CONNECTIONS FOR ORGANIC ELECTROLUMINESS DEVICES

Description

[0001] The present invention relates to heterocyclic compounds for use in electronic devices, in particular in organic electroluminescent devices, and to electronic devices, in particular organic electroluminescent devices, containing these heterocyclic compounds.

[0002] In general, there is still room for improvement with these heterocyclic compounds, for example for use as emitters, especially as fluorescent emitters, particularly with regard to lifetime and color purity, but also with regard to the efficiency and operating voltage of the device. Such compounds are known from the prior art, for example from WO 2021 / 185712 A1 and WO 2021 / 185829 A1.

[0003] 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 electroluminescence device, and which lead to good device properties when used in this device, as well as to provide the corresponding electronic device.

[0004] In particular, the object of the present invention is to provide connections that lead to a long service life, good efficiency and low operating voltage.

[0005] A further object of the present invention can be seen as providing compounds suitable for use in a phosphorescent or fluorescent electroluminescent device, in particular as emitters. In particular, it is an object of the present invention to provide emitters suitable for red, yellow, amber, or blue electroluminescent devices, especially for blue or green electroluminescent devices.

[0006] Furthermore, the compounds, especially when used as emitters in organic electroluminescent devices, should lead to devices that exhibit excellent color purity.

[0007] Furthermore, the compounds, especially when used as matrix materials, hole transport materials or electron transport materials in organic electroluminescent devices, should lead to devices that exhibit excellent color purity.

[0008] Surprisingly, it was found that certain compounds, described in more detail below, solve this problem, are very well suited for use in organic 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, especially organic electroluminescent devices containing such compounds, are therefore the subject of the present invention.

[0009] The subject of the present invention is a compound according to formula (I), where the following applies to the symbols used: Ar a< is, in each occurrence, the same or different an aryl or heteroaryl group with 5 to 18 aromatic ring atoms, which may be substituted with one or more Ar or R groups, wherein the Ar a< rings together may form a ring system; V 1< is, in each occurrence, the same or different O, S or NR; V 2< is, in each occurrence, the same or different N or CR; Ar is, in each occurrence, the same or different an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ring atoms, which may be substituted with one or more R groups; here, the Ar group may form a ring system with at least one Ar group, X 1< , R or another group; X 1< represents, in each occurrence, CR a< or different CR a< or N, preferably CR a< , provided thatthat no more than two of the groups X 1< and X 2< represent N in a cycle; X 2< represents CR b< or N in each occurrence, either the same or differently, preferably CR b< , with the proviso that no more than two of the groups X 1< and X 2< represent N in a cycle; R, R a< , R b< is the same or different in each occurrence H, D, OH, OR 1< , F, Cl, Br, I, CN, NO 2 , N(Ar') 2 , N(R 1< ) 2 , C(=O)OAr', C(=O)OR 1< , C(=O)N(Ar') 2 , C(=O)N(R 1< ) 2 , C(Ar') 3 , C(R 1< ) 3 , Si(Ar') 3 , Ge(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) 2 Ar', S(=O) 2 R 1< , OSO 2 Ar', OSO 2 R 1< , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 C atoms or an alkenyl or alkynyl group with 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 C atoms, wherein the alkyl, alkoxy, thioalkoxy,an alkenyl or alkynyl group, each of which may be substituted with one or more R1< residues, wherein one or more non-adjacent CH2 groups may be replaced by R1< C=CR1< , C≡C, Si(R1< )2 , C=O, C=S, C=Se, C=NR1< , -C(=O)O-, -C(=O)NR1< -, NR1< , P(=O)(R1< ), -O-, -S-, SO or SO2 , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R1< residues, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which may be substituted by one or more R1< residues, or an aralkyl or heteroaralkyl group with 5 to 60 aromatic ring atoms, which may be substituted with one or more R< substituents; two R< substituents may be used.R< a< or R< b< can each form a ring system with each other, or R with R< a<; Ar' is, in each occurrence, the same or different, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which can be substituted with one or more R< substituents; two Ar' substituents bonding to the same C atom, Si atom, N atom, P atom, S atom, Ge atom or B atom can also be bridged 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, SO< 2 , N(R< 1< ), P(R< 1< ) and P(=O)R< , to each other; R 1< is the same or different in each occurrence H, D, F, Cl, Br, I, CN, NO 2 , N(Ar") 2 , N(R 2< ) 2 , OR 2< , C(=O)OAr", C(=O)OR 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 , Ge(Ar") 3 , Si(R 2< ) 3 , a straight-chain alkyl,an 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 of which may be substituted with one or more R2< groups, wherein one or more non-adjacent CH2 groups may be replaced by -R2< C=CR2< -, -C=C-, Si(R2< ) 2 , C=O, C=S, C=Se, C=NR2< , -C(=O)O-, -C(=O)NR2< -, NR2< , P(=O)(R2< ), -O-, -S-, SO or SO2, and wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R 2< groups, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which may be substituted by one or more R 2< groups, or an aralkyl or heteroaralkyl group with 5 to 60 aromatic ring atoms,which may be substituted with one or more residues R 2<; in this case, two or more, preferably adjacent residues R 1< may form a ring system together, in this case, one or more residues R 1< may form a ring system with a further part of the compound; Ar" is, in each occurrence, the same or different aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which may be substituted with one or more R 2< substituents; two Ar" substituents bonding to the same C atom, Si atom, N atom, P atom, S atom, Ge atom, or B atom may also be bridged 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 , O, S, S=O, SO 2 , N(R 2< ), P(R 2< ) and P(=O)R 2< ; R 2< is, in each occurrence, the same or different selected from the group consisting of H, D, F, CN,an aliphatic hydrocarbon residue with 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, or CN and which may be substituted by one or more alkyl groups, each with 1 to 4 carbon atoms; two or more, preferably adjacent, substituents R 2< may form a ring system together.

[0010] In a preferred embodiment, V 1< is equal to or different from O, S or NR for each occurrence if V 2< represents CR in the same cycle, and V 1< is equal to or different from O or S for each occurrence if V 2< represents N in the same cycle.

[0011] In a preferred embodiment, V1< is either the same or different from O or S in each occurrence, and V2< represents CR. In a particularly preferred embodiment of the invention, V1< represents O.

[0012] In a preferred embodiment of the invention, Ar a< together with the three C atoms explicitly drawn in the same cycle, whether the same or different, at each occurrence forms a group according to one of the formulas (Ar a< -1) to (Ar a< -3), where the left dashed bond represents the bond to V 1<, the middle dashed bond represents the bond to the C atom, and the right dashed bond represents the bond to the N atom, Ar and R have the meanings mentioned above, and the following applies to the other symbols used: X 3< represents N, CR or CAR, preferably CR, in each occurrence, provided that no more than two of the groups X 3< represent N in a cycle; X 4< represents NR, O or S, in each occurrence, in each occurrence.

[0013] An aryl group according to this invention contains 6 to 40 carbon atoms, and preferably 6 to 18 carbon atoms; a heteroaryl group according to this invention contains 2 to 40 carbon atoms and at least one heteroatom, and preferably 2 to 17 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from nitrogen, oxygen, and / or sulfur. 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 fused (fused) aryl or heteroaryl group, for example, naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatic compounds linked together by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

[0014] An electron-deficient heteroaryl group according to the present invention is a heteroaryl group comprising at least one heteroaromatic six-membered ring with at least one nitrogen atom. Further aromatic or heteroaromatic five-membered or six-membered rings may be fused to this six-membered ring. Examples of electron-deficient heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, or quinoxaline.

[0015] An aromatic ring system according to this invention contains 6 to 60 carbon atoms in the ring system. A heteroaromatic ring system according to this invention contains 2 to 60 carbon atoms and at least one heteroatom in the ring system, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from nitrogen, oxygen, and / or sulfur. An aromatic or heteroaromatic ring system according to this invention is understood to be a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups may also be linked by a non-aromatic unit, such as a carbon, silicon, germanium, nitrogen, sulfur, or oxygen atom. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ethers, diaryl thioethers, stilbene, etc., are also considered to be aromatic or heteroaromatic ring systems according to this invention.These are understood to be aromatic ring systems within the meaning of this invention, and also systems in which two or more aryl groups are connected, for example, by a short alkyl group. Preferably, the aromatic ring system is selected from fluorene, 9,9'-spirobifluorene, 9,9-diarylamine, or groups in which two or more aryl and / or heteroaryl groups are linked to one another by single bonds.

[0016] Within the scope of the present invention, the following are preferably used as the groupings of an aliphatic hydrocarbon residue or an alkyl group or an alkenyl or alkynyl group, which may contain 1 to 20 carbon atoms and in which individual hydrogen atoms or CH₂ groups may also be substituted by the groups mentioned above: 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, Cyclooctyloxy, 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, i-Butylthio, s-Butylthio, t-Butylthio, n-Pentylthio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclooctylthio, 2-Ethylhexylthio, Trifluormethylthio, Pentafluorethylthio, 2,2,2-Trifluorethylthio, Ethenylthio, Propenylthio, Butenylthio, Pentenylthio, Cyclopentenylthio, Hexenylthio, Cyclohexenylthio, Heptenylthio, Cycloheptenylthio, Octenylthio, Cyclooctenylthio, Ethinylthio, Propinylthio, Butinylthio, Pentinylthio, Hexinylthio, Heptinylthio oder Octinylthio verstanden.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 groups mentioned above; furthermore, one or more H atoms can also be replaced by D, F, Cl, Br, I, CN or NO2, preferably F, Cl or CN, more preferably F or CN, particularly preferably CN.

[0017] An aromatic or heteroaromatic ring system with 5 to 60 or 5 to 40 aromatic ring atoms, respectively, which may be further substituted with the aforementioned substituents and which may be linked via any positions on the aromatic or heteroaromatic compound, is understood to include, 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, Benzothiazol, Pyridazin, Hexaazatriphenylen, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1,5-Diazaanthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1,6-Diazapyren, 1,8-Diazapyren, 4,5-Diazapyren, 4,5,9,10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1,2,3-Triazol, 1,2,4-Triazol, Benzotriazol, 1,2,3-Oxadiazol, 1,2,4-Oxadiazol, 1,2,5-Oxadiazol, 1,3,4-Oxadiazol, 1,2,3-Thiadiazol, 1,2,4-Thiadiazol, 1,2,5-Thiadiazol, 1,3,4-Thiadiazol, 1,3,5-Triazin, 1,2,4-Triazin, 1,2,3-Triazin, 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.

[0018] In the context of this description, the phrase "two or more residues can form a ring" means, among other things, that the two residues are linked to each other by a chemical bond involving the formal elimination of two hydrogen atoms. This is illustrated by the following scheme.

[0019] When, for example, two -CH=CH 2 -substituents form a ring, an fused benzo group is created.

[0020] 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 diagram:

[0021] In a preferred embodiment, the compounds according to the invention can represent a structure of formula (II): where the symbols correspond to the symbols of formula (I) and additionally the following applies: X 3< represents N, CR or CAR, preferably CR, in each occurrence, provided that no more than two of the groups X 3< represent N in a cycle; V 1< , V 3< represents O, S or NR in each occurrence, in each occurrence, in each occurrence, in each occurrence, in each occurrence, in each occurrence, in each occurrence, or CR or N.

[0022] Preferably, V 1< and V 3< are chosen to be the same, and V 2< and V 4< are chosen to be the same.

[0023] In a preferred embodiment of the invention, the compound is a compound of formula (II), wherein for formulas (II-1) to (II-36) the following additionally applies: Formula V 1< V 2< V 3< V 4< II-1 O N O CR II-2 S N O CR II-3 NO N O CR II-4 O N S CR II-5 S N S CR II-6 NO N S CR II-7 O N NO CR II-8 S N NO CR II-9 NO N NO CR II-10 O N O N II-11 S N O N II-12 NO N O N II-13 O N S N II-14 S N S N II-15 NO N S N II-16 O N NO N II-17 S N NO N II-18 NO N NO N II-19 O CR O CR II-20 S CR O CR II-21 NO CR O CR II-2 O CR S CR II-2 S CR S CR II-2 NO CR S CR II-2 O CR NO CR II-26 S CR NO CR II-27 NO CR NO CR II-28 O CR O N II-2 S CR O N II-30 NO CR O N II-31 O CR S N II-32 S CR S N II-33 NO CR S N II-34 O CR NO N II-35 S CR NO N II-36 NO CR NO N

[0024] Preferably, it may be provided that in formulas (I), (II) and / or (II-1) to (II-36) no more than four, preferably no more than two, groups X 1< , X 2< and X 3< represent N. Particularly preferably, all groups X 1< , X 2< and X 3< represent CR or CR a< .

[0025] As shown in the examples, some processes for the preparation of compounds according to the invention result in mixtures that generally lead to a broadened emission spectrum and are therefore not preferred. For this reason, it may be advantageous to separate these mixtures. The advantages of a narrow emission spectrum can be achieved by suitable substitution, as shown in the examples.

[0026] A preferred embodiment of the invention is the compounds according to formula (III) or (IIIa), where the symbols correspond to the symbols of formula (I) and (II).

[0027] In a preferred embodiment of the invention, the compound is a compound of formula (III) or (IIIa), wherein for formulas (III-1) to (III-36) the following additionally applies: Formula V 1< V 2< V 3< V 4< III-1 O N O CR III-2 S N O CR III-3 NO N O CR III-4 O N S CR III-5 S N S CR III-6 NO N S CR III-7 O N NO CR III-8 S N NO CR III-9 NO N NO CR III-10 O N O N III-11 S N O N III-12 NO N O N III-13 O N S N III-1 S N S N III-15 NO N S N III-1 O N NO N III-17 S N NO N III-18 NO N NO N III-19 O CR O CR III-2 S CR O CR III-2 NO CR O CR III-2 O CR S CR III-2 S CR S CR III-2 NO CR S CR III-2 O CR NO CR III-2 S CR NO CR III-27 NO CR NO CR III-2 O CR O N III-2 S CR O N III-3 NO CR O N III-31 O CR S N III-32 S CR S N III-33 NO CR S N III-34 O CR NO N III-35 S CR NO N III-36 NO CR NO N

[0028] In a preferred embodiment, V1< and V3< are the same, preferably V1< and V3< are the same, as are V2< and V4<. V1< and V3< are preferably equal to O or S, in particular equal to O, and V2< and V4< are preferably equal to CR.

[0029] In a preferred embodiment, the compound is selected from the compounds of formula (IV-1) to (IV-6): where the symbols have the meanings previously given for formula (I). The residues R, which in formula (IV-1) are bonded to the furan groups and in formula (IV-2) to the thiophene groups, are preferably not equal to H or D.

[0030] Compounds according to formulas (IV-1) to (IV-6) are also suitable, which instead of the two R groups in ortho position to the nitrogen atom have a single bond, analogous to the compound of formula (IIIa).

[0031] Structures of formula (IV-1) are particularly preferred, where the residues R, which are bonded to the furan groups, are not equal to H or D.

[0032] In a particularly preferred embodiment, the compound is selected from the compounds of formula (IV-1a) to (IV-6a): where the symbols have the meanings previously given for formula (I). The R groups bonded to the furan groups in formula (IV-1a) and to the thiophene groups in formula (IV-2a) are preferably not H or D. The compounds of formula (IV-1a) are particularly preferred.

[0033] Compounds according to formulas (IV-1a) to (IV-6a) are also suitable, which instead of the two R groups in ortho position to the nitrogen atom have a single bond, analogous to the compound of formula (IIIa).

[0034] In a preferred embodiment of the present invention, it can be provided that at least two residues R, R a< , R b< form a condensed ring with the further groups to which the two residues R, R a< , R b< bind, wherein the two residues R, R a< form at least one structure of formulas (RA-1) to (RA-12), where R 1< has the meaning set out above, the dashed bonds represent the attachment points through which the two residues R, R a< , R b< bind, and the other symbols have the following meaning: Y 5< is the same or different for each occurrence C(R 1< ) 2 , (R 1< ) 2 CC(R 1< ) 2 , (R 1< )C=C(R 1< ), NR 1< , NAr', O or S, preferably C(R 1< ) 2 , (R 1< ) 2 CC(R 1< ) 2 , (R 1< )C=C(R 1< ), O or S;R< is the same or different in each occurrence F, a straight-chain alkyl, alkoxy, or thioalkoxy group with 1 to 40 C atoms, or an alkenyl or alkynyl group with 2 to 40 C atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group with 3 to 20 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group may each be substituted with one or more R< 2< substituents, wherein one or more non-adjacent CH2 groups are replaced by R< 2< C=CR2, C≡C, Si(R2)2, C=O, C=S, C=Se, C=NR2, -C(=O)O-, -C(=O)NR2-, NR2 P(=O)(R 1< ), -O-, -S-, SO or SO 2 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R 2< residues, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which may be substituted by one or more R 2< residues;Two residues R< can also form a ring system with each other, or one residue R< can form a ring system with one residue R< or with another group; sist 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3, or 4, particularly preferably 0, 1 or 2; tist 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3, or 4, particularly preferably 0, 1 or 2; vist 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 0, 1, 2, 3, or 4, particularly preferably 0, 1 or 2. ;

[0035] In a preferred embodiment of the invention, the at least two residues R, Ra< , Rb< form a condensed ring with the further groups to which the two residues R, Ra< , Rb< bind, wherein the two residues R, Ra< , Rb< preferably form at least one of the structures of formulas (RA-1a) to (RA-4f), wherein the dashed bonds represent the attachment points through which the two residues R, R a< , R b< 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 forth above, in particular for formula (I) and / or formulas (RA-1) to (RA-12).

[0036] Furthermore, it can be provided that the at least two residues R, R a< , R b< , form the structures of formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) and form a condensed ring, represent residues R, R a< , R b< from adjacent groups X 1< , X 2< , X 3< or represent residues R which each bond to adjacent C atoms, these C atoms preferably being connected via a bond.

[0037] In a further preferred embodiment, at least two residues R, Ra< , Rb< form a condensed ring with the further groups to which the two residues R, Ra< , Rb< bind, wherein the two residues R, Ra< , Rb< form structures of the formula (RB), where R 1< has the meaning given for formula (I), the dashed bonds represent the attachment points through which the two residues R, R a< , R b< bind, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y 6< is C(R 1< ) 2 , NR 1< , NAr', BR 1< , BAr', O or S, preferably C(R 1< ) 2 , NAr' or O.

[0038] It can be provided that the at least two residues R, R a< , R b< , form the structures of formula (RB) and form a condensed ring, that residues R, R a< , R b< are from neighboring groups X 1< , X 2< , X 3< or that residues R are each bound to neighboring C atoms, wherein these C atoms are preferably connected to each other via a bond.

[0039] Furthermore, it may be provided that the substituents R, R a< , R b< and R g< , R 1< and R 2< according to the formulas above do not form a condensed aromatic or heteroaromatic ring system with the ring atoms of the ring system to which the R, R a< , R b< and R g< , R 1< and R 2< bind. This includes the formation of a condensed aromatic or heteroaromatic ring system with possible substituents R 1< and R 2< that may be bonded to the residues R, R a< , R b< , R g< and R 1<.

[0040] When two substituents, which may in particular be selected from R, Ra<, Rb<, Rg<, R1< and / or R2<, form a ring system, this system may be monocyclic or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic. The substituents forming the ring system may be adjacent, i.e., bonded to the same carbon atom or to carbon atoms directly bonded to one another, or they may be further apart. Furthermore, the ring systems provided with the substituents R, Ra<, Rb<, Rg<, R1< and / or R2< may also be linked to one another by a bond, thus resulting in ring closure. In this case, each of the corresponding bonding sites is preferably provided with a substituent R, Ra<, Rb<, Rg<, R1< and / or R2<.

[0041] In one embodiment of the invention, the substituents R, R a< and R b< form a ring system together only when they are bound to the same cycle.

[0042] Preferably, compounds of the invention of formulas (I), (II), (II-1) to (II-36), (III), (IIIa), (III-1) to (III-36), (IV-1) to (IV-6) or (IV-1a) to (IV-6a) have a molecular weight of less than or equal to 5000 g / mol, preferably less than or equal to 4000 g / mol, in particular 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.

[0043] Furthermore, preferred compounds according to the invention are characterized by being sublimable. These compounds generally have a molar mass of less than approximately 1200 g / mol.

[0044] Preferred aromatic or heteroaromatic ring systems R, R a< , R b< , Ar' 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 2-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 may be linked to position 1, 2, 3 or 4, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene,which can each be substituted with one or more residues R 1< or R.

[0045] Preferably, it can be provided that at least one substituent R, R< a< and / or R b< is selected as the same or different for each occurrence from the group consisting of H, D or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, preferably with 6 to 24 aromatic ring atoms, particularly preferably selected from the groups of the following formulas Ar-1 to Ar-78, and / or the group Ar' being selected from the same or different groups at each occurrence from the groups of the following formulas Ar-1 to Ar-78, where R 1< has the meanings mentioned above, the dashed bond represents the attachment point and the following also applies: Ar 1< is, in each occurrence, either the same or different, a bivalent aromatic or heteroaromatic ring system with 6 to 18 aromatic ring atoms, each of which may be substituted with one or more R 1< substituents; A is, in each occurrence, either the same or different, C(R 1< ) 2 , NR 1< , O 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 HetAr; q is 0 or 1, where q = 0 means that no group A is bonded at this position and instead R 1< substituents are bonded to the corresponding carbon atoms.

[0046] If the aforementioned groups for Ar or aromatic groups R have multiple groups A, then all combinations from the definition of A are possible. Preferred embodiments are those in which one group A represents NR 1< and the other group A represents C(R 1< ) 2, or in which both groups A represent NR 1<, or in which both groups A represent O.

[0047] When A stands for NR 1<, the substituent R 1< bonded to the nitrogen atom preferably represents an aromatic or heteroaromatic ring system with 5 to 24 aromatic ring atoms, which may also be substituted by one or more R 2< groups. In a particularly preferred embodiment, this substituent R 1< represents, in each instance, an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, in particular with 6 to 18 aromatic ring atoms, which has no fused aryl groups and no fused heteroaryl groups in which two or more aromatic or heteroaromatic 6-ring groups are directly fused to one another, and which may also be substituted by one or more R 2< groups.Phenyl, biphenyl, terphenyl, and quaterphenyl with linkage patterns as listed above for Ar-1 to Ar-11 or Ar-76 to Ar-78 are preferred, wherein these structures may be substituted by one or more R2< groups instead of R1<, but are preferably unsubstituted. Triazine, pyrimidine, and quinazoline as listed above for Ar-47 to Ar-50, Ar-57, and Ar-58 are also preferred, wherein these structures may be substituted by one or more R2< groups instead of R1<.

[0048] Preferred substituents R, R a< , R b< and R g< are described below.

[0049] In a preferred embodiment of the invention, R, R a< and R b< are selected, either the same or different, from the group consisting of H, D, F, CN, Si(R 1< ) 3 , N(R 1< ) 2 , N(Ar') 2 , a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the alkyl group may be substituted with one or more R 1< residues, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, preferably with 6 to 30 aromatic ring atoms, which may each be substituted by one or more R 1< residues.In a particularly preferred embodiment of the invention, R, R< a< and R< b< are selected, either identically or differently, from the group consisting of H, D, F, CN, a straight-chain alkyl group with 1 to 10 carbon atoms, in particular with 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group with 3 to 10 carbon atoms, in particular with 3 to 6 carbon atoms, wherein the alkyl group may be substituted with one or more R< substituents, or an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, preferably with 6 to 13 aromatic ring atoms, each of which may be substituted by one or more R< substituents. The aromatic or heteroaromatic ring system is preferably selected from the groups of formulas Ar-1 to Ar-78 shown above.

[0050] As described above, it is preferred if the substituent bonded to the furan or thiophene group is not H or D. Preferred substituents bonded at this position are aromatic or heteroaromatic ring systems with 6 to 24 aromatic ring atoms, preferably with 6 to 13 aromatic ring atoms, each of which may be substituted by one or more R1 groups. The aromatic or heteroaromatic ring system is preferably selected from the groups of formulas Ar-1 to Ar-78 shown above.

[0051] Furthermore, it can be provided that at least one substituent R, R and / or R< is selected, either the same or different, in each occurrence from the group consisting of H, D, an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, which may be substituted with one or more R< groups. In a further preferred embodiment of the invention, R is selected, either the same or different, in each occurrence from the group consisting of H, D, an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, which may be substituted with one or more R< groups, or from the group N(Ar)2.Particularly preferred is the substituent R, R a< and R b< being the same or different in each occurrence selected from the group consisting of H or an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, preferably with 6 to 18 aromatic ring atoms, particularly preferably with 6 to 13 aromatic ring atoms, each of which may be substituted with one or more R 1< groups.

[0052] In a preferred embodiment of the invention, R< is the same or different at each occurrence selected from the group consisting of a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the alkyl group may be substituted with one or more R< groups, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ring atoms, which may be substituted by one or more R< groups.

[0053] In a further preferred embodiment of the invention, R< is selected, whether the same or different, from the group consisting of a straight-chain alkyl group with 1 to 10 C atoms or a branched or cyclic alkyl group with 3 to 10 C atoms, wherein the alkyl group may be substituted with one or more R< groups, or an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, which may be substituted with one or more R< groups.Particularly preferred is R a< selected from the group consisting of a straight-chain alkyl group with 1 to 5 C atoms or a branched or cyclic alkyl group with 3 to 5 C atoms, wherein the alkyl group may be substituted with one or more R 1< groups, or an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, preferably with 6 to 18 aromatic ring atoms, particularly preferably with 6 to 13 aromatic ring atoms, which may each be substituted with one or more R 1< groups.

[0054] In a preferred embodiment of the invention, R<g> is selected, in each occurrence, as the same or different from the group consisting of a straight-chain alkyl group with 1 to 6 C atoms or a cyclic alkyl group with 3 to 6 C atoms, wherein the alkyl group may be substituted with one or more R< groups, or an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, which may each be substituted by one or more R< groups; two R< groups may also form a ring system together.Particularly preferred is R<g< selected, in each occurrence, either identically or differently from the group consisting of a straight-chain alkyl group with 1, 2, 3, or 4 carbon atoms, or a branched or cyclic alkyl group with 3 to 6 carbon atoms, wherein the alkyl group may be substituted with one or more residues R<1<, but is preferably unsubstituted, or an aromatic ring system with 6 to 12 aromatic ring atoms, in particular with 6 aromatic ring atoms, which may be substituted by one or more, preferably non-aromatic, residues R<1<, but is preferably unsubstituted; two residues R<g< may form a ring system together. Most particularly preferred is R<g< selected, in each occurrence, either identically or differently from the group consisting of a straight-chain alkyl group with 1, 2, 3, or 4 carbon atoms, or a branched alkyl group with 3 to 6 carbon atoms.R< particularly preferably represents a methyl group or a phenyl group, wherein two phenyl groups can form a ring system together, with a methyl group being preferred over a phenyl group.

[0055] Further suitable groups R, R a< and R b< are groups of the formula -Ar 4< -N(Ar 2< )(Ar 3< ), where Ar 2< , Ar 3< and Ar 4< represent, in each instance, an aromatic or heteroaromatic ring system with 5 to 24 aromatic ring atoms, each of which may be substituted with one or more R 1< groups. The total number of aromatic ring atoms of Ar 2< , Ar 3< and Ar 4< is at most 60 and preferably at most 40.

[0056] Ar4< and Ar2< can be linked to each other and / or Ar2< and Ar3< can also be linked to each other by a group selected from C(R1<)2, NR1<, O, or S. Preferably, the linkage of Ar4< and Ar2< to each other or of Ar2< and Ar3< to each other occurs ortho to the position of the linkage with the nitrogen atom. In a further embodiment of the invention, none of the groups Ar2<, Ar3<, or Ar4< are linked to each other.

[0057] Preferably, Ar 4< is an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, preferably with 6 to 12 aromatic ring atoms, each of which may be substituted with one or more R 1< groups. Particularly preferably, Ar 4< is selected from the group consisting of ortho-, meta-, or para-phenylenes or ortho-, meta-, or para-biphenyls, each of which may be substituted by one or more R 1< groups, but preferably are unsubstituted. Most preferably, Ar 4< is an unsubstituted phenylene group.

[0058] Preferably, Ar 2< and Ar 3< are the same or different at each occurrence an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, each of which may be substituted with one or more R 1< residues. Particularly preferred groups Ar 2< and Ar 3< are selected, either identically or differently at each occurrence, 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-spirobifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene, 1-, 2-, 3- or 4-carbazole, 1-, 2-, 3- or 4-dibenzofuran, 1-, 2-, 3- or 4-dibenzothiophene, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2-, 4- or 5-pyrimidine, pyrazine, Pyridazine, triazine, phenanthrene or triphenylene, each of which may be substituted with one or more R 1< residues.Particularly preferred are Ar 2< and Ar 3<, whether identical or different in 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-spirobibfluorene.

[0059] In a further preferred embodiment of the invention, R 1< is selected, whether the same or different at each occurrence, from the group consisting of H, D, F, CN, a straight-chain alkyl group with 1 to 10 C atoms or a branched or cyclic alkyl group with 3 to 10 C atoms, wherein the alkyl group may be substituted with one or more R 2< groups, or an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, which may be substituted by one or more R 2< groups.In a particularly preferred embodiment of the invention, R 1< is selected, whether the same or different, from the group consisting of H, a straight-chain alkyl group with 1 to 6 C atoms, in particular with 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group with 3 to 6 C atoms, wherein the alkyl group may be substituted with one or more R 2< groups, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system with 6 to 13 aromatic ring atoms, which may each be substituted by one or more R 2< groups, but is preferably unsubstituted.

[0060] In a further preferred embodiment of the invention, R 2< is the same or different at each occurrence H, an alkyl group with 1 to 4 C atoms or an aryl group with 6 to 10 C atoms, which may be substituted with an alkyl group with 1 to 4 C atoms, but preferably is unsubstituted.

[0061] In compounds according to the invention, which are processed by vacuum evaporation, the alkyl groups preferably have no more than five carbon atoms, particularly preferably no more than four carbon atoms, and most preferably no more than one carbon atom. For compounds processed from solution, compounds substituted with alkyl groups, in particular branched alkyl groups, with up to 10 carbon atoms, or substituted with oligoarylene groups, for example ortho-, meta-, para- or branched terphenyl or quaterphenyl groups, are also suitable.

[0062] Examples of preferred connections according to the embodiments listed above are the connections listed in the following table:

[0063] Preferred embodiments of the compounds according to the invention are described in more detail in the examples, wherein these compounds can be used alone or in combination with others for all uses according to the invention.

[0064] Provided that the conditions specified in claim 1 are met, the preferred embodiments mentioned above can be combined with one another as desired. In a particularly preferred embodiment of the invention, the preferred embodiments mentioned above apply simultaneously.

[0065] The compounds according to the invention can in principle be produced by various methods.

[0066] Another object of the present invention is a method for producing the compounds according to the invention, in which a substituted amine is synthesized which is then cyclized intramolecularly to the basic structure of formula (I).

[0067] These connections can be implemented with other connections through known coupling reactions, the necessary conditions for which 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 conversions.

[0068] Particularly suitable and preferred coupling reactions, all leading to CC and / or CN couplings, are those according to ULLMANN, BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA, and HIYAMA. These reactions are widely known, and the examples provided offer further guidance to those skilled in the art.

[0069] The principles of the manufacturing processes described above are known from the literature for similar compounds and can be easily adapted by a person skilled in the art to produce the compounds according to the invention. Further information can be found in the examples.

[0070] By these methods, 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).

[0071] The compounds according to 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 with reactive leaving groups, such as bromine, iodine, chlorine, boronic acid or boronic acid esters, or with reactive, polymerizable groups, such as olefins or oxetanes. These can be used as monomers for the production of corresponding oligomers, dendrimers, or polymers. The oligomerization or polymerization preferably proceeds via the halogen functionality or the boronic acid functionality, or via the polymerizable group. It is also possible to crosslink the polymers via such groups. The compounds and polymers according to the invention can be used as crosslinked or uncrosslinked layers.

[0072] A further aspect of the invention is therefore oligomers, polymers, or dendrimers containing one or more of the structures of formula (I) and preferred embodiments of this formula listed above, or compounds according to the invention, wherein one or more bonds of the compounds according to the invention or of the structures of formula (I) and preferred embodiments of this formula are present with the polymer, oligomer, or dendrimer. Depending on the linkage of the structures of 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 apply to the repeating units of the compounds according to the invention in oligomers, dendrimers and polymers as described above.

[0073] Of particular interest are compounds according to the invention which are characterized by a high glass transition temperature. Therefore, compounds according to the invention are particularly preferred which have a glass transition temperature of at least 70 °C, particularly preferably at least 110 °C, very preferably at least 125 °C and especially preferably at least 150 °C, as determined according to DIN 51005 (version 2005-08).

[0074] For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes, formulations of the compounds according to 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 include, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin. Dodecyl benzene, ethyl benzoate, indane, NMP, p-cymene, phenetol,1,4-Diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacic acid ester, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents.

[0075] A further object of the present invention is therefore a formulation or composition comprising at least one compound according to the invention and at least one further compound. The further compound may, for example, be a solvent, in particular one of the solvents mentioned above or a mixture of these solvents. If the further compound comprises a solvent, this mixture is referred to herein as the formulation. The further compound may also be at least one further organic or inorganic compound that is also 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 later in connection with the organic electroluminescence device. The further compound may also be a polymer.

[0076] A further object of the present invention is a composition comprising a compound according to the invention and at least one further organically functional material. Functional materials are generally the organic or inorganic materials introduced between the anode and cathode. Preferably, the organically functional material is selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole guide materials, hole injection materials, electron blocking materials, hole blocking materials, wide-band-gap materials, and n-dopeds.

[0077] A further object of the present invention is the use of a compound according to the invention in an electronic device, in particular in an organic electroluminescent device, preferably as an emitter, and especially preferably as a blue, green, yellow, or red emitter. The compounds according to the invention are particularly suitable as fluorescent emitters. Furthermore, compounds according to the invention can be used as host materials, electron transport materials, and / or hole-conducting materials.

[0078] A further object of the present invention is 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 comprising at least one layer containing at least one organic compound. The component may also contain inorganic materials or layers composed entirely of inorganic materials.

[0079] The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and 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.). Organic electroluminescent devices (organic light-emitting diodes, OLEDs) are preferred.

[0080] 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, such as 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 may, for example, have an exciton blocking function, may also be introduced between two emitting layers. It should be noted, however, that not every one of these layers is necessarily present. The organic electroluminescent device may contain a single emitting layer, or it may contain multiple emitting layers.If multiple emission layers are present, these preferably exhibit several emission maxima between 380 nm and 750 nm, resulting in overall white emission. This means that different emitting compounds capable of fluorescence or phosphorescence are used in the emitting layers. Systems with three emitting layers exhibiting blue, green, and orange or red emission are particularly preferred. The organic electroluminescence device according to the invention can also be a tandem electroluminescence device, especially for white-emitting OLEDs.

[0081] The compound according to the invention can be used in different layers, depending on the precise structure. A preferred application is an organic electroluminescent device containing a compound according to formula (I) or the preferred embodiments described above in an emitting layer as an emitter, preferably as a blue or green emitter. Furthermore, the compound according to the invention can also be used in an electron transport layer and / or in a hole-blocking layer and / or in an exciton-blocking layer. In this case, the compound can be used as an emitter in a conventional fluorescent OLED.Furthermore, the compound according to the invention can be used in a hyperfluorescent OLED, as described, for example, in WO 2015 / 135624, which contains a fluorescent compound according to the invention and a sensitizer, wherein the sensitizer is a TADF compound (TADF = thermally activated delayed fluorescence) and wherein the energy of the sensitizer is transferred to the fluorescent emitter via Förster energy transfer. Furthermore, the compound according to the invention can be used in a hyperphosphorescent OLED, as described, for example, in WO 2001 / 08230, which contains a fluorescent compound according to the invention and a phosphorescent compound as a sensitizer, wherein the energy of the sensitizer is transferred to the fluorescent emitter via Förster energy transfer.

[0082] 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.

[0083] A preferred mixture of the compound according to the invention and a matrix material contains between 99.9 and 50 vol%, preferably between 99.5 and 80 vol%, and particularly preferably between 99 and 90 vol% of matrix material based on the total mixture of emitter and matrix material. Correspondingly, the mixture contains between 0.1 and 50 vol%, preferably between 0.5 and 20 vol%, and particularly preferably between 1 and 10 vol% of the emitter based on the total mixture of emitter and matrix material.

[0084] When the compound according to the invention is used as a fluorescent emitter in a fluorescent OLED, suitable matrix materials are selected from the group consisting of oligoarylenes (e.g., 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthylanthracene), in particular oligoarylenes containing fused aromatic groups, oligoarylene vinylenes (e.g., DPVBi or Spiro-DPVBi according to EP 676461), polypodial metal complexes (e.g., according to WO 2004 / 081017), hole-transporting compounds (e.g., according to WO 2004 / 058911), electron-transporting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (e.g., according to WO 2005 / 084081 or WO 2005 / 084082), atropisomers (e.g., according to WO 2006 / 048268) or benzanthracenes (e.g. according to WO 2008 / 145239). Particularly preferred matrix materials are selected from the group consisting of oligoarylenes containing naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds.An oligoarylene within the meaning of this invention is a compound in which at least three aryl or arylene groups are bonded to one another.

[0085] Examples of suitable matrix materials are the compounds shown in the following table:

[0086] The compounds according to the invention can also be used in combination with one or more other fluorescent compounds.

[0087] Suitable matrix materials that can be used in combination with the compounds according to the invention in hyperfluorescent or hyperphosphorescent OLEDs 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, azaborols or boron esters, e.g. according to WO 2006 / 117052, triazine derivatives, e.g.according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877, pyrimidine derivatives, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, diazaphosphole derivatives, e.g. according to WO 2010 / 054730, bridged carbazole derivatives, e.g. according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080, triphenylene derivatives, e.g. B. according to WO 2012 / 048781, 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.

[0088] Furthermore, a compound that does not participate, or does not participate to a significant extent, in charge transport, as described, for example, in WO 2010 / 108579, can be used as a co-host. In particular, compounds with a large band gap that do not participate, or at least not to a significant extent, in charge transport of the emitting layer are suitable as co-matrix materials in combination with the compound according to the invention. Such materials are preferably pure hydrocarbons. Examples of such materials can be found, for example, in WO 2009 / 124627 or WO 2010 / 006680.

[0089] Furthermore, for hyperfluorescent and hyperphosphorescent OLEDs, it is preferably the case that the lowest triplet energy of the matrix is ​​no more than 0.1 eV lower than the triplet energy of the sensitizer. Preferably: T₁(matrix) ≥ T₁(sensitizer). Particularly preferably: T₁(matrix) - T₁(sensitizer) ≥ 0.1 eV. Most preferably: T₁(matrix) - T₁(sensitizer) ≥ 0.2 eV. Here, T₁(matrix) is the lowest triplet energy of the matrix compound and T₁(sensitizer) is the lowest triplet energy of the sensitizer.

[0090] In a preferred embodiment, a compound according to the invention, which is used as an emitter, is preferably used in combination with one or more phosphorescent materials (triplet emitters) and / or with a compound that represents a TADF (thermally activated delayed fluorescence) host material. A hyperfluorescence and / or hyperphosphorescence system is preferably formed in this way.

[0091] 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, with energy being transferred from the phosphorescent compound to the fluorescent emitter (hyperphosphorescence). In this context, the phosphorescent compound behaves like a host material. As is known to those skilled in the art, host materials have higher singlet and triplet energies compared to the emitters, so that the energy of the host material is transferred to the emitter as efficiently as possible. The systems disclosed in the prior art exhibit precisely such an energy ratio.

[0092] Phosphorescence within the meaning of this invention is understood to mean 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 iridium, platinum, and copper complexes, are to be considered phosphorescent compounds.

[0093] Suitable phosphorescent compounds (= triplet emitters) are, in particular, compounds that emit light, preferably in the visible range, upon suitable excitation and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, and especially preferably greater than 56 and less than 80, particularly a metal with this atomic number. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are preferred as phosphor emitters, especially compounds containing iridium or platinum.

[0094] Examples of the issuers described above can be found in 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 in phosphorescent electroluminescence devices according to the prior art and as known to the skilled person in the field of organic electroluminescence are suitable, and the skilled person can use further phosphorescent complexes without inventive effort.

[0095] Examples of suitable phosphorescent sensitizers include iridium and platinum complexes containing carbene ligands, such as the structures shown below. Complexes with carbene ligands are particularly interesting because they can also produce blue phosphorescence, which is important for use in hyperphosphorescent OLEDs. The following compounds (Pt-1) are also suitable as blue phosphorescent metal complexes, where: Y1<, Y2<, Y3<, Y4<, Y5< is the same or different CR Y< or N in each occurrence; or Y1< -Y2< and / or Y3< -Y4< or Y4< -Y5< form a fused aryl or heteroaryl ring with 5 to 18 aromatic ring atoms, each of which may also be substituted by one or more R' groups; E50< is the same or different C(R CO0<)2, NR N0<, O or S in each occurrence; Ar50< is an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may also be substituted by one or more R' groups; Ar 51< , Ar 52< , Ar 53< represents, or is different from, a condensed aryl or heteroaryl group with 5 to 18 aromatic ring atoms, each of which may also be substituted by one or more R' residues; RY< represents, or is different from, a residue selected from H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, P(=O)(Ar) 2 , S(=O)Ar, S(=O) 2 Ar,N(R') 2 , N(Ar) 2 , NO 2 , Si(R') 3 , B(OR') 2 , OSO 2 R', a straight-chain alkyl, alkoxy or thioalkyl group with 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 40 C atoms, each of which may be substituted by one or more R' groups, wherein one or more non-adjacent CH 2 groups may be replaced by R'C=CR', C=C, Si(R') 2 , Ge(R') 2 , Sn(R') 2 , C=O, C=S, C=Se, P(=O)(R'), SO, SO 2 , O, S or CONR' and wherein one or more H atoms are replaced by D, F, Cl, Br, I, CN or NO 2 can be replaced, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which can be substituted by one or more R' groups, and an aryloxy group with 5 to 60 aromatic ring atoms, which can be substituted by one or more R' groups, wherein two RY< groups together form an aliphatic, aromatic or heteroaromatic ring system,which may be substituted by one or more R' groups; RC0< is the same or different for each occurrence for a group selected from H, D, a straight-chain alkyl group with 1 to 40 C atoms, which may be substituted by one or more R' groups, an aryl or heteroaryl group with 6 to 18 aromatic ring atoms, each of which may be substituted by one or more R groups, wherein two RC< groups together may form an aliphatic, aromatic or heteroaromatic ring system, which is substituted by one or more R' groups; R N0< is the same or different for each occurrence for a residue selected from H, D, F, a straight-chain alkyl group with 1 to 40 C atoms or a branched or cyclic alkyl group with 3 to 40 C atoms, each of which is substituted by one or more residues R' and wherein one or more H atoms may be replaced by D, F or CN,an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R' groups; R' and Ar have the same meaning as described above.

[0096] Preferably, Ar 50< is, in each occurrence, the same or different, an aromatic or heteroaromatic ring system with 5 to 40, particularly preferably with 5 to 30 and most preferably with 6 to 18 aromatic ring atoms, which may also be substituted by one or more R' groups.

[0097] Preferably, Ar 51< , Ar 52< , Ar 53< represent, equally or differently, a condensed aryl or heteroaryl ring with 6 aromatic ring atoms, each of which may also be substituted by one or more R' groups.

[0098] Preferably, RY< in each occurrence represents H, D, F, a straight-chain alkyl, alkoxy, or thioalkyl group with 1 to 40, preferably 1 to 20, and more preferably 1 to 10 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group with 3 to 40, preferably 3 to 20, and more preferably 3 to 10 carbon atoms, each of which may be substituted by one or more R' groups, wherein one or more non-adjacent CH₂ groups may be replaced by R'C=CR', C=C, O, or S, and wherein one or more hydrogen atoms may be replaced by D or F, an aromatic or heteroaromatic ring system with 5 to 60, preferably 5 to 40, more preferably 5 to 30, and particularly preferably 5 to 18 aromatic ring atoms, each of which may be substituted by one or more R' groups may be substituted.

[0099] Preferably, R C0< represents, in each instance, the same or different substituents selected from H, D, a straight-chain alkyl group with 1 to 10, preferably 1 to 6 and further preferably 1 to 3 C atoms, which may be substituted by one or more substituents R', an aryl or heteroaryl group with 6 to 18 and preferably 6 to 12 aromatic ring atoms, each of which may be substituted by one or more substituents R', wherein two substituents R C0< together may form an aliphatic, aromatic or heteroaromatic ring system which is substituted by one or more substituents R'.

[0100] Preferably, R N0< represents, in each instance, the same or different, a residue selected from an aromatic or heteroaromatic ring system with 5 to 60, preferably 5 to 40, more preferably 5 to 30 and even more preferably 5 to 18 aromatic ring atoms, each of which may be substituted by one or more residues R'.

[0101] Examples of suitable blue phosphorescent metal complexes are shown below: Formula (Pt-1) 2460488-41-7 2446281-11-2 2347434-79-9 2347434-76-6 2737339-59-0 2417635-93-7 2347434-88-0 2347434-87-9 2347434-80-2 2347434-78-8 2347434-94-8 2347434-89-1 2347434-91-5 2347434-86-8 2347434-82-4 2347434-85-7 2347434-84-6 2567761-13-9 2567761-57-1 2460488-29-1 2567761-20-8 256722-51-2 2567722-23-8

[0102] A compound according to the invention can also be used in combination with a TADF host material and / or a TADF emitter, as previously explained.

[0103] The process known as thermally activated delayed fluorescence (TADF) is described, for example, by BH Uoyama et al., Nature 2012, Vol. 492, 234. To enable this process, a relatively small singlet-triplet distance ΔE(S1 - T1) of, for example, less than approximately 2000 cm⁻¹ is required in the emitter. To open the otherwise spin-forbidden transition T1 → S1, another compound with strong spin-orbit coupling can be included in the matrix next to the emitter. This allows inter-system crossing via 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.

[0104] In the further layers of the organic electroluminescent device according to the invention, all materials commonly used in the prior art can be employed. Therefore, without any inventive effort, a person skilled in the art can use all materials known for organic electroluminescent devices in combination with the compounds according to formula (I) or the preferred embodiments described above.

[0105] A further preferred organic electroluminescent device is characterized in that one or more layers are coated using a sublimation process. The materials are deposited 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 for the initial pressure to be even lower, for example less than 10⁻⁷ mbar.

[0106] A preferred method is also an organic electroluminescence device, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or with the aid of carrier gas sublimation. The materials are applied 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.

[0107] A further preferred organic electroluminescent device is characterized in that one or more layers are produced from solution, e.g., by spin coating, or by any printing process, e.g., 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 purpose, which can be obtained, for example, by suitable substitution.

[0108] Formulations for applying a compound according to formula (I) or its previously described preferred embodiments are novel. A further object of the present invention is therefore a formulation comprising at least one solvent and a compound according to formula (I) or its previously described preferred embodiments.

[0109] Hybrid processes are also possible, in which, for example, one or more layers of solution are applied and one or more further layers are vapor-deposited.

[0110] These methods are generally known to those skilled in the art and can be applied by them without inventive effort to organic electroluminescent devices containing the compounds according to the invention.

[0111] The electronic devices according to the invention, in particular organic electroluminescence devices, are characterized by one or more of the following surprising advantages over the prior art: 1. Electronic devices, in particular organic electroluminescent devices containing compounds according to formula (I) or the previously and subsequently described preferred embodiments as emitters, exhibit very narrow emission bands with low FWHM values ​​( F ull W idthH alf Maximum) and lead to particularly color-pure emission, recognizable by the small CIE y-values. It is particularly surprising that both blue emitters with low FWHM values ​​and emitters with low FWHM values ​​that emit in the green and, depending on the substitution, also in the yellow or red region of the color spectrum are provided. 2. Electronic devices, in particular organic electroluminescent devices containing compounds according to formula (I) or the preferred embodiments described above and below, especially as emitters, hole conductor material, and / or electron transport material, exhibit a very good lifetime. These compounds, in particular, result in a low roll-off, i.e., a low decrease in the power efficiency of the device at high luminances. 3. Electronic devices, in particular organic electroluminescent devices containing compounds according to formula (I) orThe previously and subsequently described preferred embodiments as emitters, hole conductor materials, and / or electron transport materials exhibit excellent efficiency. In this context, the compounds according to formula (I) or the previously and subsequently described preferred embodiments result in a low operating voltage when used in electronic devices. 4. The compounds according to formula (I) or the previously and subsequently described preferred embodiments exhibit very high stability and lifetime. 5. With compounds according to formula (I) or the previously and subsequently described preferred embodiments, the formation of optical loss channels can be avoided in electronic devices, particularly organic electroluminescent devices. This results in these devices exhibiting high PL and thus high EL efficiency of emitters.6. Compounds according to formula (I) or the preferred embodiments described above and below exhibit excellent glass film formation. 7. Compounds according to formula (I) or the preferred embodiments described above and below form very good films from solutions and show excellent solubility.

[0112] These aforementioned advantages do not come at the cost of an excessively high deterioration of other electronic properties.

[0113] It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Unless explicitly excluded, each feature disclosed in the present invention may be replaced by alternative features serving the same, an equivalent, or a similar purpose. Thus, unless otherwise stated, each feature disclosed in the present invention is to be considered as an example of a generic series or as an equivalent or similar feature.

[0114] All features of the present invention can be combined with one another 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 can be used separately (and not in combination).

[0115] It should further be noted that many of the features, and in particular those of the preferred embodiments of the present invention, are themselves inventive and not merely to be considered part of the embodiments of the present invention. Independent protection for these features may be sought in addition to or as an alternative to any currently claimed invention.

[0116] The teaching on technical action disclosed in the present invention can be abstracted and combined with other examples.

[0117] The invention is further explained by the following examples, without being intended to limit it. A person skilled in the art can implement the invention in its entire disclosed scope from the descriptions and, without inventive effort, create further connections according to the invention and use them in electronic devices or apply the method according to the invention. Examples:

[0118] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be obtained, for example, from Sigma-Aldrich or ABCR. The information in square brackets and the numbers given for individual compounds refer to the CAS numbers of the compounds known from the literature. For compounds that can have several enantiomeric, diastereomeric, or tautomeric forms, one form is shown as a representative example. Synthesis of Int-1a

[0119]

[0120] 2 g (11.3 mmol) of 4-chloro-2,3-dihydro-1-benzofuran-3-one are dissolved in 50 ml of dichloromethane. At room temperature, 3.12 ml (22.6 mmol) of triethylamine are added dropwise and the mixture is cooled to 0 °C. At this temperature, 2.23 ml (13.6 mmol) of trifluoromethanesulfonic anhydride are added dropwise, and the reaction mixture is stirred for six hours until complete conversion. The solvents are reduced under reduced pressure, the residue is purified by filtration over silica gel (DCM / heptane 1:2), and the product is obtained. Yield: 5.1 g (17 mmol; 86%).

[0121] The following compounds can be synthesized analogously: Connecting SM Product Int-1b Int-3f Int-1c Int-3g Int-1d CAS 72002-03-0 Synthesis of Int-2a

[0122]

[0123] The reaction proceeds analogously to that described by Anna Osichow et al., Organometallics (2013), 32(18), 5239-5242. The following compounds can be synthesized in the same manner: Connecting SM Product Int-2b CAS 344-18-3 Synthesis of Int-3a

[0124]

[0125] 5.1 g (17 mmol) of Int-1a, 2.8 g (8.1 mmol) of Int-2a, 3.8 g (36 mmol) of sodium carbonate, and Pd(PPh₃)₄ are dissolved in 50 mL of toluene / dioxane / water (2:1:1) and refluxed overnight. After complete conversion, the reaction mixture is cooled to room temperature, the organic phase is washed with water (2 x 40 mL), and dried over magnesium sulfate. After removal of the solvents under reduced pressure, the crude product is purified by column chromatography (ethyl acetate: heptane) and the product is isolated. Yield: 2.5 g (6.3 mmol; 78%).

[0126] The following compounds can be synthesized analogously: Connecting SM-1 SM-2 Product Int-3b Int-2a Int-1b Int-3c Int-2a Int-1c Int-3d Int-2b Int-1a Int-3e Int-2a Int-1d Int 3f 1344891-19-5 100379-00-8 Int-3g 1344899-88-2 100379-00-8 Synthesis of Compounds 1.a

[0127]

[0128] 6 g (15.2 mmol) of Int-3a, 9.4 g (97.4 mmol) of sodium tert-butoxide, 560 mg (1.4 mmol) of S-Phos, and 154 mg (0.7 mmol) of palladium acetate are dissolved in 200 mL of toluene and stirred overnight at 95°C. After complete reaction, the mixture is brought to room temperature and filtered through Celite. The solvents are removed under reduced pressure, and the residue is purified by several crystallizations from DCM / heptane. Yield: 3.4 g (10.5 mmol; 70%)

[0129] The following compounds can be synthesized analogously: Connecting SM Product 1.b Int-3b 1.c Int-3c 1.d Int-3d 1.e Int-3e Synthesis of Int-4a

[0130]

[0131] 15 g (47 mmol) of compound 1.a, 13.0 g (51 mmol) of bis(pinacolato)diborane, 310 mg (0.47 mmol) of (1,5-cyclooctadiene)(methoxy)iridium(I) dimer, and 251 mg (0.94 mmol) of 4,4'-di-tert-butyl-2,2'-dipyridyl are mixed in 400 ml of heptane and stirred at 90 °C for 16 hours. The solvents are removed under reduced pressure, and the residue is filtered over silica gel (heptane / THF) to obtain the product as a solid. Yield: 21.2 g (37 mmol; 78%).

[0132] The following compounds can be synthesized analogously: Connection SM product Int-4b Connection 1.b Int-4c Connection 1.c Int-4d Connection 1.d Int-4e Connection 1.e Synthesis of Int-5a

[0133]

[0134] 9 g (28 mmol) of compound 1.a, 10 g (56 mmol) of N-bromosuccinimide, 150 mL of acetic acid, and 150 mL of dichloromethane are stirred for 3 hours at 25 °C. The solvents are removed under reduced pressure, and the residue is filtered through silica gel (toluene) and recrystallized from THF / heptane to obtain the product as a solid. Yield: 1.8 g (4 mmol; 13%).

[0135] The following compounds can be synthesized analogously: Connection SM product Int-5b Connection 1.b Int-5c Connection 1.c Int-5d Connection 1.d Int-5e Connection 1.e Synthesis of Compound 2

[0136]

[0137] 6 g (12 mmol) of Int-5a, 3.6 g (24 mmol) of 2,6-dimethylphenylboronic acid, 27.6 g (0.1 mol) of tripotassium phosphate, and 400 mg (0.5 mmol) of tris-(dibenzylideneacetone)dipalladium(0), as well as 800 mg (0.2 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, are dissolved in 300 ml of dioxane and heated under reflux overnight. After complete reaction, the mixture is allowed to cool to room temperature. The solvents are removed under reduced pressure. The residue is purified by column chromatography (silica gel, heptane / ethyl acetate). Yield: 2 g (4 mmol; 16%). Synthesis of Compound 2

[0138]

[0139] 26.7 g (47 mmol) of Int-4a, 19.0 g (103 mmol) of 2-bromo-1,3-dimethylbenzene, 47.2 g (205 mmol) of tripotassium phosphate, and 1.7 g (2 mmol) of X-Phos Pd G3 are dissolved in 400 mL of toluene / water (2:1) and heated overnight under reflux. After complete reaction, the mixture is allowed to cool to room temperature. The organic phase is washed with water (2 x 150 mL), dried over magnesium sulfate, and concentrated under reduced pressure. The residue is purified by column chromatography (silica gel, heptane / ethyl acetate, and heptane / toluene). Yield: 15.4 g (29 mmol; 62%). The product is further purified by crystallization from toluene / heptane and sublimation under reduced pressure to an HPLC purity of >99.9%. Yield: 3.7 g (7 mmol; 15%).

[0140] The following compounds can be synthesized in an analogous manner: Connection SM-1 SM-2 product 3 Int-4a 19715-32-3 4 Int-4a 95-46-5 5 Int-4a 126866-29-3 6 Int-4a 10368-73-7 7 Int-4a 1890136-54-5 8 Int-5b 100379-00-8 9 Int-5c 100379-00-8 10 Int-5d 100379-00-8 11 Int-5e 100379-00-8 12 Int-4a 3842-55-5 Example 1: Photophysical measurements 1.) Determination of the peak wavelength λ max

[0141] To determine the maximum emission wavelength of the fluorescent emitter, the emitter is dissolved in toluene at a concentration of 1 mg / 100 ml. The solution is excited in a Hitachi F-4500 fluorescence spectrometer at a wavelength tailored to the material. The measurement is performed at room temperature. The maximum emission wavelength, λmax, is the wavelength of the first maximum in the emission spectrum. Typically, this first maximum is also the global maximum of the spectrum. 1. Determination of the spectral width (FWHM)

[0142] To determine the spectral width of the fluorescent emitter, the values ​​for the wavelengths (X1, X2) at half the maximum of the peak emission wavelength are subtracted. The full width at half the maximum is calculated according to formula (1). FWHM = X 2 − X 1

[0143] The following properties are obtained for the fluorescent emitters using the described methods and are shown in Table 1. Table 1. Properties of fluorescent emitters material λ max [nm] FWHM [nm] CIE y Connection 1.a 433 42 0.078 Connection 2 459 50 0.143 Manufacturing of OLEDs

[0144] Glass plates coated with structured ITO (50 nm, indium tin oxide) are wet-cleaned (dishwasher, Merck Extran cleaner). The substrates are then heated under nitrogen at 250 °C for 15 minutes. All materials are thermally evaporated in a vacuum chamber. In this case, the emission layer always consists of two materials. A specification such as H-01 (98%): Compound 1.a (2%) means that material H-01 is present in the emission layer at a volume fraction of 98% and material Compound 1.a at a volume fraction of 2%.

[0145] OLEDs consist of the following layer sequence, which is deposited onto the substrate after heat treatment: 20 nm HTM (95%):pD (5%), 160 nm HTM, 20 nm emissive layer, 10 nm ETM, 20 nm ETM (50%):LiQ (50%), 1 nm LiQ, 100 nm aluminum. The composition of the emissive layer is given in Table 2. The materials for OLED fabrication are listed in Table 3.

[0146] The OLEDs are characterized using standard methods. This involves recording the electroluminescence spectra and measuring the current-voltage-luminance (IUL) characteristics. (The luminance is measured perpendicular to the substrate.) The external quantum efficiency (EQE) is calculated as a function of the luminance, assuming Lambertian emission. The value U100 denotes the voltage required for a luminance of <100 cd / m². EQE100 refers to the external quantum efficiency at an operating luminance of <100 cd / m². The OLED performance data is given in Table 2.

[0147] It is shown in Table 2 that the compounds 1.a and 2 according to the invention are suitable as blue emitters for use in an organic electroluminescence device. Table 2: Nr. Emission layer EQE100 [%] Color 1 H-01(98%): Compound 1.a (2%) 5.0 blue 2 H-01 (98%): Compound 2 (2%) 5.5 blue Table 3: HTM pD [US2010102709A1 ; WO2015007729A1] ETM LiQ H-01 Connection 1.a Connection 2

Claims

1. A compound of formula (I), wherein the symbols used are as follows: Ara is the same or different at each occurrence and is an aryl or heteroaryl group with 5 to 18 aromatic ring atoms, which may be substituted with one or more radicals Ar or R, wherein the rings Ara together may form a ring system; V1 is the same or different at each occurrence and is O, S, or NR; V2 is the same or different at each occurrence and is N or CR; Ar is the same or different at each occurrence and is an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which may be substituted with one or more radicals R, wherein the group Ar may form a ring system with at least one group Ar, X1, R or a further group; X1 is the same or different at each occurrence and is N or CRa, with the proviso that not more than two of the groups X1, X2 are N in a cycle; X2 is the same or different at each occurrence and is N or CRb, preferably CRb, with the proviso that not more than two of the groups X1, X2 are N in a cycle; R, Ra ,Rb is the same or different at each occurrence and is H, D, OH, OR1, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R1)2, C(=O)OAr', C(=O)OR1, C(=O)N(Ar')2, C(=O)N(R1)2, C(Ar')3, C(R1)3, Si(Ar')3, Ge(Ar')3, Si(R1)3, B(Ar')2, B(R1)2, C(=O)Ar', C(=O)R1, P(=O)(Ar')2, P(=O)(R1)2, P(Ar')2, P(R1)2, S(=O)Ar', S(=O)R1, S(=O)2Ar', S(=O)2R1, OSO2Ar', OSO2R1, 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 40 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may each be substituted by one or more radicals R1, wherein one or more non-adjacent CH2 groups are replaced by R1C=CR1, C≡C, Si(R1)2, C=O, C=S, C=Se, C=NR1, -C(=O)O-, -C(=O)NR1-, NR1, P(=O)(R1), -O-, -S-, SO or SO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may each be substituted by one or more radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1; wherein two radicals R, Ra or Rb may also form a ring system with each other, or R may form a ring system with Ra; Ar' is the same or different at each occurrence and is an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which may be substituted with one or more radicals R1, wherein two radicals Ar' bonded to the same C atom, Si atom, N atom, P atom, S atom, Ge atom, or B atom may also be connected by a single bond or a bridge selected from B(R1), C(R1)2, Si(R1)2, C=O, C=NR1, C=C(R1)2, O, S, S=O, SO2, N(R1), P(R1) and P(=O)R1; R1 is the same or different at each occurrence and is H, D, F, Cl, Br, I, CN, NO2, N(Ar")2, N(R2)2, OR2, C(=O)OAr", C(=O)OR2, C(=O)Ar", C(=O)R2, P(=O)(Ar")2, P(Ar")2, B(Ar")2, B(R2)2, C(Ar")3, C(R2)3, Si(Ar")3, Ge(Ar")3, Si(R2)3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more radicals R2, wherein one or more non-adjacent CH2 groups may be replaced by -R2C=CR2-, - C≡C-, Si(R2)2, C=O, C=S, C=Se, C=NR2, -C(=O)O-, -C(=O)NR2-, NR2, P(=O)(R2), -O-, -S-, SO or SO2, and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which may each be substituted by one or more radicals R2, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R2, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R2; wherein two or more radicals R1 may form a ring system with each other, wherein one or more radicals R1 may form a ring system with another part of the compound; Ar" is the same or different in each occurrence, an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which may be substituted with one or more radicals R2, wherein two radicals Ar" bonded 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(R2), C(R2)2, Si(R2)2, C=O, C=NR2, C=C(R2)2, O, S, S=O, SO2, N(R2), P(R2) and P(=O)R2; R2 is selected, each occurrence being the same or different, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, Cl, Br, I, or CN, and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, wherein two or more substituents R2 may together form a ring system.

2. The compound of claim 1 according to formula (II), wherein the symbols have the meanings given in claim 1 and the following applies to the other symbols: X3 is the same or different at each occurrence and is N, CR, CAr, with the proviso that not more than two of the groups X3 in a cycle are N; V1, V3 is the same or different at each occurrence and is O, S, or NR; V2, V4 is the same or different at each occurrence and is N or C in each occurrence.

3. The compound of claim 2 according to one of formulas (II-1) to (II-36), FormulaV1V2V3V4II-1OONCII-2SONCII-3NRONCII-4OSNCII-5SSNCII-6NRSNCII-7ONRNCII-8SNRNCII-9NRNRNCII-10OONNII-11SONNII-12NRONNII-13OSNNII-14SSNNII-15NRSNNII-16ONRNNII-17SNRNNII-18NRNRNNII-19OOCCII-20SOCCII-21NROCCII-22OSCCII-23SSCCII-24NRSCCII-25ONRCCII-26SNRCCII-27NRNRCCII-28OOCNII-29SOCNII-30NROCNII-31OSCNII-32SSCNII-33NRSCNII-34ONRCNII-35SNRCNII-36NRNRCN4. The compound of to one or more of claims 1 to 3 according to formula (III) or (IIIa), wherein the symbols have the meanings given in claim 1.

5. The compound of claim 4, wherein the structure is selected from one of formulae (III-1) to (III-36): FormulaV1V2V3V4III-1OONCIII-2SONCIII-3NRONCIII-4OSNCIII-5SSNCIII-6NRSNCIII-7ONRNCIII-8SNRNCIII-9NRNRNCIII-10OONNIII-11SONNIII-12NRONNIII-13OSNNIII-14SSNNIII-15NRSNNIII-16ONRNNIII-17SNRNNIII-18NRNRNNIII-19OOCCIII-20SOCCIII-21NROCCIII-22OSCCIII-23SSCCIII-24NRSCCIII-25ONRCCIII-26SNRCCIII-27NRNRCCIII-28OOCNIII-29SOCNIII-30NROCNIII-31OSCNIII-32SSCNIII-33NRSCNIII-34ONRCNIII-35SNRCNIII-36NRNRCN6. The compound of one or more of claims 1 to 5, wherein the compound is selected from the compounds of formulae (IV-1) to (IV-6): wherein the symbols have the meanings given in claim 1.

7. An oligomer, polymer, or dendrimer containing one or more compounds according to one or more of claims 1 to 6, wherein one or more bonds of the compounds to the polymer, oligomer, or dendrimer are present instead of a hydrogen atom or a substituent.

8. A formulation comprising at least one compound according to one or more of claims 1 to 6 and / or an oligomer, polymer or dendrimer according to claim 7, and at least one solvent.

9. A composition comprising at least one compound according to one or more of claims 1 to 6 and / or an oligomer, polymer or dendrimer according to claim 7, 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 conductor materials, hole injection materials, electron blocking materials and hole blocking materials.

10. A method for producing a compound according to one or more of claims 1 to 6, characterized in that a substituted amine is synthesized, which is then intramolecularly cyclized to the basic structure of formula (I).

11. Use of a compound according to one or more of claims 1 to 6 or an oligomer, polymer, or dendrimer according to claim 7 in an electronic device.

12. An electronic device comprising at least one compound according to one or more of claims 1 to 6 and / or an oligomer, polymer or dendrimer according to claim 7.