Nitrogen-containing heterocyclic compounds for organic electroluminescent devices

Description

[0001] The present invention relates to nitrogen-containing 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 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.

[0003] Polycyclic compounds that can be used in organic electroluminescent devices are known from US Pat. No. 6,322,908, WO 03 / 001569 A2, and US Pat. No. 2019 / 0074445 A1. Compounds according to the present invention are not disclosed. Furthermore, the publication J. Org. Chem. 1995, 60, 2344-2352 describes the photochemical properties of compounds, obtaining, among other things, nitrogen-containing heterocyclic compounds. The synthesis of nitrogen-containing heterocyclic compounds is described in Chin. J. Chem. 2011, 29, 2769. However, the use of these compounds in organic electroluminescent devices is not described in the cited publications.

[0004] In general, there is still room for improvement in these nitrogen-containing 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.

[0005] 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.

[0006] 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.

[0007] Furthermore, the compounds should have excellent processability, with the compounds particularly showing good solubility.

[0008] A further object of the present invention can be seen in providing compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, particularly as emitters. In particular, it is an object of the present invention to provide emitters suitable for red, green, or blue electroluminescent devices.

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

[0010] 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 matrix materials. In particular, it is an object of the present invention to provide matrix materials suitable for red, yellow, and blue phosphorescent electroluminescent devices.

[0011] Furthermore, the compounds should lead to devices with excellent color purity, especially when used as matrix materials or as electron transport materials in organic electroluminescent devices.

[0012] Another task can be seen in providing electronic devices with excellent performance as cost-effectively as possible and in consistent quality

[0013] 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), where the ring Ar a< is, identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms which may be substituted by one or more radicals Ar or R a<, the ring Ar b< is, identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms which may be substituted by one or more radicals Ar or R b<; and the following applies to the other symbols and indices used: W a< . W b< is, identical or different on each occurrence, O or S, preferably O; Ar is, identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms which may be substituted by one or more radicals R, here the group Ar can form a ring system with at least one group Ar, R, R a< , R b< or one further group; R, R a< ,R b< is, at each occurrence, the same or different, H, D, OH, F, Cl, Br, I, CN, NO 2 , N(Ar') 2 , N(R 1< ) 2 , C(=O)N(Ar') 2 , C(=O)N(R 1< ) 2 , C(Ar') 3 , C(R 1< ) 3 , Si(Ar') 3 , Si(R 1< ) 3 , B(Ar') 2 , B(R 1< ) 2 , C(=O)Ar', C(=O)R 1< , P(=O)(Ar') 2 , P(=O)(R 1< ) 2 , P(Ar') 2 , P(R 1< ) 2 , S(=O)Ar', S(=O)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 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 may each be substituted by one or more radicals R 1<, where one or more non-adjacent CH 2 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 SO 2 can be replaced,or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R 1<, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1<; or heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1<, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1<, 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 1<; two radicals R, R a< ,R b< may also form a ring system with each other or with a further group; Ar' is, on each occurrence, the same or different, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms which may be substituted by one or more radicals R 1<, where two radicals Ar' which are bonded to the same C atom, Si atom, N atom, P atom or B atom may also be bridged to each other 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 1< ; R 1< is, identically or differently at each occurrence, H, D, F, Cl, Br, I, CN, NO 2 , N(Ar") 2 , N(R 2< ) 2 , C(=O)Ar", C(=O)R 2< , P(=O)(Ar") 2 , P(Ar") 2 , B(Ar") 2 , B(R 2< ) 2 , C(Ar") 3 , C(R 2< ) 3 , Si(Ar") 3 , Si(R 2< ) 3 , a 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 may be substituted by one or more radicals R 2<, where one or more non-adjacent CH 2 groups may be 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 SO 2 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO 2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be 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<, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2<,or a combination of these systems; two or more, preferably adjacent, radicals R 1< can form a ring system with one another, and one or more radicals R 1< can form a ring system with another part of the compound; Ar" is, at each occurrence, identical or different, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 2<; two radicals Ar" which are bound to the same C atom, Si atom, N atom, P atom or B atom may also be bridged to one another 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, at each occurrence, identical or different, selected 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, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, two or more, preferably adjacent, substituents R 2< may form a ring system with each other; where compounds of the formulas (A), (B) and (C), are excluded from protection.

[0016] Compounds of formulas (A), (B), and (C) are excluded from protection. Compound (A), which has CAS No. 125213-40-3, compound (B), which has CAS No. 131847-09-1, and compound (C), which has CAS No. 166042-85-9, are known from the prior art, but their use in an electronic device is not.

[0017] 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.

[0018] 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.

[0019] An aromatic ring system within the meaning of this invention contains 6 to 60 C atoms in the ring system. A heteroaromatic ring system within the meaning of this invention contains 2 to 60 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 understood to mean a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be linked 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.

[0020] 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 CH 2 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, 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 may be straight-chain, branched, or cyclic, wherein one or more non-adjacent CH 2 groups may be replaced by the above-mentioned groups; furthermore, one or more H atoms may also be replaced by D, F, Cl, Br, I, CN, or NO 2 , preferably F, Cl, or CN, more preferably F or CN, particularly preferably CN.

[0021] An aromatic or heteroaromatic ring system with 5 - 60 or 5 to 40 aromatic ring atoms, which may each be substituted by 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, 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.,

[0022] 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.

[0023] 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:

[0024] In a preferred embodiment, the compounds according to the invention can comprise a structure of the formulas (II-1) to (II-42), particularly preferably the compounds according to the invention can be selected from the compounds of the formulas (II-1) to (II-42), where the symbols W a< and W b< have the meanings given above, in particular for formula (I), and the following applies to the other symbols: Y a< is equal or different N(Ar), N(R a< ), P(Ar), P(R a< ), P(=O)Ar, P(=O)R a< , P(=S)Ar, P(=S)R a< , B(Ar), B(R a< ), Al(Ar) 2 , Si(R a< ) 2 , Ge(R a< ) 2 , C=NR a< , C=NAr, C=C(R a< ) 2 , C=C(R a< )(Ar), O, S, Se, S=O, oder SO 2 , vorzugsweise N(Ar), N(R a< ) , B(R a< ) , P(R), B(R), P(O) P(=O)Ar, C=O, C(R a< ) 2 , C=C(R a< ) 2 , C=C(R a< )(Ar), Si(R a< ) 2 , O, S, Se, S=O or SO 2 , especially preferred N(Ar), C(R a< ) 2 , O or S, R< (I) omits contemporaneous meaning;Y b< is, the same or different at each occurrence, N(Ar), N(R b< ), P(Ar), P(R b< ), P(=O)Ar, P(=O)R b< , P(=S)Ar, P(=S)R b< , B(Ar), B(R b< ), Al(Ar), Al(R a< ), Ga(Ar), Ga(R b< ), C=O, C(R b< ) 2 , Si(R b< ) 2 , Ge(R b< ) 2 , C=NR b< , C=NAr, C=C(R b< ) 2 , C=C(R b< )(Ar), O, S, Se, S=O, or SO 2 , preferably N(Ar), N(R b< ), B(Ar), B(R b< ), P(=O)R b< , P(=O)Ar, C=O, C(R b< ) 2 , C=C(R b< ) 2 , C=C(R b< )(Ar), Si(R b< ) 2 , O, S, Se, S=O or SO 2 , particularly preferably N(Ar), C(R b< ) 2 , O or S, where R b< has the meaning set out above, in particular for formula (I);Y 1< , Y 2< is the same or different each time it occurs C=NAr, C=C(R) 2 , C=C(R)(Ar), O, S, Se, S=O, or SO 2 , preferably N(Ar), N(R), B(Ar), B(R), P(=O)R, P(=O)Ar, C=O, C(R) 2 , C=C(R) 2 , C=C(R)(Ar), Si(R) 2 , O, S, Se, S=O or SO2, especially preferably N(Ar), C(R) 2 , O or S, where R has the meaning set out above, in particular for formula (I); X, identically or differently on each occurrence, represents N or CR, preferably CR, with the proviso that no more than two of the groups X in a cycle represent N, where R has the meaning set out above, in particular for formula (I);X a< stands on each occurrence, identically or differently, for N or CR a< , preferably for CR a< , with the proviso that no more than two of the groups X a< in a cycle stand for N, where R a< has the meaning set out above, in particular for formula (I); X b< stands on each occurrence, identically or differently, for N or CR b< , preferably for CR b< , with the proviso that no more than two of the groups X b< in a cycle stand for N, where R b< has the meaning set out above, in particular for formula (I). ;

[0025] Structures of the formulas (II-1) to (II-31) are preferred and structures of the formulas (II-1) to (II-4), (II-6), (II-8), (II-10), (II-12), (II-14), (II-16) to (II-19), (II-21), (II-23), (II-25), (II-27), (II-29), (II-31) are particularly preferred.

[0026] Furthermore, in particular for compounds comprising structures of the formulas (I) and (II-1) to (II-42), it can be provided that at least one of the groups W a< , W b< stands for O, preferably both groups W a< , W b< stand for O.

[0027] If a compound contains two or more nitrogen atoms, these nitrogen atoms are preferably not adjacent, so that no N-N bonds are present.

[0028] In a further preferred embodiment, it can be provided that the compounds according to the invention comprise a structure of the formulas (III-1) to (III-41), wherein the compounds according to the invention can particularly preferably be selected from the compounds of the formulas (III-1) to (III-41), where the symbols Y 1< , Y 2< , Y a< , Y b< , X, X a< and X b< have the meanings given above, in particular for formulas (II-1) to (II-42).

[0029] Structures of the formulas (III-1) to (III-31) are preferred and structures of the formulas (III-1) to (III-4), (III-6), (III-8), (III-10), (III-12), (III-14), (III-16) to (III-19), (III-21), (III-23), (III-25), (III-27), (III-29), (III-31) are particularly preferred.

[0030] Preferably, it can be provided that in formulas (II-1) to (II-42) and / or (III-1) to (III-41) not more than four, preferably not more than two groups X, X a< and X b< stand for N, particularly preferably all groups X, X a< and X b< stand for CR, CR a< or CR b<.

[0031] In a further preferred embodiment, it can be provided that the compounds according to the invention comprise a structure of the formulas (IV-1) to (IV-41), wherein the compounds according to the invention can particularly preferably be selected from the compounds of the formulas (IV-1) to (IV-41), where the symbols R, R a< and R b< have the meanings given above, in particular for formula (I), the symbols Y 1< , Y 2< , Y a< and Y b< have the meanings given above, in particular for formulas (II-1) to (II-42) and the other symbols have the following meaning: m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2; j is 0, 1 or 2, preferably 0 or 1.

[0032] Structures / compounds of the formulas (IV-1) to (IV-31) are preferred, structures / compounds of the formulas (IV-1) to (IV-4), (IV-6), (IV-8), (IV-10), (IV-12), (IV-14), (IV-16) to (IV-19), (IV-21), (IV-23), (IV-25), (IV-27), (IV-29), (IV-31) are particularly preferred.

[0033] Furthermore, it can be provided that the residues Y a< and Y b< are identical. Furthermore, the residues Y a< and Y b< can be different.

[0034] In a further embodiment, it can be provided that one of the radicals Y a< and Y b< stands for O and one of the radicals Y a< and Y b< stands for C(R a< ) 2 or C(R b< ) 2 .

[0035] In a further embodiment, it can be provided that one of the radicals Y a< and Y b< stands for NAr and one of the radicals Y a< and Y b< stands for C(R a< ) 2 or C(R b< ) 2 .

[0036] Furthermore, the residues Y 1< and Y 2< can be identical. Furthermore, the residues Y 1< and Y 2< can be different.

[0037] In a further embodiment, it can be provided that one of the radicals Y 1< and Y 2< stands for O and one of the radicals Y 1< and Y 2< stands for C(R a< ) 2 or C(R b< ) 2 .

[0038] In a further embodiment, it can be provided that one of the radicals Y 1< and Y 2< stands for NAr and one of the radicals Y 1< and Y 2< stands for C(R a< ) 2 or C(R b< ) 2 .

[0039] In a further preferred embodiment, it can be provided that the compounds according to the invention comprise a structure of the formulas (V-1) to (V-8), wherein the compounds according to the invention can particularly preferably be selected from the compounds of the formulas (V-1) to (V-8), where the symbols R a< and R b< have the meanings given above, in particular for formula (I), and the other symbols have the following meaning: R c< , R d< is the same or different at each occurrence 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) 2 Ar', S(=O) 2 R 1< , OSO 2 Ar', OSO 2 R 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, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may each be substituted by one or more radicals R 1<, where one or more non-adjacent CH 2 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 SO 2 can be replaced,or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R 1<, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1<; or heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1<, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1<, 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 1<; wherein a radical R c< forms a ring system with a radical R, R a< , R b< , R d< or another group; wherein a radical R d< forms a ring system with a radical R, R a< , R b< ,R c< or another group form a ring system; m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2; n is 0, 1, 2 or 3, preferably 0, 1 or 2. ,

[0040] Furthermore, especially for structures / compounds of formulas (V-1) to (V-8), it can be provided that the radicals R c< and R d< are identical. Furthermore, the radicals R c< and R d< can be different.

[0041] The sum of the indices j, m and n, in particular in structures / compounds of the formulas (IV-1) to (IV-41) and / or (V-1) to (V-8), is preferably at most 10, preferably at most 8, particularly preferably at most 6 and particularly preferably at most 4.

[0042] Furthermore, in formulas (I), (II-1) to (II-42), (III-1) to (III-42), (IV-1) to (IV-41), (V-1) to (V-8) and / or the preferred embodiments of these formulas set out below, it can be provided that at least one radical R, R a< , R b< , R c< , R d< represents 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 can each be substituted by one or more radicals R 1<, where one or more non-adjacent CH 2 groups can be replaced 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 SO 2 , or for an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms,which may be substituted by one or more radicals R 1<, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1<; or a heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1<, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1<, 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 1<.

[0043] Preferably, in formulas (I), (II-1) to (II-42), (III-1) to (III-42), (IV-1) to (IV-41), (V-1) to (V-8) and / or the preferred embodiments of these formulas set out below, it can be provided that at least one radical R, R a< , R b< , R c< , R d< represents an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 1<, or represents an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1<;or represents a heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1<, or represents a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1<, or represents 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 1<, particularly preferably represents an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R 1<.;

[0044] In a preferred development of the present invention, it can be provided that at least two radicals R, R a< , R b< , R c< , R d< form a condensed ring with the further groups to which the two radicals R, R a< , R b< , R c< , R d< are bonded, wherein the two radicals R, R a< , R b< , R c< , R d< form at least one structure of the formulas (RA-1) to (RA-12) where R 1< has the meaning set out above, the dashed bonds represent the attachment points via which the two radicals R, R a< , R b< , R c< , R d< bind to the other groups, and the other symbols have the following meaning: Y 3< is, identically or differently at 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 e< 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 may each be substituted by one or more radicals R 2<, where one or more non-adjacent CH 2 groups are substituted 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 1< ), -O-, -S-, SO or SO 2 , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R 2<, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2<;two radicals R e< can also form a ring system with one another or one radical R e< can form a ring system with one radical R 1< or with another group; 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.

[0045] In a preferred embodiment of the invention, the at least two radicals R, R a< , R b< , R c< , R d< form a condensed ring with the further groups to which the two radicals R, R a< , R b< , R c< , R d< are bonded, wherein the two radicals R, R a< , R b< , R c< , R d< preferably form at least one of the structures of the formulas (RA-1a) to (RA-4f) where the dashed bonds represent the attachment points via which the two radicals R, R a< , R b< , R c< , R d< bind to the further groups, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2 and the symbols R 1< , R 2< , R e< and the indices s and t have the meaning set out above, in particular for formula (I) and / or formulas (RA-1) to (RA-12).

[0046] Furthermore, it can be provided that the at least two radicals R, R a< , R b< , R c< , R d< form the structures of the formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) and form a condensed ring, represent radicals R, R a< , R b< , R c< , R d< from adjacent groups X, X a< , X b< or represent radicals R, R a< , R b< , R c< , R d< which each bind to adjacent C atoms, wherein these C atoms are preferably connected via a bond.

[0047] In a further preferred embodiment, at least two radicals R, R a< , R b< , R c< , R d< form a condensed ring with the further groups to which the two radicals R, R a< , R b< , R c< , R d< are bonded, wherein the two radicals R, R a< , R b< , R c< , R d< form structures of the 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< bind to the further groups, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y 4< is C(R 1< )2, NR 1< , NAr', BR 1< , BAr', O or S, preferably C(R 1< )2, NAr' or O.

[0048] It can be provided that the at least two radicals R, R a< , R b< , R c< , R d< , form the structures of the formula (RB) and form a condensed ring, represent radicals R, R a< , R b< , R c< , R d< from adjacent groups X, X a< , X b< , or represent radicals R, R a< , R b< , R c< , R d< which each bind to adjacent C atoms, wherein these C atoms are preferably connected to one another via a bond.

[0049] The compounds particularly preferably comprise at least one structure of the formulas (VI-1) to (VI-22), particularly preferably the compounds are selected from compounds of the formulas (VI-1) to (VI-22), wherein the compounds have at least one condensed ring where the symbols R, R a< , R b< , Y 1< and Y 2< have the meanings given above, in particular for formula (I) and / or formulas (II-1) to (II-42), the symbol o stands for the attachment points and the other symbols have the following meaning: m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2; j is 0, 1 or 2, preferably 0 or 1; k is 0 or 1.

[0050] Structures / compounds of the formula (VI-1) to (VI-4) are preferred.

[0051] The compounds particularly preferably comprise at least one structure of the formulas (VII-1) to (VII-4), particularly preferably the compounds are selected from compounds of the formulas (VII-1) to (VII-4), wherein the compounds have at least one condensed ring where the symbols R, R a< and R b< have the meanings given above, in particular for formula (I), the symbol o stands for the attachment points of the condensed ring and the other symbols have the following meaning: j is 0, 1, or 2, preferably 0 or 1; k is 0 or 1.

[0052] The condensed ring, in particular in formulas (VI-1) to (VI-22) and / or (VII-1) to (VII-4), is preferably formed by at least two radicals R, R a< , R b< , R c< , R d< and the further groups to which the two radicals R, R a< , R b< , R c< , R d< are bonded, wherein the at least two radicals R, R a< , R b< , R c< , R d< form structures of the formulas (RA-1) to (RA-12) and / or of the formula (RB), preferably structures of the formulas (RA-1) to (RA-12).

[0053] Preferably, the compounds may have at least two condensed rings, wherein at least one condensed ring is formed by structures of the formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) and a further ring is formed by structures of the formulas (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB).

[0054] In particular in the formulas (VI-1) to (VI-22) and / or (VII-1) to (VII-4), the sum of the indices k, j and m is preferably 0, 1, 2 or 3, particularly preferably 1 or 2.

[0055] Furthermore, it can be provided that the substituents R, R a< , R b< , R c< , R d< , R e< , R 1< and R 2< according to the above formulas do not form a condensed aromatic or heteroaromatic ring system with the ring atoms of the ring system to which the substituents R, R a< , R b< , R c< , R d< , R e< , R 1< and R 2< are bonded. This includes the formation of a condensed aromatic or heteroaromatic ring system with possible substituents R 1< and R 2<, which can be bonded to the radicals R, R a< , R b< , R c< , R d< , R e< and R 1<.

[0056] If two radicals, which can in particular be selected from R, Ra< , Rb< , Rc< , Rd< , Re< , R1< and / or R2< , form a ring system with one another, this can be mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic. The radicals which form a ring system with one another can be adjacent, i.e. these radicals are bonded to the same carbon atom or to carbon atoms which are directly bonded to one another, or they can be further apart from one another. Furthermore, the ring systems provided with the substituents R, Ra< , Rb< , Rc< , Rd< , Re< , R1< and / or R2< can also be linked to one another via a bond, so that a ring closure can be brought about. In this case, each of the corresponding binding sites is preferably provided with a substituent R, R a< , R b< , R c< , R d< , R e< , R 1< and / or R 2<.

[0057] According to a preferred embodiment, a compound according to the invention can be represented by at least one of the structures according to formulas (I), (II-1) to (II-42), (III-1) to (III-42), (IV-1) to (IV-41), (V-1) to (V-8), (VI-1) to (VI-22) and / or (VII-1) to (VII-4). Preferably, compounds according to the invention, preferably comprising structures according to formulas (I), (II-1) to (II-42), (III-1) to (III-42), (IV-1) to (IV-41), (V-1) to (V-8), (VI-1) to (VI-22) and / or (VII-1) to (VII-4) 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 very particularly preferably less than or equal to 1200 g / mol.

[0058] 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.

[0059] Preferred aromatic or heteroaromatic ring systems R, R a< , R b< , R c< , R d< , R e< , 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 can be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene,which may each be substituted by one or more radicals R 1< or R.,

[0060] Preferably, it can be provided that at least one substituent R, R a< , R b< 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-78, preferably the substituents R, R a< , R b< either form a condensed ring, preferably according to the structures of the formulas (RA-1) to (RA-12) or (RB) or the substituent R, R a< , R b< is 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-78, and / or the group Ar' is selected, identically or differently on each occurrence, from the groups of the following formulas Ar-1 to Ar-78, where R 1< has the meanings given above, the dashed bond represents the attachment point and furthermore: Ar 1< is, on each occurrence, identical or different, a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, each of which may be substituted by one or more radicals R 1<; A is, on each occurrence, identical 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 the corresponding radical; q is 0 or 1, where q = 0 means that no group A is bonded to this position and radicals R 1< are bonded to the corresponding carbon atoms instead.

[0061] 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-45), (Ar-47), (Ar-57), (Ar-69), (Ar-70), (Ar-75), (Ar-78) 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.

[0062] If the above-mentioned groups for structures of formulae (Ar-1) to (Ar-78) have multiple A groups, all combinations from the definition of A are possible. Preferred embodiments are then those in which one A group represents NR 1< and the other A group represents C(R 1< ) 2 , or in which both A groups represent NR 1<, or in which both A groups represent O.

[0063] When A stands for NR 1<, the substituent R 1< which is bonded to the nitrogen atom preferably stands for an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more radicals R 2<. In a particularly preferred embodiment, this substituent R 1<, identical or different on each occurrence, stands for 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 have any fused aryl groups and which does not have any fused heteroaryl groups in which two or more aromatic or heteroaromatic 6-ring groups are directly fused to one another, and which may in each case also be substituted by one or more radicals R 2<.Phenyl, biphenyl, terphenyl, and quaterphenyl with linkage patterns as listed above for Ar-1 to Ar-11 are preferred, where these structures may be substituted by one or more R 2< radicals instead of R 1<, but are preferably unsubstituted. Also preferred are triazine, pyrimidine, and quinazoline, as listed above for Ar-47 to Ar-50, Ar-57, and Ar-58, where these structures may be substituted by one or more R 2< radicals instead of R 1<.

[0064] Preferred substituents R, R a< , R b< , R c< , R d< and R e< are described below.

[0065] In a preferred embodiment of the invention, R, R a< , R b< are the same or different on each occurrence and are selected from the group consisting of H, D, F, CN, NO 2 , Si(R 1< ) 3 , 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, where the alkyl group may in each case be substituted by one or more radicals R 1<, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R 1<.

[0066] In a further preferred embodiment of the invention, substituent R, R a< , R b< is the same or different on each occurrence and is 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 may in each case be substituted by one or more radicals R 1<, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R 1<.

[0067] Furthermore, it can be provided that at least one substituent R, R a< , R b< is selected, identically or differently on each occurrence, from the group consisting of H, D, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 1<, or a group N(Ar') 2 . In a further preferred embodiment of the invention, the substituents R, R a< , R b< , R c< , R d< either form a ring according to the structures of the formulas (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB) or the substituent R, R a< , R b< is the same or different on each occurrence and is selected from the group consisting of H, D, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 1<, or a group N(Ar') 2 .Particularly preferably, substituent R, R a< , R b< is the same or different on each occurrence and is 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, which may each be substituted by one or more radicals R 1<.

[0068] Preferably, it can be provided that at least one substituent R, R a< , R b< , R c< , R d< is selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, which may each be substituted by one or more radicals R 1<. Here, the term substituent means in particular that R, R a< , R b< , R c< , R d< are not H. Furthermore, the substituents R, R a< , R b< , R c< , R d< may be the same or different if two or more substituents are present which are selected from the said aromatic or heteroaromatic group.

[0069] In a further embodiment, it can be provided that at least one substituent R, R a< , R b< , R c< , R d< is selected from o-biphenyl, o,o'-terphenyl, o,o',p-quaterphenyl, 4,6-diphenyl-pyrimidin-2-yl, 4,6-diphenyl-trianin-2-yl, naphthalene, phenanthrene, chrysene, spiro-bifluorene, triphenylene, anthracene, benzanthracene, fluorene and / or pyrene, which can each be substituted by one or more radicals R 1<. Spiro-bifluorene, o-biphenyl, o,o'-terphenyl, o,o',p-quaterphenyl, 4,6-diphenyl-pyrimidin-2-yl, 4,6-diphenyl-trianin-2yl radicals are preferred here. The substituents R, R a< , R b< , R c< , R d< may be the same or different if two or more substituents are present that are selected from the aromatic groups mentioned. Structures / compounds with a group selected from o-biphenyl, o,o'-terphenyl, o.,o',p-Quaterphenyl, 4,6-diphenyl-pyrimidin-2-yl, 4,6-diphenyl-trianin-2-yl, naphthalene, phenanthrene, chrysene, spiro-bifluorene, triphenylene, anthracene, benzanthracene, fluorene and / or pyrene are particularly suitable for use as electron transport material and / or as matrix material.

[0070] For the substituents R c< , R d<, the preferences previously set out with regard to the substituents R, R a< , R b< apply accordingly, with the aforementioned restrictions. In particular, it can be provided that at least one substituent R c< , R d< is selected, identically or differently on each occurrence, from the group consisting of an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 1<, or a group N(Ar') 2 .In addition, it can be provided that the substituents R c< , R d< either form a condensed ring, preferably according to the structures of the formulas (RA-1) to (RA-12) or (RB) or the substituent R c< , R d< is selected, identically or differently on each occurrence, from the group consisting of an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 1<, or a group N(Ar') 2 .

[0071] Particularly preferably, the substituent R c< , R d<, identically or differently on each occurrence, represents an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 1<, which is preferably selected from the groups of the formulas (Ar-1) to (Ar-78) set out above.

[0072] In a preferred embodiment of the invention, R e< is the same or different on each occurrence and is 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 may in each case be substituted by one or more radicals R 1<, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2<.

[0073] In a further preferred embodiment of the invention, R e< is the same or different on each occurrence and is 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 may be substituted in each case by one or more radicals R 2<, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 2<.Particularly preferably, R e< is selected, identically or differently on each occurrence, 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 may in each case be substituted by one or more radicals R 2< 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, which may in each case be substituted by one or more radicals R 2<.

[0074] In a preferred embodiment of the invention, R e< is selected, identically or differently at each occurrence, from the group consisting of a straight-chain alkyl group having 1 to 6 C atoms or a cyclic alkyl group having 3 to 6 C atoms, where the alkyl group may in each case be substituted by one or more radicals R 2<, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2<; two radicals R e< may also form a ring system with one another.Particularly preferably, R e< is selected, identically or differently at each occurrence, 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 may in each case be substituted by one or more radicals R 2<, but is preferably unsubstituted, or an aromatic ring system having 6 to 12 aromatic ring atoms, in particular having 6 aromatic ring atoms, which may in each case be substituted by one or more, preferably non-aromatic radicals R 2<, but is preferably unsubstituted; two radicals R e< can form a ring system with one another. Very particularly preferably, R e< is selected, identically or differently at each occurrence, 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.Most preferably, R e< represents a methyl group or a phenyl group, where two phenyl groups together can form a ring system, with a methyl group being preferred over a phenyl group.

[0075] Preferred aromatic or heteroaromatic ring systems, which are represented by substituents R, R a< , R b< , R c< , R d< , R e< or 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 can be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline,Phenanthrene or triphenylene, which may each be substituted by one or more radicals R, R 1< or R 2<. The structures Ar-1 to Ar-78 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-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-78, it should be noted that these are represented with a substituent R 1<. In the case of the ring systems Ar, these substituents R 1< are to be replaced by R and in the case R e< these substituents R 1< are to be replaced by R 2<.

[0076] Further 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<, identical or different on each occurrence, represent an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R 1<. The total number of aromatic ring atoms of Ar 2< , Ar 3< and Ar 4< is a maximum of 60 and preferably a maximum of 40.

[0077] Ar 4< and Ar 2< can be linked to one another and / or Ar 2< and Ar 3< can also be linked to one another by a group selected from C(R 1< ) 2, NR 1< , O, or S. Preferably, Ar 4< and Ar 2< are linked to one another, or Ar 2< and Ar 3< are linked to one another, in each case 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< are linked to one another.

[0078] Preferably, Ar 4< is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, each of which may be substituted by one or more R 1< radicals. Ar 4< is particularly preferably selected from the group consisting of ortho-, meta-, or para-phenylene or ortho-, meta-, or para-biphenyl, each of which may be substituted by one or more R 1< radicals, but is preferably unsubstituted. Most preferably, Ar 4< is an unsubstituted phenylene group.

[0079] Preferably, Ar 2< and Ar 3<, identical or different on each occurrence, are an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R 1<. Particularly preferred groups Ar 2< and 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-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 by one or more radicals R 1<.Very particularly preferably, Ar 2< and Ar 3< are selected, identically or differently on each occurrence, 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.

[0080] In a further preferred embodiment of the invention, R 1< is selected, identically or differently on each occurrence, 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 may in each case be substituted by one or more radicals R 2<, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2<.In a particularly preferred embodiment of the invention, R 1< is selected, identically or differently on each occurrence, 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 may be substituted by one or more radicals R 5<, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, each of which may be substituted by one or more radicals R 5<, but is preferably unsubstituted.

[0081] In a further preferred embodiment of the invention, R 2< is identical or different on each occurrence and is 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.

[0082] 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.

[0083] Furthermore, it can be provided that the compound comprises exactly two or exactly three structures according to formula (I), (II-1) to (II-42), (III-1) to (III-41), (IV-1) to (IV-41), (V-1) to (V-8), (VI-1) to (VI-22) and / or (VII-1) to (VII-4).

[0084] In a preferred embodiment, the compounds are selected from compounds of formula (D-1) or (D-2), where the group L' represents a linking 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 1<, and the other symbols used have the meanings given above, in particular for formula (I).

[0085] 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 1<, but is preferably unsubstituted, where R 1< may have the meaning given above, in particular for formula (I). More preferably, L' represents an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which may be substituted by one or more radicals R 2<, but is preferably unsubstituted, where R 2< may have the meaning given above, in particular for formula (I).

[0086] Furthermore, the symbol L' shown inter alia in formula (D2) preferably represents, identically or differently on each occurrence, 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.

[0087] Furthermore, it can be provided that the group L 1< shown in formula (D2) comprises an aromatic ring system with at most four, preferably at most three, particularly preferably 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.

[0088] Particularly preferred are structures that do not exhibit condensation, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0089] Examples of suitable aromatic or heteroaromatic ring systems L 1< are 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, which may each be substituted by one or more radicals R 1<, but are preferably unsubstituted.

[0090] 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.

[0091] Examples of preferred compounds according to the embodiments listed above are the compounds listed in the following table: 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152

[0092] 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.

[0093] Provided that the conditions stated in claim 1 are met, the above-mentioned preferred embodiments can be combined with one another in any way. In a particularly preferred embodiment of the invention, the above-mentioned preferred embodiments apply simultaneously.

[0094] The compounds of the invention can, in principle, be prepared by various methods. However, the methods described below have proven particularly suitable.

[0095] Therefore, a further object of the present invention is a process for preparing the compounds according to the invention, in which a basic skeleton with at least one of the groups W a< or a precursor of one of the groups W a< is synthesized and an aromatic or heteroaromatic radical is introduced by means of a nucleophilic aromatic substitution reaction or a coupling reaction.

[0096] Suitable compounds comprising a basic skeleton with a group W a< can often be obtained commercially, the starting compounds presented in the examples being obtainable by known processes, so that reference is made thereto.

[0097] These compounds can be reacted with other compounds by known coupling reactions, the necessary conditions for this being known to the person skilled in the art and detailed information in the examples assisting the person skilled in the art in carrying out these reactions.

[0098] Particularly suitable and preferred coupling reactions, all of which lead to CC and / or CN 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.

[0099] 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.

[0100] 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).

[0101] 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 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 according to the invention can be used as crosslinked or uncrosslinked layers.

[0102] 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.

[0103] 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.

[0104] 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).

[0105] 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, α-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, Decalin, dodecylbenzene, 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 sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents.

[0106] 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.

[0107] Yet another subject of the present invention is therefore a composition comprising at least one compound of formula (I) where the symbols used have the meanings given above, preferably at least one compound according to the invention or an oligomer, polymer, or dendrimer comprising structures according to formula (I) and at least one further organic functional material. Functional materials are generally the organic or inorganic materials introduced between the anode and cathode. The organic functional material is preferably 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 conductor materials, hole injection materials, electron blocking materials, hole blocking materials, wide-band gap materials, and n-dopants.

[0108] Another object of the present invention is the use of a compound according to formula (I) where the symbols used have the meanings given above, preferably a compound according to the invention or an oligomer, polymer, or dendrimer comprising structures according to formula (I) in an electronic device, in particular in an organic electroluminescent device, preferably as an emitter, particularly preferably as a green, red, or blue emitter. Compounds according to the invention preferably exhibit fluorescent properties and thus preferably provide fluorescent emitters.

[0109] Preferably, it can be provided that structures / compounds according to formulas (II-2) to (II-8), (II-17) to (II-23), (III-2) to (III-8), (III-17) to (III-23), (IV-2) to (IV-8), (IV-17) to (IV-23), (V-1), (V-2), (V-5) and / or (V-6) are used as emitters.

[0110] Furthermore, compounds according to formula (I) or an oligomer, polymer, or dendrimer comprising structures according to formula (I) can be used as host materials and / or electron transport materials. Preferably, it can be provided that structures / compounds with an anthracene group (Ar-76) to (Ar-78), preferably (Ar-78), and / or compounds according to formulas (II-9), (II-10), (II-24), (II-25), (III-9), (III-10), (III-24), (III-25), (IV-9), (IV-10), (IV-24) and / or (IV-25) are used as electron transport material and / or matrix material.

[0111] A further subject of the present invention is an electronic device comprising at least one compound of formula (I) where the symbols used have the meanings given above, preferably a compound according to the invention or an oligomer, polymer, or dendrimer comprising structures according to formula (I). An electronic device within the meaning of the present invention is a device that contains at least one layer containing at least one organic compound. The component can also contain inorganic materials or layers composed entirely of inorganic materials.

[0112] 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.

[0113] 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.

[0114] 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 structure / compound according to formula (I) or the preferred embodiments outlined above in an emitting layer as an emitter, preferably a red, green, or blue emitter. Very preferred is an organic electroluminescent device comprising a structure / compound according to formula (I) or the preferred embodiments outlined above in an emitting layer as a fluorescent blue emitter. In this case, compounds, structures / compounds according to formulae (II-2) to (II-8), (II-17) to (II-23), (III-2) to (III-8), (III-17) to (III-23), (IV-2) to (IV-8), (IV-17) to (IV-23), (V-1), (V-2), (V-5), and / or (V-6) are particularly preferred.

[0115] When the compound according to the invention is used as an emitter in an emitting layer, a suitable matrix material (also called host material) is preferably used, which is known as such.

[0116] 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.

[0117] 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. B. according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776, azacarbazole derivatives, e.g. B. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, e.g. B. according to WO 2007 / 137725, silanes, e.g. B. according to WO 2005 / 111172, azaboroles or boronic esters, e.g. B. according to WO 2006 / 117052, triazine derivatives, e.g.according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, 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. B. according to WO 2012 / 048781, dibenzofuran derivatives, e.g. B. according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565 or biscarbazoles, e.g. B. according to JP 3139321 B2.

[0118] 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 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.

[0119] In a preferred embodiment, a compound containing a structure / compound according to formula (I) or the preferred embodiments described above, which is 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. This preferably forms a hyperfluorescence system as described in WO 2012 / 133188 and / or a hyperphosphorescence system as described in US 2017271611. This combination represents a preferred composition according to the present invention.

[0120] WO 2015 / 091716 A1 and WO 2016 / 193243 A1 disclose OLEDs containing both a phosphorescent compound and a fluorescent emitter in the emission layer, with the energy being 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.

[0121] For the purposes of this invention, phosphorescence refers to luminescence from an excited state with higher spin multiplicity, i.e., a spin state > 1, in particular from an excited triplet state. For the purposes of this application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum, and copper complexes, are considered phosphorescent compounds.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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 comparatively small singlet-triplet separation ΔE(S 1 - T 1 ) of, for example, less than about 2000 cm -1 is required in the emitter. To open the inherently spin-forbidden transition T 1 → S 1 , another compound can be provided in the matrix next to the emitter. This compound 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.

[0126] Further valuable information on hyperfluorescence systems is provided in WO2012 / 133188 (Idemitsu), WO2015 / 022974 (Kyushu Univ.), WO2015 / 098975 (Idemitsu), WO2020 / 053150 (Merck) and DE202019005189 (Merck), among others.

[0127] Further valuable information on hyperphosphorescence systems is provided, among others, in WO2015 / 091716 A1, WO2016 / 193243 A1 (BASF), WO01 / 08230 A1 (Princeton Univ. (Mark Thompson)), US2005 / 0214575A1 (Fuji), WO2012 / 079673 (Merck), WO2020 / 053314 (Merck) and WO2020 / 053315 (Merck).

[0128] 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 as a hole-transport or hole-injection material directly adjacent to the emitting layer, as described, for example, in WO 2009 / 030981.

[0129] Furthermore, an organic electroluminescent device is preferred, comprising a structure / compound according to formula (I) or the preferred embodiments outlined above in an electron-conducting layer as electron-transport material. In particular, compounds having an anthracene group, preferably a group according to formulas (Ar-76) to (Ar-78), preferably (Ar-78), and / or structures / compounds according to formulas (II-9), (II-10), (II-24), (II-25), (III-9), (III-10), (III-24), (III-25), (IV-9), (IV-10), (IV-24) and / or (IV-25) are preferred.

[0130] 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 structure / compound according to formula (I) or the preferred embodiments described above.

[0131] Also preferred is an organic electroluminescent device characterized in that one or more layers are coated using a sublimation process. The materials are vapor-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.

[0132] 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 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 patterned.

[0133] 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.

[0134] 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.

[0135] Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are deposited by vapor deposition.

[0136] These processes are generally known to the person skilled in the art and can be applied by him without inventive step to organic electroluminescent devices containing the compounds according to the invention.

[0137] The compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished from the prior art, in particular by an improved lifetime. The other electronic properties of the electroluminescent devices, such as efficiency or operating voltage, remain at least as good. In a further variant, the compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished from the prior art, in particular by an improved efficiency and / or operating voltage and a longer lifetime.

[0138] 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: 1. Electronic devices, in particular organic electroluminescent devices comprising structures / compounds according to formula (I) or the preferred embodiments set out 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, as 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 region of the color spectrum are provided. 2. Electronic devices, in particular organic electroluminescent devices comprising structures / compounds according to formula (I) or the preferred embodiments set out above and below, in particular as emitters, as hole-conductor material, and / or as electron-transport material, have a very good lifetime.In particular, these compounds bring about a low roll-off, i.e. a slight drop in the power efficiency of the device at high luminance levels. 3. Electronic devices, in particular organic electroluminescent devices comprising structures / compounds according to formula (I) or the preferred embodiments set out above and below as emitters and / or as electron transport material, have excellent efficiency. In this case, structures / compounds according to the invention according to formula (I) or the preferred embodiments set out above and below result in a low operating voltage when used in electronic devices. 4. The structures / compounds according to the invention according to formula (I) or the preferred embodiments set out above and below display very high stability and lifetime. 5. Structures / compounds according to formula (I) orThe preferred embodiments described above and below prevent the formation of optical loss channels in electronic devices, particularly 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. Exciton energy is typically transferred from a matrix or host in the emission layer to the emitter either via so-called Dexter or Förster transfer. 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 data (e.g., efficiency, voltage, and lifetime).It has been shown that energy transfer from a host or a matrix to the compounds of the invention preferably occurs via Förster transfer. 6. Structures / compounds according to formula (I) or the preferred embodiments described above and below exhibit excellent glass film formation. 7. Structures / compounds according to formula (I) or the preferred embodiments described above and below form very good films from solutions and exhibit excellent solubility.

[0139] These advantages mentioned above are not accompanied by an excessive deterioration of the other electronic properties.

[0140] 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.

[0141] 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).

[0142] 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.

[0143] The teaching of technical action disclosed in the present invention can be abstracted and combined with other examples.

[0144] 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. Examples:

[0145] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The metal complexes are also handled in the absence of light or under yellow light. The solvents and reagents can be obtained from Sigma-ALDRICH or ABCR, for example. The respective information in square brackets or the numbers given for individual compounds refer to the CAS numbers of the known compounds. For compounds that can exhibit multiple enantiomeric, diastereomeric, or tautomeric forms, one form is shown as a representative example. Literature-known Synthone LS:

[0146] LS1 LS2 LS3 Synthesis of synthons S: Literature-known starting materials: 1) 1,2-Dihydroindazol-3-one:

[0147] 2) Acid chlorides:

[0148] Example S1:

[0149]

[0150] Performed according to Z. Wang et al., Chin. J. Chem., 29, 2769, 2011. A mixture of 21.3 g (100 mmol) of 7-bromo-1,2-dihydro-3H-indazol-3-one [887578-57-6], 39.1 g (130 mmol) of 2-chloro-6-iodobenzoyl chloride [1261850-84-3], 97.8 g (300 mmol) of anhydrous cesium carbonate, 3.6 g (20 mmol) of 1,10-phenanthroline, 1.9 g (10 mmol) of copper iodide, 200 g of glass beads (3 mm diameter) and 800 ml of toluene is stirred for 16 h at 100 °C (TLC monitoring for complete conversion of the 7-bromo-1,2-dihydro-3H-indazol-3-one). The mixture is allowed to cool to 80 °C, filtered through a bed of Celite pre-slurried with hot toluene, and the filtrate is concentrated to dryness in vacuo. The residue is taken up in 500 ml of dichloromethane (DCM), applied to approximately 400 g of silica gel, packed onto a silica gel column (800 g) pre-slurried with DCM, and the anti-dibenzobimane regioisomer is eluted with DCM.The desired syn-dibenzobimane regioisomer was then eluted with DCM:methyl tert-butyl ether (MTBE) 8:2 and recrystallized once from acetonitrile. Yield: 9.5 g (27 mmol), 27%. Purity: 97% according to 1< H NMR.

[0151] The following connections can be represented analogously: e.g. reactants product yield S2 885521-92-6 30 % 1261850-84-3 S3 7364-27-4 30 % 1261850-84-3 S4 864845-15-8 28 % 1261850-84-3 S5 887578-57-6 32 % 171256-81-8 S6 885521-92-6 35 % 171256-81-8 S7 7364-27-4 33 % 171256-81-8 S8 864845-15-8 32 % 171256-81-8 S9 887578-57-6 29 % 476619-76-8 S10 885521-92-6 38 % 476619-76-8 S11 7364-27-4 35 % 476619-76-8 S12 864845-15-8 33 % 476619-76-8 S13 887578-57-6 20 % 1017540-70-3 S14 885521-92-6 26 % 1017540-70-3 S15 7364-27-4 29 % 1017540-70-3 S16 864845-15-8 27 % 1017540-70-3 S17 1500638-10-7 30 % 476619-76-8 S18 885518-58-1 34 % 171256-81-8 S19 885518-58-1 31 % 476619-76-8 S20 108961-61-1 27 % 171256-81-8 S21 108961-61-1 26 % 476619-76-8 S22 887568-17-4 28 % 171256-81-8 S23 887568-17-4 23 % 476619-76-8 S24 82722-04-1 30 % 1261850-84-3 S25 51033-99-9 35 % 171256-81-8 S26 82722-04-1 32 % 476619-76-8 S27 33149-32-5 31 % 476619-76-8 S28 2379460-30-5 32 % 7364-27-4 S29 30726-57-9 26 % 864845-15-8 S30 2581709-21-7 29 % 1500638-10-7 S31 887578-57-6 23 % 28384-45-4 S32 864845-15-8 17 % 173068-99-0 50 mmol S33 885518-58-1 33 % 2254443-37-1 S34 2488802-49-7 32 % 885521-92-6 S35 609-67-6 21 % 1278518-53-8 S36 2055586-96-2 50 mmol 16 % 609-67-6 S37 609-67-6 29 % 1946843-47-5 S38 2055586-97-3 50 mmol 16 % 609-67-6 S39 887578-57-6 28 % 609-67-6 S40 885521-92-6 36 % 609-67-6 S41 7364-27-4 35 % 609-67-6 S42 864845-15-8 31 % 609-67-6 S43 108961-61-1 17 % 1210022-59-5 Example S50:

[0152]

[0153] A well-stirred solution of 23.6 g (100 mmol) of syn-dibenzobimane [125213-40-3] LS1 in 500 mL of DCM is added portionwise at room temperature under exclusion of light with 37.4 g (210 mmol) of N-bromosuccinimide, and then stirred for 12 h. The reaction mixture is washed three times with 300 mL of water each time, once with 300 mL of saturated sodium chloride solution, and dried over sodium sulfate. The drying agent is removed by filtration, 100 mL of methanol is added, and the filtrate is concentrated to approximately 80 mL in a rotary evaporator. The crystallized product is filtered off with suction and washed twice with a small amount of methanol. Yield: 26.7 g (68 mmol), 68%. Purity: 97% according to 1< H NMR.

[0154] The following connections can be represented analogously: e.g. reactants product yield S51 LS2 63 % S52 LS3 Addition of 1 TR HBr in glacial acetic acid (47 wt.%) 37 % S53 S30 110 mmol NBS 54 % Example Int-D1: a) Int-B1

[0155] 26.0 g (33.7 mmol) of Int-A1 [2171483-83-1] are dissolved in 600 ml of dichloromethane. A drop of HBr (33%, aqueous) is added under exclusion of light, followed by 7.2 g (44.0 mmol) of N-bromosuccinimide in portions, and the mixture is stirred at room temperature for 48 h. After 48 h, 200 ml of saturated aqueous sodium bisulfite solution is added, and the mixture is stirred for 1 h. The two phases are then separated, the organic phase is washed three times with 200 ml of water each time, and then concentrated under reduced pressure. The residue is treated with 300 ml of n-heptane, and the mixture is heated under reflux for 1 h. After the mixture has cooled, the colorless solid is filtered off, washed twice with 50 ml of n-heptane each time, and dried in vacuo. Yield: 25.3 g (32 mmol), 97%. Purity: approximately 98% by HPLC. b) Int-C1:

[0156] 28.0 g (35.5 mmol) of Int-B1, 33.6 g (35.5 mmol) of [2171483-74-0], and 9.8 g (71 mmol) of potassium carbonate were treated with 1100 ml of THF and 550 ml of water. 373 mg (1.4 mmol) of triphenylphosphine and 325 mg (0.4 mmol) of tri(dibenzylideneacetone)dipalladium were then added, and the mixture was heated under reflux for 16 h. The cooled reaction mixture was treated with 500 ml of water and 500 ml of toluene, and the phases were separated. The aqueous phase was extracted twice with 200 ml of toluene each time, and the combined organic phases were washed once with 500 ml of water. The organic phase was filtered through aluminum oxide and then evaporated to dryness. The product was purified by repeated crystallization from toluene / n-heptane (1:10) and obtained as a solid. Yield: 41.0 g (28.8 mmol), 81%. Purity: approximately 98% by HPLC. c) Int-D1:

[0157] 25.3 g (18.7 mmol) of Int-C1, 8.6 g (33.7 mmol) of bis(pinacolato)diborane, 5.5 g (56 mmol) of potassium acetate, and 830 mg (1.1 mmol) of trans-dichlorobis(tricyclohexylphosphine)palladium(II) are treated with 750 ml of dioxane and heated under reflux for 48 h. The reaction mixture is then treated with 1000 ml of toluene and 1000 ml of water, and the phases are separated. The aqueous phase is extracted twice with 200 ml of toluene each time. The combined organic phases are washed twice with 500 ml of water each time, then filtered through aluminum oxide and evaporated to dryness. The residue is triturated with hot ethanol. Yield: 16.0 g (11.1 mmol), 60%. Purity: approx. 99% by HPLC. Preparation of the compounds V according to the invention: Example V1

[0158]

[0159] A mixture of 27.1 g (100 mmol) of S39, 39.6 g (110 mmol) of 9,9'-spiro-bi-fluorene-2-boronic acid [236389-21-2], 21.2 g (100 mmol) of tripotassium phosphate, 1.64 g (4 mmol) of S-Phos, 499 mg (2 mmol) of palladium(II) acetate, 300 ml of toluene, 100 ml of dioxane, and 300 ml of water was stirred at 70 °C for 12 h (alternatively, AmPhosPdCl 2 [887919-35-9] can be used). After cooling, the organic phase was separated and washed twice with 300 ml of water each time and once with 300 ml of saturated sodium chloride solution. The organic phase was concentrated. The phase is evaporated to dryness, the residue is taken up in dichloromethane (DCM), filtered through a silica gel bed pre-slurried with DCM, and the filtrate is concentrated in a rotary evaporator, continuously replacing the evaporated DCM with methanol. The crystallized product is filtered off with suction, washed twice with 50 ml of methanol, and dried in vacuo.Further purification is carried out by hot extraction crystallization (solvent mixtures of DCM / acetonitrile 1:3 to 3:1) and fractional sublimation. Yield: 31.5 g (57 mmol), 57%. Purity: approximately 99.9% according to HPLC.

[0160] The following connections can be represented analogously: e.g. reactants product yield V2 S40 67 % 2363139-27-7 V3 S41 70 % 2201147-30-8 V4 S42 51 % 881911-75-7 V5 S40 56 % 2088929-31-9 V6 S41 65 % 2418007-78-8 V7 S39 43 % 1257321-47-3 50 mmol V8 S42 58 % 2249944-12-3 50 mmol V9 S39 61 % 1326240-20-3 50 mmol V10 S41 44 % 1216638-44-6 30 mmol V11 S32 40 % 2368221-45-6 220 mmol V12 S39 43 % 796071-96-0 V13 S40 69 % 2345673-16-5 V14 S41 65 % 2247722-85-4 V15 S42 56 % 2411326-31-1 V16 S42 47 % 2375083-92-2 50 mmol V17 S41 61 % 2375083-93-3 50 mmol V18 S42 53 % 1644606-71-2 V19 S40 67 % 1822320-55-7 V20 S33 51 $ 108847-20-7 210 mmol V21 S41 70 % 1822311-37-4 V22 S39 44 % 1379585-25-7 V23 S41 69 % 2241229-08-1 V24 S41 67 % 1547397-15-8 V25 S42 55 % 2128290-87-7 V26 S25 67 % 2241229-08-1 V27 S28 66 % 1369587-64-3 V28 S30 53 % 1637323-05-7 V29 S34 72 % 1398394-64-3 V30 S42 56 % 1802233-05-1 V31 S40 68 % 2319558-93-3 V32 S41 64 % 1813537-09-5 V33 S39 47 % 1801325-80-3 V34 S42 54 % 1612243-82-9 V35 S41 69 % 2138490-96-5 V36 S42 56 % 2305626-41-7 V37 S42 55 % 1313018-07-3 V38 S40 71 % 2268674-03-7 V39 S34 71 % 1642121-58-1 V40 S24 56 % 1637377-61-7 V41 S40 73 % 1642121-58-1 V42 S42 57 % 1133318-06-5 V43 S40 70 % 1609021-60-4 V44 S42 52 % 1188095-78-4 V45 S41 67 % 2241542-34-5 V46 S42 55 % 1304130-07-1 V47 S7 58 % 50 mmol 1271726-52-3 V48 S6 50 % 50 mmol 1835251-21-2 V49 S10 48 % 50 mmol 2305718-67-4 V50 S12 53 % 50 mmol 2458817-52-0 V51 S18 46 % 30 mmol 1246022-50-3 V52 S23 39 % 30 mmol 864377-33-3 V53 S50 70% 50 mmol 98-80-6 V54 S51 67 % 50 mmol 98-80-6 V55 S52 74 % 50 mmol 98-80-6 V56 S50 46 % 50 mmol 154549-38-9 V57 S51 43 % 50 mmol 154549-38-9 V58 S50 67 % 50 mmol 1912467-76-5 V59 S51 59 % 50 mmol 1562418-16-9 V60 S27 60 % 169126-63-0 V61 S28 65 % 1801624-63-4 V62 S50 57 % 50 mmol 5122-94-1 V63 S50 53 % 50 mmol 1057654-43-9 V64 S50 51 % 50 mmol 4688-76-0 V65 S50 62 % 50 mmol 1205748-34-0 V66 S51 41 % 50 mmol 1602576-91-9 V67 S50 47 % 50 mmol 1004321-87-2 V68 S50 63 % 50 mmol 333432-28-3 V69 S50 60 % 50 mmol 400607-31-0 V70 S24 59 % 50 mmol 1207559-33-8 V71 S25 72 % 50 mmol 1241891-39-3 V72 S43 31 % 25 mmol 1246022-50-3 V73 S50 61 % 50 mmol 2597100-63-3 V74 S51 59 % 50 mmol 1092576-56-1 V75 S53 51 % 50 mmol 1224976-40-2 V76 S50 66 % 50 mmol 1421789-05-0 V77 S34 70% 2540904-37-6 V78 S50 50 % 50 mmol 2364629-32-1 V79 S50 49 % 50 mmol 1630795-54-8 V80 S50 50 % 50 mmol 2549197-79-5 V81 S43 21 % 25 mmol 612086-25-6 V82 S43 23 % 25 mmol 2605856-02-6 V83 S50 60 % 50 mmol 2402769-87-1 V84 S50 51 % 50 mmol 2049003-24-7 V85 S29 59 % 2377545-64-5 V86 S30 62 % 2035080-71-6 V87 S28 60 % 2606072-21-1 V88 S50 54 % 50 mmol 1651221-10-1 V89 S29 59 % 654664-63-8 V90 S28 68 % 1430392-46-3 V91 S50 51 % 50 mmol 1370555-65-9 V92 S28 62 % 2361216-20-6 V93 S30 67 % 854952-58-2 V94 S24 53 % 1001911-63-2 V95 S31 43 % 2193827-55-1 V96 S50 61 % 50 mmol 2144406-20-0 V97 S50 50 % 50 mmol 2595368-09-3 V98 S50 66 % 50 mmol 85199-06-0 V99 S50 61 % 50 mmol 1246022-49-0 Example V200: Step 1: Bromine -Suzuki clutch

[0161]

[0162] A mixture of 35.0 g (100 mmol) of S1, 1 g (110 mmol) of 1-dibenzofuranylboronic acid [162607-19-4], 10.6 g (100 mmol) of sodium carbonate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 400 ml of toluene, 200 ml of dioxane, and 400 ml of water was heated under reflux for 24 h. After cooling, the organic phase was separated and washed twice with 300 ml of water each time and once with 300 ml of saturated sodium chloride solution. The organic phase was concentrated. The phase is evaporated to dryness, the residue is taken up in dichloromethane (DCM), filtered through a silica gel bed pre-slurried with DCM, and the filtrate is concentrated in a rotary evaporator, continuously replacing the evaporated DCM with methanol. The crystallized product is filtered off with suction, washed twice with 50 ml of methanol, and dried in vacuo. The crude product is recrystallized from acetonitrile. Yield: 30.3 g (69 mmol), 69%. Purity: approximately 98% according to 1< H NMR. Step 2: Chlorine Suzuki clutch

[0163]

[0164] Procedure analogous to Example V1, using 3-(9H-carbazol-9-yl)phenylboronic acid [864377-33-3]. Yield: 30.3 g (47 mmol), 47%. Purity: approximately 99.9% according to HPLC.

[0165] The following connections can be represented analogously: e.g. reactants product yield V201 S2 35 % 2128290-87-7 5122-95-2 V202 S3 31 % 1028648-22-7 654664-63-8 V203 S4 30 % 1174032-85-9 4688-76-0 V204 S5 28 % 126747-14-6 1174032-92-8 V205 S6 46 % 1214723-25-7 108847-24-1 V206 S7 45 % 1401068-23-2 215527-70-1 V207 S8 41 % 2395777-93-0 68572-87-2 V208 S9 36 % 1978347-56-6 1801624-63-4 V209 S10 45% 2454395-23-2 1822320-55-7 V210 S11 44 % 123324-71-0 2222276-71-1 V211 S12 41 % 2241870-66-4 1900681-96-0 V212 S13 22 % 2230311-62-1 2271286-98-5 V213 S14 37 % 2217618-64-7 1205748-34-0 V214 S15 35 % 1609088-39-2 150255-96-2 V215 S16 31 % 2093171-71-0 1430392-46-3 V216 S17 43 % 1224976-40-2 168267-41-2 V217 S18 35 % 1801624-61-2 200 mmol 1822320-55-7 V218 S19 33 % 4688-76-0 200 mmol 1233200-59-3 V219 S20 29 % 177171-16-3 200 mmol 1612243-82-9 V220 S21 37 % 98-80-6 200 mmol 2111193-19-0 V221 S22 35 % 1251825-65-6 98-80-6 210 mmol V222 S23 31 % 98-80-6 1251825-65-6 220 mmol V223 S7 48 % 154549-38-9 2402769-87-1 V224 S7 47 % 2361216-20-6 1004321-87-2 Example V300:

[0166]

[0167] A mixture of 13.6 g (50 mmol) S4, 31.2 g (110 mmol) 5,7-dihydro-7,7-dimethylindeno[2,1-b]carbazole [1257220-47-5], 14.4 g (150 mmol) sodium tert-butoxide, 2.65 g (4 mmol) rac-BINAP (alternatively S-Phos, X-Phos, tri-tert-butylphosphine can be used), 674 mg (3 mmol) palladium(II) acetate, 100 g glass beads (3 mm diameter) and 300 ml toluene is stirred at 110 °C for 24 h. The filtrate is filtered with suction while still hot through a bed of silica gel pre-slurried with hot toluene. The filtrate is concentrated to dryness in vacuo, and the solid is stirred with 300 ml of hot methanol. The solid is filtered with suction while still warm, washed twice with 50 ml of methanol, and dried in vacuo. Further purification is carried out by hot extraction crystallization (solvent mixtures DCM / acetonitrile 1:3 to 3:1) and fractional sublimation. Yield: 20.1 g (25 mol), 50%. Purity: approximately 99.9% according to HPLC.

[0168] The following connections can be represented analogously: e.g. reactants product yield V301 S2 46 % 109606-75-9 V302 S3 44 % 103012-26-6 V303 S10 40 % 1819346-21-8 V304 S35 57 % 100 mmol 1161009-88-6 110 mmol V305 S35 59 % 100 mmol 3842-55-5 120 mmol 110 mmol NaO-t-Bu V306 S35 56 % 100 mmol 2401923-63-3 130 mmol 110 mmol NaO-t-Bu dimethylacetamide instead of toluene V307 S35 54 % 100 mmol 2226747-65-3 130 mmol 110 mmol NaO-t-Bu dimethylacetamide instead of toluene V308 S36 60 % 100 mmol 1852465-53-2 120 mmol 110 mmol NaO-t-Bu dimethylacetamide instead of toluene V309 S37 34 % 50 mmol 2541485-90-7 110 mmol V310 S38 47 % 50 mmol 89827-45-2 110 mmol Example L1:

[0169] 8.27 g (21 mmol) of S50, 32.60 g (46 mmol) of OA1, and 4.5 g (42.4 mmol) of sodium carbonate were suspended in 600 ml of a mixture of toluene / ethanol / water (2:1:1) and degassed with argon. After adding 613 mg (0.53 mmol) of tetrakis(triphenylphosphine)palladium(0), the mixture was stirred at 110°C. After six hours, the reaction mixture was allowed to cool to room temperature, and a further 200 ml of toluene was added. The organic phase was separated, washed twice with 300 ml of water and once with 300 ml of saturated sodium chloride solution, dried over sodium sulfate, and filtered through a Celite bed pre-slurried with toluene. The filtrate is evaporated to dryness, the residue is dissolved in 300 ml of dichloromethane, mixed with 200 ml of methanol, and concentrated to approximately 300 ml using a rotary evaporator. The precipitated solid is filtered off with suction and washed three times with 50 ml of methanol each time.The resulting solid was purified by column chromatography and repeated recrystallization from toluene / n-heptane to an HPLC purity of >99.9%, and finally annealed at 10 -6 < mbar and 250 °C. Yield: 6.85 g (4.9 mmol), 24%.

[0170] The following compounds can be synthesized in an analogous manner: L Educt 1 Educt 2 product L2 S50 CAS 2171483-75-1 L3 S50 G10 from WO2018 / 0 07421 L4 S50 Int-D1 L5 S51 Int-D1 L6 S52 Int-D1 Measurement of photoluminescence spectra (PL spectra):

[0171] Figure 1 shows PL spectra of the compounds V53, V98 and V99 according to the invention, measured with a PL spectrometer from Hitachi, F-4500 PL, in approx. 10 -5< molar, degassed toluene solution at room temperature (approx. 25 °C).

[0172] The PL spectra exhibit very narrow emission bands with low FWHM values ​​(< 0.18 eV) and lead to particularly color-pure emission. Manufacturing of OLED components 1) Vacuum-processed devices:

[0173] The production of OLEDs according to the invention as well as OLEDs according to the prior art is carried out according to a general process according to WO 2004 / 058911, which is adapted to the conditions described here (layer thickness variation, materials used).

[0174] 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-ethylenedioxythiophene)poly(styrenesulfonate), purchased as CLEVIOS™< P VP AI 4083 from Heraeus Precious Metals GmbH, Germany, spin-coated from aqueous solution) for improved processing. They are then baked at 180 °C for 10 minutes. These coated glass plates form the substrates onto which the OLEDs are applied. 1a) Blue and Green Fluorescence OLED Devices - BF and GF:

[0175] All materials are thermally vapor-deposited in a vacuum chamber. The emission layer (EML) always consists of at least one matrix material (host material) SMB (see Table 1) and an emitting dopant (emitter) V, which is admixed to the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as SMB:V (97:3%) means that the SMB material is present in the layer in a volume fraction of 97% and the dopant V in a volume fraction of 3%. Analogously, the compounds V44, V45, and V46 according to the invention can be used as hosts for green fluorescent components. Analogously, the electron-transport layer can also consist of a mixture of two materials (see Table 1). The materials used to produce the OLEDs are shown in Table 7.

[0176] The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, current efficiency (measured in cd / A), power efficiency (measured in λ / W), and external quantum efficiency (EQE, measured in percent) are determined as a function of luminance, calculated from current-voltage-luminance curves (IUL curves) assuming a Lambertian radiation pattern, as well as the lifetime. The electroluminescence spectra are determined at a luminance of <1000 cd / m², and the CIE 1931 x and y color coordinates and the full width half maximum (FWHM) are determined from these values. The OLEDs have the following layer structure: Substrat

[0177] Hole injection layer 1 (HIL1) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm. Hole transport layer 1 (HTL1) made of HTM1, 140 nm. Hole transport layer 2 (HTL2) made of HTM2, 10 nm. Emission layer (EML), see Table 1. Electron transport layer (ETL2), see Table 1. Electron transport layer (ETL1), see Table 1. Electron injection layer (EIL) made of ETM2, 1 nm. Cathode made of aluminum, 100 nm. Table 1: Structure of Blue BF and Green GF Fluorescence OLED devices e.g. EML ETL2 ETL1 BF1 SMB1:V64 (97:3%) --- ETM1:ETM2 (50:50%) 20 nm 30 nm BF2 SMB2:V65 (97:3%) --- ETM1:ETM2 (50:50%) 20 nm 30 nm BF3 SMB3:V67 (97:3%) ETM1 5 nm ETM1:ETM2 (50:50%) 20 nm 30 nm BF4 SMB1:V83 (97:3%) V5 5 nm V5:ETM2 (50:50%) 20 nm 30 nm BF5 SMB1:V53 (97:3%) --- ETM1:ETM2 (50:50%) 20 nm 30 nm BF6 SMB1:V98 (97:3%) --- ETM1:ETM2 (50:50%) 20 nm 30 nm BF7 SMB1:V99 (97:3%) --- ETM1:ETM2 (50:50%) 20 nm 30 nm GF1 V44:V54 (95:5%) --- ETM1:ETM2 (50:50%) 20 nm 30 nm GF2 V45:V57 (95:5%) V4 5 nm V4:ETM2 (50:50%) 20 nm 30 nm Table 2: Results of blue fluorescent OLED devices e.g. EQE (%) 1000 cd / m 2 Voltage (V) 1000 cd / m 2< CIE (x / y) BF1 6.8 3.5 0.16 / 0.06 BF2 7.5 3.4 0.16 / 0.10 BF3 6.7 3.3 0.15 / 0.08 BF4 7.2 3.1 0.15 / 0.09 BF5 6.3 3.5 0.15 / 0.11 BF6 7.4 3.6 0.15 / 0.08 BF7 7.0 3.5 0.16 / 0.13 GF1 28.0 3.0 0.26 / 0.64 GF2 25.6 2.8 0.24 / 0.59 1b) Phosphorescent OLED components - BP, GP, RP:

[0178] The compounds according to the invention can be used, among other things, as electron-conducting host material eTMM in the emission layer EML of a phosphorescent OLED and as electron transport material in the HBL and ETL.

[0179] For this purpose, all materials are thermally evaporated in a vacuum chamber. The emission layer always consists of at least one or more matrix materials M (host materials) and a phosphorescent dopant Ir, which is added to the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as M1:M2:Ir (55%:35%:10%) means that the material M1 is present in the layer at a volume fraction of 55%, M2 at a volume fraction of 35%, and Ir at a volume fraction of 10%. Analogously, the electron-transport layer can also consist of a mixture of two materials. The exact structure of the OLEDs can be found in Table 3. The materials used to manufacture the OLEDs are shown in Table 7.

[0180] The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, current efficiency (measured in cd / A), power efficiency (measured in λm / W), and external quantum efficiency (EQE, measured in percent) are determined as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming a Lambertian radiation pattern, as well as the lifetime. The electroluminescence spectra are determined at a luminance of <1000 cd / m², and the CIE 1931 x and y color coordinates are calculated from them. The OLEDs have the following layer structure: Substrat

[0181] Hole injection layer 1 (HIL1) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm. Hole transport layer 1 (HTL1) made of HTM1, 170 nm for blue, 40 nm for green / yellow, and 90 nm for red components. Hole transport layer 2 (HTL2), see Table 3. Emission layer (EML), see Table 3. Electron transport layer (ETL2), see Table 3. Electron transport layer (ETL1), see Table 3. Electron injection layer (EIL) made of ETM2, 1 nm. Cathode made of aluminum, 100 nm. Table 3: Structure of phosphorescent OLED components e.g. HTL2 thickness EML thickness ETL2 thickness ETL1 thickness Blue OLEDs BP1 HTM3 10 nm M3:M4:IrB1 (30%:60%:10%) ETM3 10 nm V1:ETM2 (70%:30%) 30 nm 30 nm BP2 HTM3 10 nm M3:M4:IrB1 (30%:60%:10%) ETM3 10 nm V6:ETM2 (60%:40%) 30 nm 30 nm Green and Yellow OLEDs GP1 HTM2 20 nm V9:M1:IrG1 (50%:40%:10%) ETM1 5 nm ETM1:ETM2 (50%:50%) 40 nm 30 nm GP2 HTM2 20 nm V12:M2:IrG2 (50%:35%:15%) ETM1 5 nm ETM1:ETM2 (50%:50%) 40 nm 30 nm GP3 HTM2 20 nm V24:M1:IrG3 (45%:45%:10%) ETM1 5 nm ETM1:ETM2 (50%:50%) 40 nm 30 nm GP4 HTM2 20 nm V32:M2:IrG3 (45%:45%:10%) V3 5 nm ETM1:ETM2 (50%:50%) 40 nm 30 nm GP5 HTM2 20 nm V35:M1:IrG3 (45%:45%:10%) V5 5 nm V5:ETM2 (60%:40%) 40 nm 30 nm Red OLEDs RP1 HTM2 10 nm V94:IrR1 (97%:3%) ETM1 10 nm ETM1:ETM2 (50%:50%) 35 nm 30 nm Table 4: Results of phosphorescent OLED devices e.g. EQE (%) 1000 cd / m 2 Voltage (V) 1000 cd / m 2< CIE x / y 1000 cd / m 2 Blue OLEDs BP1 20.6 3.5 0.16 / 0.36 BP2 22.3 3.4 0.16 / 0.36 Green and Yellow OLEDs GP1 23.2 3.3 0.34 / 0.62 GP2 21.9 3.2 0.35 / 0.65 GP3 27.7 3.2 0.49 / 0.51 GP4 28.3 3.1 0.49 / 0.51 GP5 28.5 3.0 0.50 / 0.50 Red OLEDs RP1 18.6 2.7 0.70 / 0.30 2) Solution-processed components: 2a) Solution-processed phosphorescent OLED devices - Sol-GP and Sol-RP:

[0182] The iridium complexes according to the invention can also be processed from solution, resulting in OLEDs that are significantly simpler in terms of process technology than vacuum-processed OLEDs, yet still offer good properties. The production of such components is based on the production of polymer light-emitting diodes (PLEDs), which has been described many times in the literature (e.g., in WO 2004 / 037887). The structure consists of: The structure used is therefore as follows: Substrate, ITO (50 nm), hole injection layer (60 nm), interlayer (20 nm), made of HTL-S1 emission layer (60 nm), see Table 5, hole blocking layer (10 nm), made of ETM-1, electron transport layer (40 nm), made of ETM-1 / ETM-2 (50:50), cathode (Al) (100 nm)

[0183] For this purpose, substrates from Technoprint (sodium tin oxide, a transparent, conductive anode) are used, onto which the ITO structure (indium tin oxide, a transparent, conductive anode) is applied. The substrates are cleaned in a cleanroom with DI water and a detergent (Deconex 15 PF) and then activated by a UV / ozone plasma treatment. A 20 nm hole-injection layer (PEDOT:PSS from Clevios™< ) is then applied by spin coating, also in a cleanroom. The required spin rate depends on the degree of dilution and the specific spin coater geometry. To remove residual water from the layer, the substrates are baked for 10 minutes at 180 °C in air on a hot plate. The interlayer used serves to transport the holes; in this case, HTL-S1 from Merck (WO2013156130) is used. The solid content is approximately 5 g / l to achieve a layer thickness of 20 nm by spin coating.The interlayer is baked on a hot plate in an inert gas atmosphere, in this case argon, for 30 minutes at 220 °C. Alternatively, the interlayer can be replaced by one or more layers, which only have to meet the condition of not being removed again during the subsequent processing step of EML deposition from solution. To create the emission layer, the triplet emitters Ir are dissolved together with the matrix materials in toluene or chlorobenzene. The typical solids content of such solutions is between 16 and 25 g / L if, as in this case, the layer thickness of 60 nm typical for a device is to be achieved by spin coating. The solution-processed devices contain an emission layer of Ma:Mb:Ir (w%:x%:z%), see Table 5. The emission layer is spin-coated in an inert gas atmosphere, in this case argon, and baked for 10 minutes at 160 °C.The hole-blocking layer and the electron-transport layer are then evaporated on top (evaporation systems from Lesker et al., typical deposition pressure 5 x 10 -6 < mbar). Finally, a cathode made of aluminum (high-purity metal from Aldrich) is evaporated. To protect the device from air and humidity, the device is finally encapsulated and then characterized. The OLED examples mentioned are not yet optimized. Table 5 summarizes the obtained data. Table 5: Results with materials processed from solution e.g. Emission layer EQE (%) 1000 cd / m 2< Tension (V) 1000 cd / m2< CIE x / y 1000 cd / m 2 Sol-GP1 V22:M5:IrG-Sol1 (20%:58%:22%) 22.0 4.4 0.34 / 0.62 Sol-GP2 V200:M5:IrG-Sol1 (20%:58%:22%) 22.7 4.3 0.34 / 0.63 Sol-GP3 V213:M5:IrG-Sol1 (30%:50%:20%) 22.5 4.3 0.34 / 0.62 Sol-RP1 V307:M5:IrR1 (25%:57%:18%) 17.7 3.8 0.70 / 0.30 2b) Solution-processed fluorescent OLED devices - Sol-BF:

[0184] The fluorescence emitters L according to the invention can also be processed from solution and lead to good properties. The production of such components is analogous to the solution-processed phosphorescence OLED components – GP, RP, with the following adaptations being made during construction: Substrate, ITO (50 nm), hole injection layer (20 nm), interlayer (20 nm), emission layer (40 nm) made of HTL-S1, hole blocking layer (10 nm) made of fluorescence emitter L and matrix MS, electron transport layer (40 nm) made of ETM-1, cathode (Al) (100 nm) made of ETM-1 / ETM-2 (50:50).

[0185] To produce the emission layer, the fluorescence emitters L (5 wt%) according to the invention are dissolved together with the matrix material MS (95 wt%) in toluene or chlorobenzene. The typical solids content of such solutions is 14 g / L if, as in this case, the layer thickness of 40 nm typical for a device is to be achieved by spin coating. The emission layer is spin-coated in an inert gas atmosphere, in this case argon, and annealed for 10 min at 160 °C. Table 6 summarizes the data obtained. Table 6: Results with materials processed from solution e.g. Emission layer EQE (%) 1000 cd / m 2< Tension (V) 1000 cd / m2< CIE x / y Host Emitter 1000 cd / m 2 Sol-BF1 MS L1 3.9 4.3 0.14 / 0.14 Sol-BF2 MS L2 4.3 4.3 0.14 / 0.14 Sol-BF3 MS L3 4.5 4.4 0.14 / 0.13 Sol-BF4 MS L4 5.9 4.4 0.14 / 0.13 Table 7: Structural formulas of the materials used HTM1 136463-07-5 HTM2 1450933-44-4 HTM3 1206465-62-4 M1 1643479-47-3 M2 1357150-54-9 M3 = ETM3 1201800-83-0 M4 550378-78-4 M5 1246496-85-4 SMB1 [1087346-88-0] SMB2 [667940-34-3] SMB3 [1627916-48-6] MS [1273319-88-2] ETM1 1233200-52-6 ETM2 25387-93-3 IrB1 1541114-98-0 IrG1 1562420-772 IrG2 2245866-06-0 IrG3 2245945-28-0 IrR1 1562420-79-4 IrG-Sol1 1989601-89-9 HTL-S1 WO2013156130

[0186] The abbreviations shown in Tables 1, 3, 5 and 6 with respect to the materials according to the invention, such as L1, L2, L3, L4, V1, V4, V5, V6, V9, V12, V22, V24, V32, V35, V44, V45, V54, V57, V64, V65, V67, V83, V94, V200, V213 and V307 etc. refer to the compounds detailed in the synthesis examples above.

Claims

1. Compound including at least one structure of the formula (I) where the ring Ara is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more Ar or Ra radicals, the ring Arb is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more Ar or Rb radicals; and where the further symbols and indices used are as follows: Wa, Wb is the same or different at each instance and is O or S; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R radicals; the Ar group here may form a ring system with at least one Ar, R, Ra, Rb group or a further group; R, Ra, Rb is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R1)2, C(=O)N(Ar')2, C(=O)N(R1)2, C(Ar')3, C(R1)3, Si(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 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R1 radicals, where one or more nonadjacent CH2 groups may be 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 which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R1 radicals; or heteroarylthio group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R1 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R1 radicals, or an aralkyl or heteroarylalkyl group which has 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl radical and may be substituted by one or more R1 radicals; at the same time, two R, Ra, Rb radicals together or with a further group may also form a ring system; Ar' is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R1 radicals; at the same time, it is possible for two Ar' radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge 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 instance and is H, D, F, Cl, Br, I, CN, NO2, N(Ar'')2, N(R2)2, 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, 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 R2 radicals, where one or more nonadjacent 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 where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R2 radicals, or a combination of these systems; at the same time, two or more R1 radicals together may form a ring system; at the same time, one or more R1 radicals may form a ring system with a further part of the compound; Ar'' is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more R2 radicals; at the same time, it is possible for two Ar'' radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge 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 the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more substituents R2 together may form a ring system; with exclusion of compounds of the formulae (A), (B) and (C) from protection.

2. Compound according to Claim 1, comprising at least one structure of the formula (II-1) to (II-42): where the symbols Wa and Wb have the definitions given in Claim 1 and the further symbols are as follows: Ya is the same or different at each instance and is N(Ar), N(Ra), P(Ar), P(Ra), P(=O)Ar, P(=O)Ra, P(=S)Ar, P(=S)Ra, B(Ar), B(Ra), Al(Ar), Al(Ra), Ga(Ar), Ga(Ra), C=O, C(Ra)2, Si(Ra)2, Ge(Ra)2, C=NRa, C=NAr, C=C(Ra)2, C=C(Ra)(Ar), O, S, Se, S=O or SO2, preferably N(Ar), N(Ra), B(Ar), B(Ra), P(=O)Ra, P(=O)Ar, C=O, C(Ra)2, C=C(Ra)2, C=C(Ra)(Ar), Si(Ra)2, O, S, Se, S=O or SO2, more preferably N(Ar), C(Ra)2, O or S, where Ra has the definition detailed in Claim 1; Yb is the same or different at each instance and is N(Ar), N(Rb), P(Ar), P(Rb), P(=O)Ar, P(=O)Rb, P(=S)Ar, P(=S)Rb, B(Ar), B(Rb), Al(Ar), Al(Ra), Ga(Ar), Ga(Rb), C=O, C(Rb)2, Si(Rb)2, Ge(Rb)2, C=NRb, C=NAr, C=C(Rb)2, C=C(Rb)(Ar), O, S, Se, S=O or SO2, preferably N(Ar), N(Rb), B(Ar), B(Rb), P(=O)Rb, P(=O)Ar, C=O, C(Rb)2, C=C(Rb)2, C=C(Rb)(Ar), Si(Rb)2, O, S, Se, S=O or SO2, more preferably N(Ar), C(Rb)2, O or S, where Rb has the definition detailed in Claim 1; Y1, Y2 is the same or different at each instance and is N(Ar), N(R), P(Ar), P(R), P(=O)Ar, P(=O)R, P(=S)Ar, P(=S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C=O, C(R)2, Si(R)2, Ge(R)2, C=NR, C=NAr, C=C(R)2, C=C(R)(Ar), O, S, Se, S=O or SO2, preferably N(Ar), N(R), B(Ar), B(R), P(=O)R, P(=O)Ar, C=O, C(R)2, C=C(R)2, C=C (R) (Ar), Si(R)2, O, S, Se, S=O or SO2, more preferably N(Ar), C(R)2, O or S, where R has the definition detailed in Claim 1; X is the same or different at each instance and is N or CR, with the proviso that not more than two of the X groups in one cycle are N, where R has the definition detailed in Claim 1; Xa is the same or different at each instance and is N or CRa, with the proviso that not more than two of the Xa groups in one cycle are N, where R2 has the definition detailed in Claim 1; Xb is the same or different at each instance and is N or CRb, with the proviso that not more than two of the Xb groups in one cycle are N, where Rb has the definition detailed in Claim 1.

3. Compound according to Claim 1 or 2, including at least one structure of the formulae (III-1) to (III-41): where the symbols Y1, Y2, Ya, Yb, X, Xa and Xb have the definitions given in Claim 2.

4. Compound according to one or more of Claims 1 to 3, including at least one structure of the formulae (IV-1) to (IV-41): where the symbols R, Ra and Rb have the definitions given in Claim 1, the symbols Y1, Y2, Ya and Yb have the definitions given in Claim 2, and the further symbols have the following definition: m is 0, 1, 2, 3 or 4; j is 0, 1 or 2.

5. Compound according to one or more of Claims 1 to 4, including at least one structure of the formulae (V-1) to (V-8): where the symbols Ra and Rb have the definitions given in Claim 1 and the further symbols have the following definition: Rc, Rd is the same or different at each instance and is N(Ar')2, N(R1)2, C(=O)N(Ar')2, C(=O)N(R1)2, C(Ar')3, C(R1)3, Si(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 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R1 radicals, where one or more nonadjacent CH2 groups may be 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 which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R1 radicals; or heteroarylthio group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R1 radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R1 radicals, or an arylalkyl or heteroarylalkyl group which has 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl radical and may be substituted by one or more R1 radicals; at the same time, one Rc radical may form a ring system with an R, Ra, Rb, Rd radical or a further group; at the same time, an Rd radical may form a ring system with an R, Ra, Rb, Rc radical or a further group; m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3.

6. Compound according to one or more of Claims 1 to 5, characterized in that at least one R, Ra, Rb, Rc, Rd radical is a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may be substituted in each case by one or more R1 radicals, where one or more nonadjacent CH2 groups may be 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 which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R1 radicals.

7. Compound according to one or more of Claims 1 to 6, characterized in that at least two R, Ra, Rb, Rc, Rd radicals together with the further groups to which the two R, Ra, Rb, Rc, Rd radicals bind form a fused ring, where the two R, Ra, Rb, Rc, Rd radicals form at least one structure of the formulae (RA-1) to (RA-12): where R1 has the definition detailed above, the dotted bonds represent the sites of attachment via which the two R, Ra, Rb, Rc, Rd radicals bind to the further groups, and the further symbols have the following definition: Y3 is the same or different at each instance and is C(R1)2, (R1)2C-C(R1)2, (R1)C=C(R1), NR1, NAr', O or S; Re is the same or different at each instance and is F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R2 radicals, where one or more nonadjacent 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)(R1), -O-, -S-, SO or SO2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R2 radicals; at the same time, two Re radicals together or one Re radical together with an R1 radical or with a further group may also form a ring system; 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.

8. Compound according to one or more of Claims 1 to 7, characterized in that at least two R, Ra, Rb, Rc, Rd radicals together with the further groups to which the two R, Ra, Rb, Rc, Rd radicals bind form a fused ring, where the two R, Ra, Rb, Rc, Rd radicals form structures of the formula (RB): where R1 has the definition detailed in Claim 1, the dotted bonds represent the sites of attachment via which the two R, Ra, Rb, Rc, Rd radicals bind to the further groups, the index m is 0, 1, 2, 3 or 4 and Y4 is C(R1)2, NR1, NAr', BR1, BAr', O or S.

9. Compound according to one or more of Claims 1 to 8, comprising at least one structure of the formulae (VI-1) to (VI-22), where the compounds have at least one fused ring, where the symbols R, Ra, Rb, Y1 and Y2 have the definitions given in Claim 1 or Claim 2, the symbol o represents the sites of attachment, and the further symbols have the following definition: m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3; j is 0, 1 or 2.

10. Compound according to one or more of Claims 1 to 9, characterized in that at least one substituent R, Ra, Rb is the same or different at each instance and is selected from the group consisting of H, D, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms or an aromatic or heteroaromatic ring system selected from the groups of the following formulae Ar-1 to Ar-78: where R1 has the definitions given above, the dotted bond represents the bond on the corresponding group and in addition: Ar1 is the same or different at each instance and is a bivalent aromatic or heteroaromatic ring system which has 6 to 18 aromatic ring atoms and may be substituted in each case by one or more R1 radicals; A is the same or different at each instance and is C(R1)2, NR1, O or S; p is 0 or 1, where p = 0 means that the Ar1 group is absent and that the corresponding aromatic or heteroaromatic group is bonded directly to the corresponding radical; q is 0 or 1, where q = 0 means that no A group is bonded at this position and R1 radicals are bonded to the corresponding carbon atoms instead.

11. Compound according to at least one of the preceding Claims 5 to 10, characterized in that the substituent Rc, Rd is the same or different at each instance and represents an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted by one or more R1 radicals selected from the groups of the formulae (Ar-1) to (Ar-78) shown in Claim 10.

12. Compound according to at least one of the preceding Claims 1 to 11, characterized in that the compound includes exactly two or exactly three structures of formula (I), (II-1) to (II-42), (III-1) to (III-41), (IV-1) to (IV-41), (V-1) to (V-8) and / or (VI-1) to (VI-22).

13. Oligomer, polymer or dendrimer containing one or more compounds according to any of Claims 1 to 11, wherein, rather than a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

14. Formulation comprising at least one compound according to one or more of Claims 1 to 12 or an oligomer, polymer or dendrimer according to Claim 13 and at least one further compound, where the further compound is preferably selected from one or more solvents.

15. Composition comprising at least one compound of the formula (I) wherein the symbols used have the definitions given in Claim 1, or an oligomer, polymer or dendrimer as claimed in Claim 13 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF, host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

16. Process for preparing a compound according to one or more of Claims 1 to 12, characterized in that a base skeleton having at least one of the Wa groups or a precursor of one of the Wa groups is synthesized, and an aromatic or heteroaromatic radical is introduced by means of a nucleophilic aromatic substitution reaction or a coupling reaction.

17. Use of a compound of formula (I) where the symbols used have the definitions given in Claim 1, or an oligomer, polymer or dendrimer according to Claim 13 in an electronic device.

18. Electronic device comprising at least one compound of formula (I) where the symbols used have the definitions given in Claim 1, or an oligomer, polymer or dendrimer according to Claim 13.