituted, but is preferably unsubstituted, where R 1 which may have the meaning given above, in particular for formula (I).

[0188] Furthermore, the symbol L shown inter alia in formula (D3) is preferably 1 identical or different on each occurrence for a bond or an aryl or heteroaryl radical having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, particularly preferably 6 to 10 ring atoms, so that an aromatic or heteroaromatic group of an aromatic or heteroaromatic ring system is bonded directly, ie via an atom of the aromatic or heteroaromatic group, to the respective atom of the further group.

[0189] Furthermore, it can be provided that the group L shown in formula (D3) 1 an aromatic ring system with at most two fused aromatic and / or heteroaromatic 6-membered rings, preferably no fused aromatic or heteroaromatic ring system. Accordingly, naphthyl structures are preferred over anthracene structures. Furthermore, fluorenyl, spirobifluorenyl, dibenzofuranyl, and / or dibenzothienyl structures are preferred over naphthyl structures.

[0190] Particularly preferred are structures which do not exhibit condensation, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0191] Examples of suitable aromatic or heteroaromatic ring systems L 1are selected from the group consisting of ortho-, meta- or para-phenylene, ortho-, meta- or para-biphenylene, terphenylene, in particular branched terphenylene, quaterphenylene, in particular branched quaterphenylene, fluorenylene, spirobifluorenylene, dibenzofuranylene, dibenzothienylene and carbazolylene, each of which is substituted by one or more radicals R 1 may be substituted, but are preferably unsubstituted.

[0192] The above-mentioned preferred embodiments can be combined with each other as desired within the limitations defined in claim 1. In a particularly preferred embodiment of the invention, the above-mentioned advantages occur simultaneously.

[0193] In a further embodiment of the present invention, compounds comprising a structure according to formula (I), preferably compounds according to formula (I), are preferred in which at least one ring C chas the following properties:

[0194] In a further embodiment of the present invention, compounds comprising a structure according to formula (I), preferably compounds according to formula (I), are preferred in which at least one ring C c has the following properties:

[0195] In a further embodiment of the present invention, compounds comprising a structure according to formula (II-1), preferably compounds according to formula (II-1), are preferred in which the ring C c and the residues R a , R b , R c and R d have the following meanings, the same or different, whenever they occur:

[0196] In a further embodiment of the present invention, compounds comprising a structure according to formula (II-2), preferably compounds according to formula (II-2), are preferred, wherein the index I is preferably less than or equal to 3, particularly preferably 0, 1 or 2, and especially preferably 0 or 1, and in which the ring C c and the residues R a , R b , R c and R d have the following meanings, the same or different, whenever they occur:

[0197]

[0198] In the tables above, the columns under group R d mentioned radicals for the substituents on the phenyl ring of the basic structure, which is also represented by the mentioned radical R b is substituted (see for example formula (11-1 )), or for the substituents on the phenyl ring, which is attached to the phenyl ring of the basic structure, which is also represented by the said radical R bis substituted (see, for example, formula (II-2). R is most preferably d represents a methyl group or a phenyl group. The radicals R d also form a ring system with each other, which leads to a spiro system.

[0199] The term "alkyl" in the tables above particularly encompasses straight-chain alkyl groups or branched or cyclic alkyl groups according to the previously set forth definition for the respective group. The term "aryl, heteroaryl" in the tables above particularly encompasses aryl or heteroaryl groups having 5 to 40 aromatic ring atoms according to the previously set forth definition for the respective group, where the aryl groups preferably have 6 to 12, particularly preferably 6, ring atoms, and the heteroaryl groups preferably have 5 to 13, particularly preferably 5, ring atoms. Heteroaryl groups particularly preferably comprise one or two heteroatoms, preferably N, O, or S.

[0200] The designations “CRA-3”, “CRA-4”, “CRA-4f”, “CRA-5”, “Ar-1”, “Ar-75” refer to the structural formulas presented above and below.

[0201] Phenyl ring formation with a group means that the two groups together form a phenyl group, each according to the previously stated definition for the respective group with residues R 1 This usually results in the formation of phenyl groups bound to the nitrogen atom, which are substituted by the radicals R b and R or R d is substituted, a naphthyl group. The same applies to the other ring formation definitions.

[0202] The term “and”, especially when describing preferred groups R b means that the two residues are different, with one of the residues R b a first and the second residue R b a second definition. The term “aryl, heteroaryl and phenyl ring formation with Rd “ means that one of the residues R b represents an aryl, heteroaryl group and the second radical R b with R d “ forms a phenyl ring. If a field does not contain the expression “and”, all residues represent a corresponding group. The expression “Ar-1 to Ar-75” for the group R d means that both residues R b represent an aryl or heteroaryl radical according to the above or following formulas Ar-1 to Ar-75. The same applies to the further use of the term "and" in the above tables.

[0203] The preferences shown for formulas (II-1 ) and (II-2) with regard to ring C b and the various substituents R a , R b , R c and R d Of course, this also applies to the other formulas (II-3) to (II-20) presented above.

[0204] Examples of preferred compounds according to the above

[0205] Embodiments are the compounds listed in the following table;

[0206] 

[0207] Preferred embodiments of compounds according to the invention are explained in more detail in the examples, whereby these compounds can be used alone or in combination with others for all purposes according to the invention.

[0208] Provided that the conditions stated in claim 1 are met, the above-mentioned preferred embodiments can be combined with one another as desired. In a particularly preferred embodiment of the invention, the above-mentioned preferred embodiments apply simultaneously.

[0209] The compounds of the invention can, in principle, be prepared by various methods. However, the methods described below have proven particularly suitable.

[0210] Therefore, a further object of the present invention is a process for preparing the compounds according to the invention, in which a basic structure with an aromatic amino group is synthesized and at least one aromatic or heteroaromatic radical is introduced, preferably by means of a nucleophilic aromatic substitution reaction or a coupling reaction.

[0211] Suitable compounds comprising a basic structure with an aromatic amino group can often be obtained commercially. The starting compounds presented in the examples are obtainable by known processes, so reference is made thereto. These compounds can be reacted with other compounds by known coupling reactions. The necessary conditions for this are known to the person skilled in the art, and detailed information in the examples assists the person skilled in the art in carrying out these reactions.

[0212] Particularly suitable and preferred coupling reactions, all of which lead to C-C bond formations and / or C-N bond formations, are those according to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA, and HIYAMA. These reactions are widely known, and the examples provide further guidance to the skilled person.

[0213] The synthesis of the compounds according to the invention can be carried out, inter alia, according to the following schemes 1, 2 and / or 3.

[0214] For example, a synthesis can be carried out in three steps, as shown in Scheme 1. First, a secondary o-chloroarylamine can be prepared from the up to halogen (Br, I) or triflate-functionalized building blocks BS in a palladium-phosphine-catalyzed Hartwig-Buchwald-type C—N coupling reaction by reaction with a primary arylamine (step 1). Exemplary building blocks BS are included in the examples section, which is referred to here in general terms. The product of the first step can be cyclized to the carbazole in step 2 in a palladium-phosphine-catalyzed C—C coupling. The carbazoles thus obtained can then be reacted with 1,4-dichloro-2,5-difluoroaromatics / heteroaromatics in an SN2Ar reaction (see stage 3, step 1). The coupling product can be cyclized in situ by adding a Pd source and a phosphine in a palladium-phosphine-catalyzed CC coupling to give the compounds according to the invention (seeStage 3, Step 2). If two different carbazoles are used in stage 3—as a mixture or by sequential addition—mixed functionalized compounds according to the invention can be obtained. This applies both to the use of two carbonyl-functionalized carbazoles and to the use of one carbonyl-functionalized carbazole and one differently functionalized carbazole.

[0215] Scheme 1 :

[0216] Alternatively, the compounds of the invention can be prepared starting from the carbazoles in four steps (see Scheme 2).

[0217] First, a regioselective NBS bromination of carbazoles with a substituent R' in the ortho-position to C=O (see Experimental Section for synthesis) can be carried out (step 1). The bromine function can be converted into the B-Pin ester in a palladium-phosphine-catalyzed borylation with B2Pin2 (step 2). Subsequently, the central ring unit is coupled in a palladium-phosphine-catalyzed Suzuki-type CC coupling (step 3). Finally, cyclization to the compounds of the invention is carried out in a palladium-phosphine-catalyzed CC coupling (step 4).

[0218] Scheme 2:

[0219] Alternatively, the compounds according to the invention can be prepared in three steps starting from the building blocks BS (see Scheme 3). First, the building blocks BS (synthesis see Experimental Section) can be prepared in a palladium-phosphine-catalyzed Hartwig-Buchwald-type CN coupling by reaction with a primary o-chloroarylamine to give a secondary o-bis-chloroarylamine (step 1). This can be cyclized in step 2 in a palladium-phosphine-catalyzed CC coupling to give the o-chlorocarbazole. The carbazole can then be cyclized in a palladium-phosphine-catalyzed CN coupling followed by a CC coupling to give the compounds according to the invention (see step 3). The CN or CC couplings can be carried out sequentially or in a dropwise reaction.If two different carbazoles are used in step 3—as a mixture or by sequential addition—mixed functionalized compounds of the invention can be obtained. This procedure has the advantage of being regioselective with respect to the carbazole with regard to the coupling and cyclization to the central building block in step 3.

[0220] Scheme 3:

[0221] The meaning of the symbols used in Schemes 1, 2 and 3 essentially corresponds to those defined for formula (I) or preferred embodiments of these structures, whereby numbering and a complete representation of all symbols have been omitted for reasons of clarity. Furthermore, for reasons of clarity, the use of symbols to represent possible nitrogen atoms in the heteroaromatic rings has been omitted in many cases, as these are represented in particular in formulas (I-1) to (I-4) by the symbols X, X a , X b and X c These details are therefore to be understood as examples, whereby the person skilled in the art is able to transfer the syntheses presented above and below, in particular in the examples, to compounds in which one or more of the symbols X, X a , X b and X c stand for nitrogen.

[0222] The principles of the preparation processes described above are, in principle, known from the literature for similar compounds and can be easily adapted by those skilled in the art to prepare the compounds of the invention. Further information can be found in the examples.

[0223] By these processes, optionally followed by purification, such as recrystallization or sublimation, the compounds according to the invention can be obtained in high purity, preferably more than 99% (determined by 1 H-NMR and / or HPLC).

[0224] The compounds of the invention can also be mixed with a polymer. It is also possible to covalently incorporate these compounds into a polymer. This is particularly possible with compounds substituted by reactive leaving groups, such as bromine, iodine, chlorine, boronic acid, or boronic acid esters, or by reactive, polymerizable groups, such as olefins or oxetanes. These can be used as monomers to produce corresponding oligomers, dendrimers, or polymers. The oligomerization or polymerization preferably takes place via the halogen functionality or the boronic acid functionality, or via the polymerizable group, respectively. It is also possible to crosslink the polymers via such groups. The compounds and polymers of the invention can be used as crosslinked or uncrosslinked layers.

[0225] The invention therefore further provides oligomers, polymers or dendrimers comprising one or more of the above-listed structures of the formula (I) and preferred embodiments of this formula or compounds according to the invention, wherein one or more bonds of the compounds according to the invention or of the structures of the formula (I) and preferred embodiments of this formula to the polymer, oligomer or dendrimer are present. Depending on the linkage of the structures of the formula (I) and preferred embodiments of this formula or of the compounds, these therefore form a side chain of the oligomer or polymer or are linked in the main chain. The polymers, oligomers or dendrimers can be conjugated, partially conjugated or non-conjugated. The oligomers or polymers can be linear, branched or dendritic.The same preferences as described above apply to the repeating units of the compounds according to the invention in oligomers, dendrimers and polymers.

[0226] To prepare the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. Copolymers are preferred, wherein the units according to formula (I) or the preferred embodiments described above and below are present in amounts of 0.01 to 99.9 mol%, preferably 5 to 90 mol%, particularly preferably 20 to 80 mol%. Suitable and preferred comonomers which form the polymer backbone are selected from fluorenes (e.g. according to EP 842208 or WO 2000 / 022026), spirobifluorenes (e.g. according to EP 707020, EP 894107 or WO 2006 / 061181), para-phenylenes (e.g. according to WO 92 / 18552), carbazoles (e.g. according to WO 2004 / 070772 or WO 2004 / 113468), thiophenes (e.g. according to EP 1028136), dihydrophenanthrenes (e.g. according to WO 2005 / 014689), cis- and trans-indenofluorenes (e.g. according to WO 2004 / 041901 or WO 2004 / 113412), ketones (e.g. according to WO 2005 / 040302), phenanthrenes (e.g.according to WO 2005 / 104264 or WO 2007 / 017066) or several of these units. The polymers, oligomers, and dendrimers may contain further units, for example hole-transport units, in particular those based on triarylamines, and / or electron-transport units.

[0227] Of particular interest are also compounds according to the invention that are characterized by a high glass transition temperature. In this context, particular preference is given to compounds according to the invention comprising structures according to formula (I) or the preferred embodiments described above and below, which have a glass transition temperature of at least 70°C, more preferably of at least 110°C, most preferably of at least 125°C, and especially preferably of at least 150°C, determined according to DIN 51005 (version 2005-08).

[0228] For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, Decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene,Phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butylmethyl ether, triethylene glycol butylmethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents.

[0229] The present invention therefore further provides a formulation or a composition comprising at least one compound according to the invention and at least one further compound. The further compound can, for example, be a solvent, in particular one of the abovementioned solvents or a mixture of these solvents. If the further compound comprises a solvent, this mixture is referred to herein as a formulation. However, the further compound can also be at least one further organic or inorganic compound which is likewise used in the electronic device, for example an emitter and / or a matrix material, wherein these compounds differ from the compounds according to the invention. Suitable emitters and matrix materials are listed below in connection with the organic electroluminescent device. The further compound can also be polymeric.

[0230] The present invention therefore further provides a composition comprising a compound according to the invention and at least one further organic functional material. Functional materials are generally the organic or inorganic materials that are introduced between the anode and cathode. The organic functional material is preferably selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocking materials, hole blocking materials, wide-band gap materials, and n-dopants, preferably host materials.

[0231] The present invention further provides for the use of a compound according to the invention in an electronic device, in particular in an organic electroluminescent device, preferably as an emitter, particularly preferably as a green, red, or blue emitter, especially preferably as a blue emitter. Compounds according to the invention preferably exhibit fluorescent properties and thus preferably provide fluorescent emitters.

[0232] The present invention further relates to an electronic device comprising at least one compound according to the invention. An electronic device within the meaning of the present invention is a device that contains at least one layer containing at least one organic compound. The component may also contain inorganic materials or layers composed entirely of inorganic materials.

[0233] The electronic device is preferably selected from the group consisting of Particularly preferred electronic device is selected from the group consisting of organic electroluminescent devices (OLEDs, sOLEDs, PLEDs, LECs, etc.), preferably organic light-emitting diodes (OLEDs), organic light-emitting diodes based on small molecules (sOLEDs), organic light-emitting diodes based on polymers (PLEDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), “organic plasmon 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 optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs) and organic electrical sensors, preferably organic electroluminescent devices (OLEDs, sOLEDs, PLEDs, LECs, etc.), particularly preferably organic light-emitting diodes (OLEDs), organic light-emitting diodes based on small molecules (sOLEDs), organic light-emitting diodes based on polymers (PLEDs), in particular phosphorescent OLEDs.

[0234] The organic electroluminescent device contains a cathode, an anode, and at least one emitting layer. In addition to these layers, it may contain further layers, for example, one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers, and / or charge-generation layers. Interlayers, which, for example, have an exciton-blocking function, may also be inserted between two emitting layers. It should be noted, however, that not all of these layers are necessarily present. The organic electroluminescent device may contain one emitting layer or it may contain multiple emitting layers.If multiple emission layers are present, they preferably have a total of multiple emission maxima between 380 nm and 750 nm, resulting in overall white emission. This means that different emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. Systems with three emitting layers are particularly preferred, with the three layers exhibiting blue, green, and orange or red emission. The organic electroluminescent device according to the invention can also be a tandem electroluminescent device, particularly for white-emitting OLEDs.

[0235] The compound according to the invention can be used in different layers, depending on the precise structure. Preference is given to an organic electroluminescent device comprising a compound according to formula (I) or the preferred embodiments described above in an emitting layer as an emitter, preferably a red, green, or blue emitter, particularly preferably as a blue emitter.

[0236] When the compound according to the invention is used as an emitter in an emitting layer, a suitable matrix material which is known as such is preferably used.

[0237] A preferred mixture of the compound according to the invention and a matrix material contains between 99 and 1 vol.%, preferably between 98 and 10 vol.%, particularly preferably between 97 and 60 vol.%, in particular between 95 and 80 vol.% of matrix material, based on the total mixture of emitter and matrix material. Accordingly, the mixture contains between 1 and 99 vol.%, preferably between 2 and 90 vol.%, particularly preferably between 3 and 40 vol.%, in particular between 5 and 20 vol.% of the emitter, based on the total mixture of emitter and matrix material.

[0238] Suitable matrix materials which can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g. according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triarylamines, carbazole derivatives, e.g. CBP (N,N-biscarbazolylbiphenyl) or those in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176, indolocarbazole derivatives, e.g. B. according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, e.g. according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776, azacarbazole derivatives, e.g. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, e.g. according to WO 2007 / 137725, silanes, e.g. according to WO 2005 / 111172, azaboroles or boronic esters, e.g. according to WO 2006 / 117052, triazine derivatives, e.g. B.according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, diazasilole or tetraazasilole derivatives, e.g. according to WO 2010 / 054729, diazaphosphole derivatives, e.g. according to WO 2010 / 054730, bridged carbazole derivatives, e.g. B. according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080, triphenylene derivatives, e.g. according to WO 2012 / 048781, dibenzofuran derivatives, e.g. according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565 or biscarbazoles, e.g. according to JP 3139321 B2.

[0239] Furthermore, a compound that does not participate, or does not participate to a significant extent, in charge transport can be used as a co-host, as described, for example, in WO 2010 / 108579. Particularly suitable co-matrix materials in combination with the compound according to the invention are compounds that have a large band gap and do not themselves participate, or at least do not participate to a significant extent, in the charge transport of the emitting layer. Such materials are preferably pure hydrocarbons. Examples of such materials can be found, for example, in WO 2009 / 124627 or WO 2010 / 006680.

[0240] In a preferred embodiment, a compound according to the invention used as an emitter is preferably used in combination with one or more phosphorescent materials (triplet emitters) and / or a compound that represents a TADF (thermally activated delayed fluorescence) host material. A hyperfluorescence and / or hyperphosphorescence system is preferably formed. WO 2015 / 091716 A1 and WO 2016 / 193243 A1 disclose OLEDs that contain both a phosphorescent compound and a fluorescent emitter in the emission layer, wherein the energy is transferred from the phosphorescent compound to the fluorescent emitter (hyperphosphorescence). In this context, the phosphorescent compound therefore behaves like a host material.As those skilled in the art know, host materials have higher singlet and triplet energies than the emitters, so that the energy of the host material is transferred to the emitter as optimally as possible. The systems disclosed in the prior art exhibit precisely such an energy relationship.

[0241] For the purposes of this invention, phosphorescence refers to luminescence from an excited state with a higher spin multiplicity, i.e., a spin state > 1, in particular from an excited triplet state. For the purposes of this application, all luminescent complexes with transition metals or lanthanides, in particular all indium, platinum, and copper complexes, are considered phosphorescent compounds.

[0242] Particularly suitable phosphorescent compounds (= triplet emitters) are compounds that emit light upon suitable excitation, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are preferably used as phosphorescent emitters, in particular compounds containing iridium or platinum.

[0243] Examples of the emitters described above can be found in the applications WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626, WO 2011 / 066898, WO 2011 / 157339, WO 2012 / 007086, WO 2014 / 008982, WO 2014 / 023377, WO 2014 / 094961, WO 2014 / 094960, WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO 2016 / 015815, WO 2016 / 124304, WO 2017 / 032439, WO 2018 / 011186, WO 2018 / 001990, WO 2018 / 019687, WO 2018 / 019688, WO 2018 / 041769, WO 2018 / 054798, WO 2018 / 069196, WO 2018 / 069197, WO 2018 / 069273, WO 2018 / 178001, WO 2018 / 177981, WO 2019 / 020538, WO 2019 / 115423, WO 2019 / 158453 and WO 2019 / 179909.In general, all phosphorescent complexes as used according to the prior art for phosphorescent electroluminescent devices and as known to the person skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art can use further phosphorescent complexes without inventive step.

[0244] A compound according to the invention can preferably be used in combination with a TADF host material and / or a TADF emitter, as previously explained.

[0245] The process known as thermally activated delayed fluorescence (TADF) is described, for example, by BH Uoyarna et al., Nature 2012, Vol. 492, 234. To enable this process, a comparatively small singlet-triplet distance AE(Si - Ti) of, for example, less than about 2000 cm -1necessary. To open the inherently spin-forbidden Ti-Si transition, another compound can be provided in the matrix next to the emitter, which exhibits strong spin-orbit coupling, enabling inter-system crossing through the spatial proximity and the resulting interaction between the molecules. Alternatively, the spin-orbit coupling can be generated via a metal atom contained in the emitter.

[0246] Further valuable information on hyperfluorescence systems is provided in WO2012 / 133188 (Idemitsu), WO2015 / 022974 (Kyushu Univ.), WO201 5 / 098975 (Idemitsu), W02020 / 053150 (Merck) and DE202019005189 (Merck), among others.

[0247] Further valuable information on hyperphosphorescence systems is provided, among others, in WO2015 / 091716 A1, WO2016 / 193243 A1 (BASF), W001 / 08230 A1 (Princeton Univ. (Mark Thompson)), US2005 / 0214575A1 (Fuji), WO2012 / 079673 (Merck), W02020 / 053314 (Merck) and W02020 / 053315 (Merck).

[0248] In a further embodiment of the invention, the organic electroluminescent device according to the invention does not contain a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, i.e. the emitting layer directly adjoins the hole injection layer or the anode, and / or the emitting layer directly adjoins the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051. Furthermore, it is possible to use a metal complex that is the same as or similar to the metal complex in the emitting layer directly adjacent to the emitting layer as a hole transport or hole injection material, as described, for example, in WO 2009 / 030981.

[0249] In the further layers of the organic electroluminescent device according to the invention, all materials commonly used in the prior art can be used. Therefore, the skilled person can, without inventive step, use all materials known for organic electroluminescent devices in combination with the compounds according to formula (I) according to the invention or the preferred embodiments described above.

[0250] Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10' 5 mbar, preferably less than 10' 6 mbar. However, it is also possible that the initial pressure is even lower, for example less than 10' 7 mbar.

[0251] Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are sublimated at a pressure between 10' 5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured.

[0252] Also preferred is an organic electroluminescent device characterized in that one or more layers are produced from solution, such as by spin coating, or by any printing process, such as screen printing, flexographic printing, offset printing, LITI (Light Induced Thermal Imaging, thermal transfer printing), inkjet printing, or nozzle printing. Soluble compounds are required for this, which are obtained, for example, by suitable substitution.

[0253] Formulations for applying a compound according to formula (I) or the preferred embodiments thereof set out above are novel. A further subject of the present invention is therefore a formulation comprising at least one solvent and a compound according to formula (I) or the preferred embodiments thereof set out above.

[0254] Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are vapor-deposited.

[0255] These processes are generally known to those skilled in the art and can be applied by them without inventive step to organic electroluminescent devices containing the compounds of the invention. The compounds of the invention and the organic electroluminescent devices of the invention are distinguished from the prior art in particular by an improved lifetime and higher color purity. The other electronic properties of the electroluminescent devices, such as efficiency or operating voltage, remain at least equally good. In a further variant, the compounds of the invention and the organic electroluminescent devices of the invention are distinguished from the prior art in particular by an improved efficiency and / or operating voltage and a longer lifetime.

[0256] The electronic devices according to the invention, in particular organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art:

[0257] 1. Electronic devices, in particular organic electroluminescent devices comprising compounds of formula (I) or the preferred embodiments described above and below as emitters, have very narrow emission bands with low FWHM (Full Width Half Maximum) values ​​and lead to particularly color-pure emission, recognizable by the small CIE y values. What is particularly surprising here is that both blue emitters with low FWHM values ​​and emitters with low FWHM values ​​that emit in the green, yellow, or red range of the color spectrum are provided.

[0258] The emission bands have a shoulder or a secondary maximum in the long-wave emission flank, each of which has an intensity of less than 40%, often less than 30%, of the main maximum. In top-emission OLED components, this leads to a favorably low viewing angle dependence of the color impression compared to narrow-band boron-containing emitters of the prior art, which often do not have such shoulders or secondary maxima and exhibit a greater viewing angle dependence of the color impression. Electronic devices, in particular organic electroluminescent devices comprising compounds of the formula (I) or the preferred embodiments described above and below, in particular as emitters, have a very long lifetime. In particular, these compounds bring about a low roll-off, i.e. a low drop in the power efficiency of the device at high luminances.Electronic devices, in particular organic electroluminescent devices containing compounds of formula (I) or the preferred embodiments described above and below as emitters, exhibit outstanding efficiency. Compounds of the invention of formula (I) or the preferred embodiments described above and below result in a low operating voltage when used in electronic devices. The compounds of the invention of formula (I) or the preferred embodiments described above and below exhibit very high stability and long service life. Compounds of formula (I) or the preferred embodiments described above and below can be used to prevent the formation of optical loss channels in electronic devices, in particular organic electroluminescent devices.As a result, these devices are characterized by high PL and thus high EL efficiency of emitters and excellent energy transfer from the matrices to dopants.

[0259] Exciton energy is transferred from a matrix or host in the emission layer to the emitter typically via either the so-called Dexter or Förster transfer.

[0260] Förster energy transfer (FRET) from a host or matrix to the emitter according to the invention is particularly preferred because it is particularly efficient, leading to electronic devices with particularly good performance characteristics (e.g., efficiency, voltage, and lifetime). It has been shown that energy transfer from a host or matrix to the compounds according to the invention preferably occurs via Förster transfer.

[0261] 6. Compounds according to formula (I) or the preferred embodiments described above and below have excellent glass film formation.

[0262] 7. Compounds according to formula (I) or the preferred embodiments described above and below form very good films from solutions and show excellent solubility.

[0263] These advantages mentioned above are not accompanied by an excessive deterioration of the other electronic properties.

[0264] It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Any feature disclosed in the present invention may, unless explicitly excluded, be replaced by alternative features serving the same, equivalent, or similar purpose. Thus, unless otherwise stated, any feature disclosed in the present invention is to be considered an example of a generic series or an equivalent or similar feature.

[0265] All features of the present invention may be combined with each other in any way, unless certain features and / or steps are mutually exclusive. This applies in particular to preferred features of the present invention. Likewise, features of non-essential combinations may be used separately (and not in combination).

[0266] It should further be noted that many of the features, and particularly those of the preferred embodiments of the present invention, are inventive in their own right and should not be considered merely part of the embodiments of the present invention. Independent protection may be sought for these features in addition to or alternatively to any presently claimed invention.

[0267] The teaching of technical action disclosed in the present invention can be abstracted and combined with other examples.

[0268] The invention is further illustrated by the following examples, without intending to limit it. From these descriptions, one skilled in the art can practice the invention within the entire disclosed scope and, without inventive step, prepare further compounds according to the invention and use them in electronic devices or apply the method according to the invention.

[0269] Examples:

[0270] Unless otherwise stated, the following syntheses were carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective information in square brackets or the numbers given for individual compounds refer to the CAS numbers of the known compounds. For compounds that can exhibit multiple configurational isomers, enantiomers, diastereomers, or tautomeric forms, one form is shown representatively. The following abbreviations are used for solvents and reagents: DCM - dichloromethane, EE - ethyl acetate, THF - tetrahydrofuran, EtOH - ethanol, NCS - N-chlorosuccinimide, NBS - N-bromosuccinimide, NIS, N-iodosuccinimide.

[0271] 1) Representation of the synthons

[0272] 1.1) Bicyclic ketones:

[0273] A) Via Grignard Route:

[0274] S1 can be prepared by the Grignard route starting from the above-mentioned starting materials, according to the following literature, in 34% yield: Step 1-4: BM Fox et al., J. Med. Chem., 2014, 52, 3464.

[0275] Level 5: I. Dragutan et al., Org. Prep. Proced., Int., 1975, 7, 2, 75.

[0276] The purification, in particular the separation of regioisomers of the cyclization in step 5, is carried out via flash chromatography on a column chromatography machine (Combi-Flash Torrent, Axel Semrau).

[0277] B) Via Suzuki route:

[0278] S50 can also be reached on the above mentioned Suzuki route starting from the above mentioned

[0279] Educts, according to the following literature, in 41% yield:

[0280] Stage 1 to 3: C. Dolente et al., WO 2011 / 120877

[0281] Level 4: I. Dragutan et al., Org. Prep. Proced., Int. , 1975, 7, 2, 75.

[0282] The purification, in particular the separation of regioisomers of the cyclization in step 4, is carried out via flash chromatography on a column chromatography machine (Combi Flash Torrent, Axel Semrau). C) Via Friedel-Crafts alkylation and acylation

[0283] S2 can be prepared in 28% yield by the above-mentioned Friedel-Crafts route, according to the following literature, using 2-chloroanisole instead of anisole:

[0284] Level 1: Ismailov, AG et al., Nauch. Tr. Azerb. lln-t. Ser. Khim. N, 1979, (4), 47.

[0285] Level 2: Ismailov, AG et al., Zhurnal Organicheskoi Khimii, 1978, 14(4), 811.

[0286] Stages 3 and 4: ML Maddess et al., Org. Process Res. Dev. 2014, 18, 528-538.

[0287] The purification, in particular the separation of regioisomers of the cyclization in step 2, is carried out via flash chromatography on a column chromatography machine (Combi-Flash Torrent, Axel Semrau).

[0288] The following synthons can be represented analogously:

[0289] S9 can be prepared in 55% yield by the Grignard route A) according to the literature mentioned above or by the Grignard route described by GM Castanedo et al., J. Med. Chem., 2017, 60, 627, by using 1-bromo-2-chloro-4-iodobenzene instead of 1-bromo-2-fluoro-4-iodobenzene.

[0290] S100 can be prepared in 69% yield by the above-mentioned route, according to the following literature: Step 1 and 2: WS Tan et al., J. Chin. Chem. Soc., 2012, 59, 399.

[0291] Stage 3: JM Herbert et al., J. Label. Compd. Radiopharm., 2007, 50, 440.

[0292] The purification is carried out via flash chromatography on a column chromatography machine (Combi-Flash Torrent, Axel Semrau).

[0293] The following synthons can be represented analogously.

[0294] Alternative representation:

[0295] Alternatively, S100 to S103 can be operated on the following route in improved

[0296] Yield can be shown:

[0297] Steps 1 and 3: Analogous to WS Tan et al., J. Chin. Chem. Soc., 2012, 59, 399. Yield of step 1 ~ 95%, yield of step 3 quantitative.

[0298] Step 2: Iodination with N-iodosuccinimide in trifluoroethanol (TFE) or hexafluoroisopropanol, analogous to R.-J. Tang et al. J. Org. Chem., 2018, 83, 930. Yield 93%.

[0299] Example S100b:

[0300] Analogously, the corresponding bromotriflates can be obtained using N-bromosuccinimide. Yield over three steps: 87%.

[0301] Example S100c: Analogously, the corresponding chlorotriflates can be obtained using N-chlorosuccinimide. Yield over three steps: 69%.

[0302] Example S110:

[0303] Procedure analogous to WS Tan et al., J. Chin. Chem. Soc., 2012, 59, 399.

[0304] Dimethylacetamide (DMAC) is used instead of DMF, resulting in improved yields. Yield: 66%.

[0305] Analogous to S110 (alternative representation), the following synthons can be represented.

[0306] Alternatively, S110 can be represented as follows: Step 1 : Analogous to MA Zolfigol et al., Molecules 2001 , 6, 614. Yield: 93 %.

[0307] Step 2: G. Ralf et al. Journal fuer Praktische Chemie 1987, 329(6), 945. Yield 89%.

[0308] Step 3: Analogous to S. Chandrappa et al., Synlett 2010, 3019. Yield: 87%.

[0309] Step 4: EA Krasnokutskaya, Synthesis 2007, (1 ), 81. Yield 70 %

[0310] Optimized synthesis of S110:

[0311] Level 1 :

[0312] A solution of 29.5 g (100 mmol) of 1-cyano-4-hydroxytriptycene, cooled to 0 °C, is added dropwise to a mixture of 19.0 g of 65 wt% nitric acid and 20.0 g of 96 wt% nitric acid over a period of 1 h. Stirring is continued for 30 min, and then the mixture is carefully poured (foaming!) into a mixture of 37.8 g (450 mmol) of sodium bicarbonate and 3 l of ice water while stirring vigorously. The organic phase is separated, the aqueous phase is extracted three times with 200 ml of DCM each time, the combined organic phases are dried with saturated brine, and the precipitated solution is placed on magnesium sulfate. The drying agent is filtered off, the DCM is removed in vacuo, and the residue is chromatographed (silica gel, n-heptane / EA 5:1). Yield: 31.5 g (93 mmol) 93%; purity approx. 98%. 1 H-NMR.

[0313] Level 2:

[0314] A well-stirred mixture of 34.0 g (100 mmol) of 1-cyano-3-nitro-4-hydroxytriptycene and 93.5 ml (1 mol) of phosphoryl chloride is treated with 21.0 ml (120 mmol) of diisopropylethylamine (DIPEA) and heated under reflux for 4 h. The reaction mixture is poured slowly (exothermally, induction period!) into 2 l of ice water with very vigorous stirring and stirred for a further 30 min. The aqueous phase is extracted five times with 200 ml of DCM each time, the combined organic phases are dried with saturated brine, and the residue is placed on magnesium sulfate. The drying agent is filtered off, the DCM is removed in vacuo, and the residue is chromatographed (silica gel, n-heptane / EA 5:1). Yield: 40.1 g (89 mmol) 89%; Purity approx. 97% ig n. 1 H-NMR.

[0315] Step 3: A well-stirred suspension of 35.9 g (100 mmol) of 1-cyano-3-nitro-4-chlorotriptycene and 25.1 g (450 mmol) of iron powder in 700 mL of EtOH is added dropwise over 30 min to 75.0 mL of 37 wt% aqueous hydrochloric acid (Caution: Evolution of hydrogen!). Stir for a further 3 h at reflux, allow to cool, dilute with 2 l water and 2 l DCM, and make alkaline (pH ~ 9) by cautiously adding (foaming!) solid sodium carbonate. The mixture is filtered off with suction through Celite, the organic phase of the filtrate is separated, the aqueous phase is extracted five times with 100 mL of DCM each time, the combined organic phases are dried by washing twice with 300 mL of saturated sodium chloride solution each time, and the mixture is placed on magnesium sulfate. The desiccant is removed by filtration, the DCM is removed in vacuo, the crude product is concentrated to isolate, and chromatographed (silica gel, n-heptane / DCM 1:1 > 1:2). If necessary, repeat the chromatography until the product is white to slightly beige.Yield: 28.5 g (87 mmol) 87%; purity approx. 98%. 1 H-NMR.

[0316] Level 4:

[0317] A solution of 32.9 g (100 mmol) of 1-cyano-3-amino-4-chloro-triptycene in 500 mL of acetonitrile (4 l four-neck flask, internal thermometer, dropping funnel, precision glass stirrer, aron blanket) is added portionwise to 57.1 g (300 mmol) of p-toluenesulfonic acid monohydrate [6192-52-5] and then cooled to 10 °C in an ice bath. A solution of 13.9 g (200 mmol) of sodium nitrite and 37.5 g (250 mmol) of potassium iodide in 60 mL of water is added dropwise to the suspension with vigorous stirring and ice cooling. The mixture is stirred for 15 min at 10 °C (caution: evolution of nitrogen - foaming). The mixture is then allowed to warm to room temperature and stirred for a further 70 min. Then, dilute with 1500 ml of water, adjust to pH 9.5 by adding saturated sodium bicarbonate solution, and add 200 ml of 2M sodium bisulfite solution. The precipitated crude product is filtered off with suction, washed twice with 50 ml of water each time, and briefly patted dry.The crude product is dissolved in 500 ml of DCM, the solution is dried over sodium sulfate, the desiccant is removed by suction, and the crude product is concentrated to an isotope. Purification is carried out by flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 31.1 g (70 mmol), 70%; Purity: approximately 97% pure. 1 H-NMR. Compounds S111 -S115 can be prepared analogously.

[0318] 1.3) Synthesis of substituted iodo-chloro-pyridines

[0319] Synthesis scheme using the example of a homoadamtane enamine:

[0320] Steps 1 to 5 are carried out analogously to known syntheses in the literature:

[0321] Levels 1 to 4: M. Adachi et al., Tetrahedron Letters, 37 (49), 8871, 1996; EP 0 556 008 B1.

[0322] Level 5: JD Eckelbarger et al., US 8835409;

[0323] EA Krasnokutskaya et al., Synthesis, 2007,1, 81.

[0324] A) Synthesis of enamines:

[0325] The enamines can be prepared from the shown ketones and morpholine in yields of approximately 60 - 80% according to the process described in WO 2020 / 064662, page 108.

[0326] B) Synthesis of substituted pyridines:

[0327] Example S200

[0328] A mixture of 23.3 g (100 mmol) of S200a (analogous for the other 6- and 7-membered-ring enamines), 22.6 g (120 mmol) of 4-(aminomethylene)-2-phenyl-5(4H)-oxazolone [3674-51-9], 47.3 ml (500 mmol) of acetic anhydride [108-24-7], and 150 ml of toluene was stirred at 100 °C for 4 h (5-membered-ring enamines are reacted in o-xylene at 130 °C for 4 h in an autoclave). The mixture was completely concentrated in vacuo, the oil was treated with 70 ml of methanol, and the mixture was stirred for 3 h. The crystallized product was filtered off with suction, washed once with 25 ml of ice-cold methanol, and dried in vacuo. The crude product thus obtained was further reacted without purification. Yield: 26.2 g (78 mmol), 78% E,Z isomer mixture; purity: approx. 95%. 1 H-NMR.

[0329] Stage 2: S200c

[0330] A mixture of 33.4 g (100 mmol) of S200b and 200 ml of 1-methyl-2-pyrrolidinone (NMP) is stirred for 1.5 h at 200-205 °C. The mixture is allowed to cool to approximately 100 °C, the NMP is largely removed in vacuo, the glassy, ​​viscous residue is taken up in 100 ml of warm acetonitrile, stirred for 12 h at room temperature, the crystallized product is filtered off with suction, and the residue is dried in vacuo. Yield: 25.1 g (75 mmol), 75%; Purity: approximately 95% pure. 1 H-NMR.

[0331] Stage 3: S200d

[0332] A suspension of 33.4 g (100 mmol) of S200c in a mixture of 150 ml of N,N-dimethylformamide (DMF) is treated dropwise with 14.0 ml (150 mmol) of phosphoryl chloride in 50 ml of DMF while cooling with ice and sodium chloride (approx. -10 °C). The mixture is then stirred at room temperature for 16 h. The reaction mixture is carefully poured into 1000 ml of ice-water, stirred for 10 min, 200 ml of dichloromethane (DCM) is added, stirred for 10 min and the organic phase is separated. The aqueous phase is made basic (pH 8-9) by cautiously adding concentrated aqueous ammonia solution, the aqueous phase is extracted three times with 200 ml of ethyl acetate each time, the combined ethyl acetate extracts are washed twice with 200 ml of ice-water each time and once with 200 ml of sat. Sodium bicarbonate solution and twice with 100 ml of saturated saline solution. The mixture is dried over a mixture of magnesium sulfate and sodium carbonate, filtered off the desiccant, and the organic solution is concentrated.Phase in vacuo and the residue was recrystallized once from acetonitrile with the addition of ethyl acetate (EE). Yield: 24.7 g (81 mmol), 81%; Purity: approximately 95% pure. 1 H-NMR.

[0333] A mixture of 30.4 g (100 mmol) of S200d, 100 ml of 3 N sulfuric acid, and 200 ml of dioxane was stirred at 100 °C for 1.5 h. After cooling, the reaction mixture was diluted with 1000 ml of ice-water and then adjusted to pH 7.5 with 3 N NaOH while cooling with ice. The aqueous phase was extracted three times with 200 ml of DCM each time. The combined organic phases were washed twice with 200 ml of water each time and once with 200 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant was removed by filtration, the filtrate was concentrated to dryness, and the residue was recrystallized from methanol. Yield: 23.1 g (93 mmol), 93%; Purity: approximately 95% pure. 1 H-NMR.

[0334] Level 5: S200

[0335] Variant 1 :

[0336] 24.9 g (100 mmol) of S200e are dissolved in 500 ml of solution with good stirring to 3 -

[0337] of concentrated hydrochloric acid cooled to 5 °C. A cold solution of 10.4 g (150 mmol) of sodium nitrite in 50 ml of water is added dropwise to the suspension over a period of 15 minutes while stirring well. The mixture is then stirred at 5 °C for approx. 20 minutes. The resulting diazonium solution is poured into a well-stirred solution of 90.0 g (600 mmol) of potassium iodide in 5000 ml of water, cooled to 5 °C, to which 1000 ml of DCM has been added (Caution: Foaming!). Once the evolution of nitrogen has ceased (approx. 25 minutes), sodium bisulfite solution is added until decolorization occurs. The mixture is carefully adjusted to pH 7.5 with 5 N NaOH while cooling very well. The mixture is diluted with a further 1500 ml of DCM, the org. The aqueous phase is re-extracted twice with 500 ml of DCM each time, the combined organic phases are washed twice with 500 ml of water each and twice with 500 ml of saturated sodium chloride solution, and then dried over magnesium sulfate.After removing the DCM under vacuum, the residue is flash chromatographed (Combi-Flash Torrent from A. Semrau). Yield:

[0338] 22.9 g (63 mmol), 63%; purity: approx. 97%. 1 H-NMR.

[0339] Variant 2:

[0340] A solution of 24.9 g (100 mmol) of S500 in 500 ml of acetonitrile is added portionwise to 57.1 g (300 mmol) of p-toluenesulfonic acid monohydrate [6192-52-5], and the mixture is then cooled to 10 °C in an ice bath. A solution of 13.9 g (200 mmol) of sodium nitrite and 37.5 g (250 mmol) of potassium iodide in 60 ml of water is added portionwise to the suspension with vigorous stirring and ice cooling, and the mixture is stirred for 15 min at 10 °C. The mixture is then allowed to warm to room temperature and stirred for a further 70 min. The mixture is then diluted with 1500 ml of water, adjusted to pH 9.5 by adding saturated sodium bicarbonate solution, and treated with 200 ml of 2M sodium bisulfite solution. The precipitated crude product is filtered off with suction, washed twice with 50 ml of water each time, and briefly dried with suction. The crude product is dissolved in 500 ml of DCM, the solution is dried over sodium sulfate, the desiccant is removed with suction, and the crude product is drawn down to an isolute solution. Purification is carried out by flash chromatography (Combi-Flash Torrent from A. Semrau).Yield: 25.0 g (72 mmol), 72%; Purity: approx. 97%. 1 H-NMR.

[0341] The following pyridines can be obtained analogously to steps 1 to 5. Yield over five steps (steps 1-5):

[0342]

[0343] 1.4) Synthesis of substituted iodo-chlorobenzenes

[0344] Example S300: Representation analogous to “Optimized synthesis of S110”. 2.

[0345] S300 Step 1 : Analogous to MA Zolfigol et al., Molecules 2001 , 6, 614. Yield: 96 %.

[0346] Step 2: G. Ralf et al. Journal of Practical Chemistry 1987, 329(6), 945. Yield 91%.

[0347] Step 3: Analogous to S. Chandrappa et al., Synlett 2010, 3019. Yield: 90%.

[0348] Step 4: EA Krasnokutskaya, Synthesis 2007, (1 ), 81. Yield: 78 %.

[0349] The following compounds can be prepared analogously, yield over four steps:

[0350] Example S400:

[0351] Suzkui coupling: 21.7 g (50 mmol) of 1,4-chloro-2,5-difluoro-3,6-diiodobenzene [2410043-16-0], 13.4 g (110 mmol) of phenylboronic acid, 31.8 g (300 mmol) of sodium carbonate, 702 mg (1 mmol) of bis(triphenylphosphino)palladium(II) chloride, 250 ml of acetonitrile, 250 ml of methanol, 60 °C, 12 h. Workup: Filter off salts, concentrate the filtrate, and extract the residue using DCM:water. Purification by flash chromatography. Yield: 12.9 g (38 mmol) 76%; Purity: approx. 97% pure. 1 H-NMR.

[0352] 2. Synthesis of carbazoles C:

[0353] Example C1 :

[0354] A well-stirred mixture of 30.0 g (100 mmol) of S1, 9.8 g (105 mmol) of aniline, 28.8 g (300 mmol) of sodium tert-butoxide, 1.11 g (2 mmol) of dppf, and 225 mg (1 mmol) of palladium(II) acetate in 500 ml of toluene is heated under reflux for 1 h. The mixture is allowed to cool to 70 °C, 500 ml of water is added, and the mixture is stirred for 10 min. The organic phase is separated, washed twice with 300 ml of water each time, once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The mixture is filtered through a Celite bed pre-slurried with toluene, the filtrate is concentrated in vacuo, the residue is dissolved in 300 ml of DCM, and the residue is removed in vacuo, with the distilled DCM being replaced by the simultaneous addition of EtOH. The crystallized product is filtered off with suction, washed three times with 50 ml of EtOH each time, and dried in vacuo. Yield: 27.7 g (89 mmol) 89%; Purity: approximately 98% by distillation. 1H-NMR. When using triflates, the triflate is added slowly, see J. Louie et al., Journal of Organic Chemistry 1997, 62(5), 1268.

[0355] Level 2:

[0356] A well-stirred mixture of 31.2 g (100 mmol) of the amine from step 1, 69.1 g (500 mmol) of potassium carbonate, 3.1 g (30 mmol) of pivalic acid, 1.16 g (4 mmol) of tri-tert-butylphosphonium tetrafluroborate, 449 mg (2 mmol) of palladium(II) acetate, 100 g of glass beads (3 mm diameter) and 1000 ml of dimethylacetamide (DMAC) is stirred for 1 h at 150 °C. The mixture is filtered while still hot through a Clite bed pre-slurried with DMAC, the filtrate is evaporated to dryness, the residue is dissolved in 500 ml of DCM and removed in vacuo, whereby the distilled DCM is substituted by the simultaneous addition of 300 ml of EtOH. The crystallized product is filtered off with suction, washed three times with 50 ml of EtOH each time, and dried in vacuo. Yield: 22.5 g (81 mmol) 81%; Purity: approximately 98% by 1 H-NMR.

[0357] The following compounds can be prepared analogously, yield over two steps:

[0358]

[0359] 

[0360] Example C600:

[0361] Level 1 :

[0362] A well-stirred solution of 42.5 g (100 mmol) of C100 in 1000 mL of DCM is added portionwise to 19.8 g (100 mmol) of N-bromosuccinimide (NBS), and the mixture is then stirred at RT for 5 h. The DCM is removed in vacuo, with the distilled DCM being replaced by simultaneous addition of MeOH; the final volume is approximately 300 mL. The crystallized product is filtered off with suction, washed twice with 50 mL of MeOH each time, and dried in vacuo. Yield: 48.0 g (95 mmol) 95%; Purity: approximately 98% by distillation. 1H-NMR.

[0363] A well-stirred mixture of 44.7 g (100 mmol) of the Br-carbazole from step 1, 7.0 ml (50 mmol) of trimethylboroxine [823-96-1], 41.5 g (300 mmol) of potassium carbonate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 449 mg (2 mmol) of palladium(II) acetate, 100 g of glass beads (3 mm diameter) and 800 ml of dimethylacetamide (DMAC) is stirred for 12 h at 120 °C. The mixture is filtered while still hot through a Clite bed pre-slurried with DMAC, the filtrate is evaporated to dryness, the residue is dissolved in 500 ml of DCM and removed in vacuo, whereby the distilled DCM is substituted by the simultaneous addition of 300 ml of EtOH. The crystallized product is filtered off with suction, washed three times with 50 ml of EtOH each time, and dried in vacuo. Yield: 31.7 g (83 mmol) 83%; Purity: approximately 98% by 1 H-NMR. The following compounds can be prepared analogously, yield in two steps:

[0364] 3. Compounds according to the invention:

[0365] Example D1 :

[0366] A well-stirred mixture of 41.0 g (100 mmol) of carbazole C1, 9.1 g (50 mmol) of 1,4-dichloro-2,5-difluorobenzene [400-05-5, ], 69.1 g (500 mmol) of potassium carbonate, 100 g of glass beads (3 mm diameter), and 1000 ml of dimethylacetamide (DMAC) is stirred at 150 °C for 3 h. The mixture is allowed to cool to 80 °C, 3.1 g (30 mmol) of pivalic acid, 1.16 g (4 mmol) of tri-tert-butylphosphonium tetrafluroborate, and 449 mg (2 mmol) of palladium(II) acetate are added, and the mixture is stirred at 140 °C for a further 2 h. The mixture is allowed to cool to 80 °C, 2000 ml of water is added dropwise, the precipitated crude product is filtered off with suction, washed three times with 200 ml of water and three times with 200 ml of ethanol, and dried in vacuo. The crude product is dissolved in 500-1000 ml of DCM (for pyridines, 10 wt.% ethyl acetate is added), filtered through a silica gel bed pre-slurried with DCM, and removed in vacuo. The distilled DCM is replaced towards the end by simultaneous addition of 300 ml of EtOH.The crystallized product is filtered off with suction, washed three times with 50 ml of EtOH each time, and dried in vacuo. Further purification is carried out by continuous hot extraction (common organic solvents or their combinations, preferably DCM or acetonitrile / DCM 3:1 to 1:3) or by flash chromatography (CombiFlash Torrent column system from A. Semrau, silica gel, RP silica gels, aluminum oxide, eluent: toluene / n-heptane / triethylamine, acetonitrile / THF, or DCM) and finally fractional sublimation or annealing under high vacuum (typically T approx. 200-400 °C, p approx. 10'). 5 up to 10' 6 mbar). Yield: 24.8 g (28 mmol) 56%; Purity: approximately 99.9% by HPLC.

[0367] If two different carbazoles C are used - as a mixture or preferably by sequential addition, ie first 50 mmol of the first carbazole then after a reaction time of about 2 h 50 mmol of the second carbazole - mixed functionalized compounds according to the invention can be obtained after chromatographic separation of the possible coupling and cyclization products.

[0368] The following connections can be represented analogously:

[0369] Step 1: Double Buchwald-Hartwig coupling, performed analogously to EP3723149A1, Example 2-5, Intermediate 12. The bis(chlorocarbazole) is isolated. Yield: 66%

[0370] Step 2: Double cyclization, carried out analogously to Example C1, Step 2, yield 57%. Instead of HP(t-Bu3)BF4, HP(t-Cys)BF4 can be used; the addition of 30 mol% pivalic acid typically increases the yield. Alternatively, the cyclization can be carried out with NHC-Pd complexes such as allyl-[1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene]-chloropalladium(II), see, for example, T. Kader et al., Chem. Europ. J., 2019, 25(17), 4412 or analogously to US 9,000,421 B1; typical yields 30-80%.

[0371] The following connections can be represented analogously:

[0372] Step 1 & 2: Procedure analogous to Taisei Taniguchi et al., Chem. Lett.

[0373] 2019, 48, 1160. Yield: 26% D300; 11% F100.

[0374] The following connections can be represented analogously: Manufacturing of OLED components 1) Vacuum-processed components

[0375] The compounds according to the invention can be used, among other things, as dopant in the emission layer in fluorescent and hyperphosphorescent OLED components.

[0376] The production of OLEDs (organic light emitting diodes) according to the invention as well as OLEDs according to the prior art is carried out according to a general process according to WO 2004 / 058911 , which is adapted to the conditions described here (layer thickness variation, materials used).

[0377] The following examples present the results of various OLEDs. Cleaned glass plates (cleaned in a Miele laboratory dishwasher using Merck Extran cleaner) coated with 50 nm thick structured ITO (indium tin oxide) are pretreated with UV ozone for 25 minutes (UV ozone generator PR-100, UVP). Within 30 minutes, they are coated with 20 nm of PEDOT:PSS (poly(3,4-ethylene-dioxythiophene)poly(styrenesulfonate), purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH, Germany, spin-coated from aqueous solution) for improved processing. These coated glass plates then form the substrates onto which the OLEDs are applied. After fabrication, the OLEDs are encapsulated to protect them from oxygen and water vapor. The exact layer structure of the electroluminescent OLEDs can be seen in the examples.The materials required to manufacture the OLEDs are shown in Table 8.

[0378] The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd / A), the power efficiency (measured in λ / W), and the external quantum efficiency (EQE, measured in percent) are determined as a function of luminance, calculated from current-voltage-luminance (IUL) curves assuming a Lambertian radiation pattern. The electroluminescence spectra are measured at a luminance of 100 or 1000 cd / m². 2 and from this the emission color and the EL-FWHM values ​​(ELectroluminescence - Full Width Half Maximum - width of the EL emission spectra at half peak height in eV, for better comparability across the entire spectral range) were taken.

[0379] Fluorescent OLED components:

[0380] All materials are thermally evaporated in a vacuum chamber. The emission layer (EML) always consists of at least one matrix material (host material) SMB and an emitting dopant (dopant, emitter) ES or EAS, which is mixed into the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as SMB:ES or EAS (97:3%) means that the material SMB is present in a volume fraction of 97% and the dopant ES or EAS is present in a volume fraction of 3% in the layer. Analogously, the electron transport layer can also consist of a mixture of two materials, e.g., as here, ETM1 (50%) and ETM2 (50%), see Table 1. The materials used to produce the OLEDs are shown in Table 8. For comparison, the compounds Ref.-D1 (see Table 8) are used.

[0381] Blue Fluorescence OLED Components BF:

[0382] The OLEDs basically have the following layer structure: Substrate

[0383] - Hole injection layer 1 (HIL1) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0384] - Hole transport layer 1 (HTL1) made of HTM1, 160 nm

[0385] - Hole transport layer 2 (HTL2), see Table 1

[0386] - Emission layer (EML), see Table 1

[0387] - Electron transport layer (ETL2), see Table 1

[0388] - Electron transport layer (ETL1) made of ETM1 (50%) and ETM2 (50%), 30 nm Electron injection layer (EIL) made of ETM2, 1 nm

[0389] - Cathode made of aluminum, 100 nm

[0390] Table 1: Structure of blue fluorescent OLED components

[0391] Table 2: Results

[0392] Hyperphosphorescent OLED components:

[0393] All materials are thermally evaporated in a vacuum chamber. The emission layer (EML) or the emission layers always consist of at least one matrix material (host material) TMM, a (phosphorescent) sensitizer PS, and a fluorescent emitter ES or EAS. The matrix material (host material) TMM can consist of two components that are evaporated as a mixture (premixed host, e.g., TMM2). The components and composition are also shown in Table 8. The sensitizer PS and the fluorescent emitter ES or EAS are mixed into the host material TMM by co-evaporation in a specific volume fraction. A specification such as TMM:PS(5%):ES or EAS(3%) means that the TMM material is present in the layer at a volume fraction of 92%, PS at a fraction of 5%, and ES or EAS at a fraction of 3%.

[0394] Blue hyperphosphorescent OLED devices BH:

[0395] The OLEDs basically have the following layer structure:

[0396] - Substrat

[0397] - Hole injection layer 1 (HIL1) made of HTM2 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0398] - Hole transport layer 1 (HTL1) made of HTM2, 30 nm

[0399] - Hole transport layer 2 (HTL2), see Table 3

[0400] - Emission layer (EML), see Table 3

[0401] - Electron transport layer (ETL2), see Table 3

[0402] - Electron transport layer (ETL1) made of ETM1 (50%) and ETM2 (50%), 20 nm

[0403] - Electron injection layer (EIL) made of ETM2, 1 nm

[0404] - Cathode made of aluminum, 100 nm

[0405] Table 3: Structure of blue hyperphosphorescent OLED components

[0406] Table 4: Results

[0407] Green hyperphosphorescent OLED devices GH:

[0408] The OLEDs basically have the following layer structure:

[0409] - Substrat

[0410] - Hole injection layer 1 (HIL1) made of HTM2 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0411] - Hole transport layer 1 (HTL1) made of HTM2, 30 nm

[0412] - Hole transport layer 2 (HTL2), see Table 5

[0413] - Emission layer (EML), see Table 5

[0414] - Electron transport layer (ETL2), see Table 5

[0415] - Electron transport layer (ETL1) made of ETM1 (50%) and ETM2 (50%), 30 nm

[0416] - Electron injection layer (EIL) made of ETM2, 1 nm

[0417] - Cathode made of aluminum, 100 nm

[0418] Table 5: Structure of green hyperphosphorescent OLED components

[0419] Table 6: Results

[0420] 2) Solution-processed components:

[0421] The production of solution-based OLEDs is generally described in the literature, e.g., in WO 2004 / 037887 and WO 2010 / 097155. In the following examples, both production methods (gas-phase deposition and solution processing) were combined, so that the layer up to and including the emission layer was processed from solution, and the subsequent layers (hole-blocking layer / electron-transport layer) were vacuum-deposited. The general processes described above are adapted and combined to the conditions described here (layer thickness variation, materials) as follows.

[0422] The structure used is as follows:

[0423] - Substrat

[0424] - ITO, 50 nm

[0425] - PEDOT, 20 nm

[0426] - Hole transport layer HIL-Sol, made of HTM-Sol, 20 nm

[0427] - Emission layer made of SMB4(97%) and ES(3%) or EAS(3%), 50 nm

[0428] - Electron transport layer (ETL1) made of ETM1 (50%) and ETM2 (50%), 25 nm

[0429] - Cathode made of aluminum, 100 nm

[0430] Glass flakes coated with structured ITO (indium tin oxide) with a thickness of 50 nm are used as the substrate. For easier processing, these are coated with the buffer (PEDOT) Clevios P ​​VP AI 4083 (Heraeus Clevios GmbH, Leverkusen) - PEDOT is written above. Spin coating takes place in air from water. The layer is then baked for 10 minutes at 180°C. The hole transport layer and the emission layer are applied to the coated glass flakes. The hole transport layer is the polymer HTM sol with the structure shown in Table 8, which was synthesized according to WO2010 / 097155. The polymer is dissolved in toluene, so that the solution typically has a solids content of approx. 5 g / l if, as here, the layer thickness of 20 nm typical for a device is to be achieved by spin coating. The layers are spun on in an inert gas atmosphere, in this case argon, and baked for 60 minutes at 180°C.

[0431] The emission layer always consists of at least one matrix material (host material) and one emitting dopant (emitter). A specification such as SMB4 (97%) and ES or EAS (3%) means that the SMB4 material is present in the emission layer at a weight fraction of 97% and the dopant ES or EAS at a weight fraction of 3%. The mixture for the emission layer is dissolved in toluene or chlorobenzene. The typical solids content of such solutions is approximately 18 g / l if, as here, the layer thickness of 50 nm typical for a device is to be achieved by spin coating. The layers are spun on in an inert gas atmosphere, in this case argon, and baked for 10 minutes at 140°C to 160°C. The materials used are shown in Table 8.

[0432] The materials for the electron-transport layer and the cathode are thermally vapor-deposited in a vacuum chamber. For example, the electron-transport layer can consist of more than one material, which are mixed together in a specific volume fraction by co-evaporation. A specification such as ETM1 (50%) and ETM2 (50%) means that the materials ETM1 and ETM2 each make up 50% of the layer. The materials used in this case are shown in Table 8.

[0433] Table 7: Results of the solution-processed OLEDs at

[0434] 1000 cd / m 2

[0435] Table 8: Structural formulas of the materials used

[0436] The abbreviations of the compounds of the invention used in the tables presented above with respect to the OLED devices refer to the abbreviations provided in the synthesis examples above.

[0437] The compounds of the invention exhibit narrower electroluminescence spectra compared to the reference, as evidenced by the lower or equal EL FWHM values ​​(electroluminescence - full width half maximum - width of the EL emission spectra in eV at half the peak height). Narrower electroluminescence spectra lead to significantly improved color purity (smaller CIE y values). Furthermore, the EQE values ​​(external quantum efficiencies) are significantly higher and the operating voltages lower compared to the reference, which leads to significantly improved device performance efficiencies and thus lower power consumption.

[0438] Production of components for color conversion

[0439] The compounds of the invention can be used for color conversion. For this purpose, the compounds are incorporated into a composition, which is then processed into pixels or flat layers using known methods (spin coating, slit coating, doctor blade coating, screen printing, nozzle printing, inkjet printing, etc.). The compositions typically consist of crosslinkable components (monomers, oligomers, polymers), e.g., based on acrylates, acrylamides, polyesters, silicones, etc., and one or more thermally or photochemically activatable starter components. In addition, other components such as organic auxiliaries (antioxidants, stabilizers, flow control agents, viscosity moderators, etc.) or inorganic fillers (SiO2, TiO2, Al2O3, etc.) can be incorporated.

[0440] General manufacturing procedure of the composition and derived layers:

[0441] 0.5 g of the compound ES or EAS according to the invention, 0.2 g of titanium dioxide (TiO2 ToyoColor, Toyo Ink Group), and 10 g of OE-6550 Optical Encapsulant (Dow Corning) are homogenized at 40 °C with very thorough stirring (magnetic stirrer) and the action of ultrasound (ultrasonic bath). Coatings approximately 15 |Lm thick are produced by doctor blade coating and then cured by annealing under a nitrogen atmosphere (150 °C, 1 hour).

[0442] Spectral measurement of the layers:

[0443] Fluorescence spectra and EQE values ​​(external quantum efficiency, EQE = emitted photons / absorbed photons) of the layers are determined in a fluorescence spectrometer (C9920, Hamamatsu photonics) with integrating sphere and fiber optics (excitation wavelength CWL: 420 - 440 nm for blue, 450 nm for green emitters, reference measurement in air at room temperature).

[0444] Results

[0445] Table 9 summarizes the results:

Claims

Patent claims Connection comprising at least one structure of formula (I), Formula (I) where A is the same or different for each occurrence for a substructure of formula (A1) or (A2), Formula (A1) Formula (A2) to which the two substructures B are condensed, and the symbols o and * represent the two condensation points of the respective substructure B, wherein one substructure B is condensed to A via the positions marked with o and one substructure B is condensed to A via the positions marked with * and at least one of the substructures B is selected from a substructure of formula (B1) Formula (B1) and another of the substructures B is selected from a substructure of the previously presented formula (B1) or a substructure of the formula (B2) where the dashed bonds represent the condensation sites of ring structure B on A, the ring C c In each instance, the same or different symbols represent a condensed aliphatic or heteroaliphatic ring with 5 to 60 ring atoms, which may be substituted with one or more R residues, the ring C b In each instance, the symbol represents a condensed aliphatic or heteroaliphatic ring with 5 to 60 ring atoms, which may be substituted with one or more R groups, and the following applies to the other symbols: Z, in each instance, stands for N, C-CN or CR, whether the same or different. C ; Y is the same or different in each occurrence CO, P(=O)R C , SO, SO2, C(O)O, C(S)O, C(O)S, C(=O)NR C , C(=O)NAr', W 1 , W 2 In each instance, it represents C(R)2, 0, S, Si(R)2, either the same or different; X represents N or CR in each instance, either the same or different, with the proviso that no more than two of the groups X, X b in a cycle for N; X a In each instance, it represents N or CR, whether the same or different. a ; X b In each instance, it represents N or CR, whether the same or different. b provided that no more than two of the groups X, X b in a cycle for N; X c In each instance, it represents N or CR, whether the same or different. C ; R is the same or different in each occurrence: H, D, OH, F, CI, Br, I, CN, NO2, N(Ar)2, N(R d )2, C(=O)N(Ar)2, C(=O)N(R d )2, C(Ar)3, C(R d )3, Si(Ar)3, Si(R d )3, B(Ar)2, B(R d )2, C(=O)Ar, C(=O)R d , P(=O)(Ar)2, P(=O)( R d )2, P(Ar)2, P(R d )2, S(=O)Ar, S(=O)R d , S(=O)2Ar, S(=O)2R d , OSO2Ar, OSO2Rd , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms, or an alkenyl or alkynyl group with 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each linked to one or more R groups d can be substituted, with one or more non-adjacent CH2 groups being replaced by R d C=CR d , C=C, Si(R d )2, C=O, C=S, C=Se, C=NR d , -C(=O)O- -C(=O)NR d -, NR d , P(=O)( R d ), -O-, -S-, SO or SO2 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each replaced by one or more R groups d may be substituted, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, separated by one or more R groups dmay be substituted, or an arylthio or heteroarylthio group with 5 to 60 aromatic ring atoms, separated by one or more R groups d may be substituted, or a Diarylamino, arylheteroarylamino, diheteroarylamino group with 5 to 60 aromatic ring atoms separated by one or more R groups d may be substituted, or an arylalkyl or heteroarylalkyl group with 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl group, separated by one or more R groups d It can be substituted; in this case, a residue R can form a ring system with another group; Ar, in each occurrence, is either the same or different, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, coupled with one or more R groups. dcan be substituted, whereby two Ar residues bonding to the same C atom, Si atom, N atom, P atom or B atom can also be connected by a single bond or a bridge selected from B(R d ), C(R d )2, Si(R d )2, C=O, C=NR d , C=C(R d )2, O, S, S=O, SO2, N(R d ), P(R d ) and P(=O)R d , be bridged together; R a , R b , R c , R d is the same or different in each occurrence H, D, OH, F, CI, Br, I, CN, NO2, 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)R 1 , S(=O)2Ar', S(=O)2R 1 , OSO2Ar', OSO2R 1, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms, or an alkenyl or alkynyl group with 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each linked to one or more R groups 1 can be substituted, where one or more non-adjacent CH2 groups are replaced by C=NR or may be replaced by SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is replaced by one or more R groups 1 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, separated by one or more R groups 1 can be substituted; in this case, two residues R can be involved. a , R b , R c , R d also form a ring system with each other or with another group; Ar' is, in each occurrence, either the same or different, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, coupled with one or more R substituents. 1 can be substituted, whereby two Ar' residues, which bond to the same C atom, Si atom, N atom, P atom or B atom, can also be connected by a single bond or a bridge, selected from B(R 1 ), C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, 0, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 , be bridged together; R 1 is the same or different in each occurrence H, D, F, CI, Br, I, CN, NO2, 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 straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 C atoms or an alkenyl group with 2 to 40 C atoms, each with one or more R groups 2 can be substituted, where one or more non-adjacent CH2 groups are replaced by -e, C=NR 2 , -C(=O)O- or SO2 may be replaced and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is replaced by one or more R groups 2 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, separated by one or more R groups 2 may be substituted, or an aralkyl or heteroaralkyl group with 5 to 60 aromatic ring atoms, coupled with one or more R groups2 may be substituted, or a combination of these systems; in this case, two or more residues R can be used. 1 together they form a ring system, whereby one or more residues R can be 1 form a ring system with another part of the compound; “Ar” is, in each occurrence, either the same or different, an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which is coupled with one or more R groups. 2 can be substituted, whereby two residues Ar”, which bond to the same C atom, Si atom, N atom, P atom or B atom, can also be connected by a single bond or a bridge, selected from B(R 2 ), C(R 2 )2, Si(R 2 )2, C=O, C=NR 2 , C=C(R 2 )2, 0, S, S=O, SO2, N(R 2 ), P(R 2 ) and P(=O)R 2 , be bridged together; R 2is selected in each occurrence, either the same or different, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon residue with 1 to 20 C atoms, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, CI, Br, I or CN, and which may be substituted by one or more alkyl groups with 1 to 4 carbon atoms each, whereby two or more substituents R 2 together form a ring system. Compound according to claim 1, comprising at least one structure of formulas (1-1) to (1-4), Formula (I-3) Formula (I-4) where the symbols C b , C c , Y, W 1 , W 2 , Z, X, X a , X b and X cthe meanings mentioned in claim 1. Compound according to claim 1 or 2, characterized in that the compound comprises at least one substructure of formulas (B1-1) to (B1-30), Formula (B1-3) Formula (B1-4) Formula (B1-13) Formula (B1-14) Formula (B1-23) Formula (B1-24) where the symbols C c , W 1 , Y, R, R b , R c and R d the meanings mentioned in claim 1, the dashed bonds represent the condensation sites of the substructure at A and the following applies to the symbols and indices used: X 1 In each instance, it represents N or CR, whether the same or different. d with the proviso that no more than two of the groups X 1 in a cycle for N; Y 1 is the same or different in each occurrence C(R) d )2, (Rd )2C-C(R d )2, (R d )C=C(R d ), NR d , NAr', 0, S, SO, SO2, Se, P(O)R d , BR d or Si(R d )2; k is 0 or 1 ; n is 0, 1, 2 or 3; m is 0, 1, 2, 3 or 4; I is 0, 1, 2, 3, 4 or 5. Compound according to one or more of claims 1 to 3, characterized in that, if the compound comprises a substructure (B2), the substructure (B2) is selected from structures of formulas (B2-1) to (B2-30). Formula (B2-29) Formula (B2-30) where the symbols C b , W 1 , W 2 , Z, R, R b , R c and R d the meanings mentioned in claim 1, the symbols X 1 , Y 1and the indices k, n, m and I have the meanings specified in claim 3 and the dashed bonds represent the condensation sites of the substructure at A. Compound according to one or more of claims 1 to 4, comprising at least one structure of formulas (11-1) to (11-21). Formula (11-1) Formula (II-2) Formula (11-21) where the symbols C b , C c , Y, W 1 , W 2 , Z, R, R a , R b , R c and R d the meanings mentioned in claim 1, the symbol Y 1 the meaning mentioned in claim 3 and the further meanings that apply to the indices used: m is 0, 1, 2, 3 or 4; I is 0, 1, 2, 3, 4 or 5. Compound according to one or more of claims 1 to 5, characterized in that the condensed ring C cselected from a structure of formulas (CCY-1 ) to (CCY-10), Formula (CCY-1) Formula (CCY-2) Formula (CCY-3) Formula (CCY-9) Formula (CCY-10) where R has the meanings mentioned in claim 1, the dashed bonds represent the bonding sites of the condensed ring to the further groups and furthermore: Z 1 , Z 4 is the same or different at each occurrence C(R 3 )2, 0, S or Si(R 3 )2; Z 2 is C(R)2, 0, S, NR or C(=0), where two adjacent groups Z 2 for -CR=CR- or an ortho-linked arylene or heteroarylene group with 5 to 14 aromatic ring atoms, which can be substituted by one or more residues R; G is an alkylene group with 1, 2 or 3 C atoms, which may be substituted with one or more R groups, -CR=CR- or an ortho-linked arylene or heteroarylene group with 5 to 14 aromatic ring atoms, which may be substituted by one or more R groups; R 3 is the same or different in each occurrence H, D, F, CI, Br, I, CN, NO2, N(Ar')2, N(R d )2, C(=O)Ar', C(=O)R d , P(=O)(Ar')2, P(Ar')2, B(Ar')2, B(R d )2, C(Ar')3, C(R d )s, Si(Ar')s, Si(R d )s, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms, or an alkenyl group with 2 to 40 carbon atoms, each coupled with one or more R groups d can be substituted, where one or more non-adjacent CH2 groups are replaced by -R d C=CR d -, -C=C-, Si(R d)2, C=O, C=S, C=Se, C=NR d , -C(=O)O-, -C(=O)NR d -, NR d , P(=O)(R d ), -O-, -S-, SO or SO2 may be replaced and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is replaced by one or more R groups d may be substituted, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, separated by one or more R groups d may be substituted, or an aralkyl or heteroaralkyl group with 5 to 60 aromatic ring atoms, coupled with one or more R groups d It can be substituted, or a combination of these systems; in this case, two residues R can be used. 3 , which are bonded to the same carbon atom, together form an aliphatic or aromatic ring system and thus span a spiro system; furthermore, R 3with a remainder R, R a , R c or R 3 form an aliphatic ring system, where Ar' and R d the meanings mentioned in claim 1; with the proviso that in these groups no two heteroatoms are directly bonded to each other and no two C=O groups are directly bonded to each other. Compound according to one or more of claims 1 to 6, characterized in that the condensed ring C c selected from a structure of formulas (CRA-1 ) to (CRA-13) Formula CRA-7 Formula CRA-8 Formula CRA-9 wherein R has the meaning specified in claim 1, the dashed bonds represent the attachment points of the condensed ring to the further groups, and the further symbols have the following meaning: Y 2 is the same or different for each occurrence C(R)2, (R)2C-C(R)2, (R)C=C(R), NR, NAr', 0 or S; Rf F is the same or different in each occurrence, a straight-chain alkyl, alkoxy, or thioalkoxy group with 1 to 40 carbon atoms, or an alkenyl or alkynyl group with 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group with 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is each linked to one or more R groups. d can be substituted, with one or more non-adjacent CH2 groups being replaced by R d C=CR d , C=C, Si(R d )2, C=O, C=S, C=Se, C=NR d , -C(=O)O-, -C(=O)NR d -, NR d , P(=O)(R d ), -0-, -S-, SO or SO2 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each replaced by one or more R groups dmay be substituted, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, separated by one or more R groups d can be substituted; in this case, two residues R can be involved. f also together or a remainder R f form a ring system with a residue R or with another group, where R d which has the meaning mentioned in claim 1; r is 0, 1, 2, 3 or 4; 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. Compound according to one or more of claims 1 to 7, wherein the condensed ring C c selected from a structure of formulas (CRA-1a) to (CRA-4f), Formula CRA-3a Formula CRA-3b Formula CRA-4d Formula CRA-4e ​​Formula CRA-4f where the dashed bonds represent the attachment sites of the condensed ring to the other groups, the index m is 0, 1, 2, 3 or 4 and the symbols R, R d , R f and the indices s, t and v have the meanings set forth above, in particular in claims 1 and 7.

9. Compound according to one or more of claims 1 to 8, characterized in that the condensed ring C b selected from a structure of formulas (BCY-1 ) to (BCY-10), Formula (BCy-1) Formula (BCy-2) Formula (BCy-3) Formula (BCy-4) Formula (BCy-9) Formula (BCy-10) wherein R has the meaning mentioned in claim 1, the symbols G, Z 1 and Z 2 the meanings mentioned in claim 6, the dashed bonds represent the attachment points of the condensed ring to the further groups and furthermore: Z3 is the same or different at each occurrence C(R 3 )2, 0, S or Si(R 3 )2, where R 3 the meaning specified in claim 6; with the proviso that in these groups no two heteroatoms are directly bonded to one another and no two C=O groups are directly bonded to one another. Compound according to one or more of claims 1 to 9, characterized in that the condensed ring C b selected from a structure of formulas (BRA-1 ) to (BRA-12) Formula BRA-1 Formula BRA-2 Formula BRA-3 Formula BRA-10 Formula BRA-11 Formula BRA-12 wherein R has the meaning specified in claim 1, the symbols Y 2 and R fand the indices r, s, t and v have the meanings specified in claim 7, the dashed bonds representing the attachment points of the condensed ring to the further groups. Compound according to one or more of claims 1 to 10, characterized in that at least two residues R, R a , R b , R c , R d with the other groups to which the two remainders R, R a , R b , R c , R d bind, forming a condensed ring, with the two residues R, R a , R b , R c , R d form at least one structure of the following formulas (Cy-1 ) to (Cy-10), Formula (Cy-1) Formula (Cy-2) Formula (Cy-3) Formula (Cy-4) Formula (Cy-5) Formula (Cy-6) Formula (Cy-7) Formula (Cy-8) Formula (Cy-9) Formula (Cy-10) where R 1the meaning mentioned in claim 1, the dashed bonds being the bonding points to the atoms of the groups to which the two residues R, R are attached a , R b , R c , R d bind, represent and the following still applies: Z 5 , Z 7 is the same or different at each occurrence C(R 4 )2, 0, S, NR 4 or C(=O); Z 6 is C(R 1 )2, 0, S, NR 1 or C(=0), where two adjacent groups Z 2 for -CR 1 =CR 1 - or an ortho-linked arylene or heteroarylene group with 5 to 14 aromatic ring atoms, which is separated by one or more R groups 1 can be substituted, can stand; G 1 is an alkylene group with 1, 2 or 3 carbon atoms, which is coupled with one or more R groups. 1 can be substituted, -CR 1 =CR 1 - or an ortho-linked arylene or heteroarylene group with 5 to 14 aromatic ring atoms, which is separated by one or more R groups. 1 may be substituted; R 4 is the same or different in each occurrence H, D, F, CI, Br, I, CN, NO2, 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 straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 C atoms or an alkenyl group with 2 to 40 C atoms, each with one or more R groups 2 can be substituted, where one or more non-adjacent CH2 groups are replaced by -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 SO2 may be replaced and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is replaced by one or more R groups 2 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, separated by one or more R groups 2 may be substituted, or an aralkyl or heteroaralkyl group with 5 to 60 aromatic ring atoms, coupled with one or more R groups 2 It can be substituted, or a combination of these systems; in this case, two residues R can be used. 4 , which are bonded to the same carbon atom, together form an aliphatic or aromatic ring system and thus span a spiro system; furthermore, R 4 with a remainder R, R a , R b , R c , R d or R 1form an aliphatic ring system, the symbols R 1 and Ar" have the meanings mentioned in claim 1; with the proviso that in these groups no two heteroatoms are directly bonded to each other and no two groups C=O are directly bonded to each other. Compound according to one or more of claims 1 to 11, characterized in that at least two residues R, R a , R b , R c , R d with the other groups to which the two remainders R, R a , R b , R c , R d bind, forming a condensed ring, with the two residues R, R a , R b , R c , R d form at least one structure of the formulas (RA-1 ) to (RA-13). Formula RA-13 where R 1 The previously explained meaning is that the dashed bonds are the bonding points to the atoms of the groups to which the two residues R, R are attached. a , Rb , R c , R d bind, represent, and the other symbols have the following meaning: Y 4 is the same or different in each occurrence C(R) 1 )2, (R 1 )2C-C(R 1 )2, (R 1 )C=C(R 1 ), NR 1 , NAr', 0 or S; R g F is the same or different in each occurrence, a straight-chain alkyl, alkoxy, or thioalkoxy group with 1 to 40 carbon atoms, or an alkenyl or alkynyl group with 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group with 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group is each linked to one or more R groups. 2 can be substituted, whereby one or more non-adjacent CH2 groups are replaced by -C(=O)NR 2 -, NR 2 , P(=O)(R 2), -O-, -S-, SO or SO2 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each replaced by one or more R groups 2 may be substituted, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, separated by one or more R groups 2 can be substituted; in this case, two residues R can be involved. g also together or a remainder R g with a remainder R 1 or form a ring system with another group, where R 2 the meaning specified in claim 1; r is 0, 1, 2, 3 or 4; 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.

13. Compound according to one or more of claims 1 to 12, characterized in that at least two residues R, R a , R b , R c , R d with the other groups to which the two remainders R, R a, R b , R c , R d bind, forming a condensed ring, with the two residues R, R a , R b , R c , R d Forming structures of the formula (RB), Formula RB where R 1 the meaning set out in claim 1, the dashed bonds representing the attachment points via which the two residues R, R a , R b , R c , R d bind, the index m is 0, 1, 2, 3 or 4, and Y 5 C(R 1 )2, NR 1 , NAr', BR 1 , BAr', 0 or S is.

14. Compound according to at least one of the preceding claims, characterized in that the remainder R b and / or R d at least one group selected from C(Ar')s, C(R 1 )3, Si(Ar')s, Si(R 1 )3, B(R 1 )2 represents or a fluorene group containing one or more R residues 1may be substituted, includes, represents, or has a residual R b or R d educates.

15. Oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 14, wherein instead of a hydrogen atom or a substituent, one or more bonds of the compounds to the polymer, oligomer or dendrimer are present.

16. Formulation comprising at least one compound according to one or more of claims 1 to 14 or an oligomer, polymer or dendrimer according to claim 15 and at least one further compound, wherein the further compound is preferably selected from one or more solvents. Composition comprising at least one compound according to one or more of claims 1 to 14 or an oligomer, polymer or dendrimer according to claim 15 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 guide materials, hole injection materials, electron blocking materials and hole blocking materials, preferably host materials.A composition according to claim 17, characterized in that the composition comprises at least one further compound representing a TADF host material and / or at least one further compound representing a phosphorescent emitter (triplet emitter), wherein the further compounds preferably form a hyperfluorescence and / or hyperphosphorescence system with a compound according to one or more of claims 1 to 14 or an oligomer, polymer, or dendrimer according to claim 15. A process for preparing a compound according to one or more of claims 1 to 14, characterized in that a core structure with an aromatic amino group is synthesized and at least one aromatic or heteroaromatic residue is introduced, preferably by means of a nucleophilic aromatic substitution reaction or a coupling reaction.Use of a compound according to one or more of claims 1 to 14 or an oligomer, polymer, or dendrimer according to claim 15 in an electronic device. Electronic device comprising at least one compound according to one or more of claims 1 to 14 or an oligomer, polymer, or dendrimer according to claim 15.

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