Materials for organic light-emitting devices and organic sensors

Abstract

The present invention relates to OLED materials which are suitable for use in electronic devices, and to electronic devices, in particular photoelectric devices such as organic light-emitting devices or organic sensors containing these materials.

Description

[0001] Materials for organic light-emitting devices and organic sensors

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

[0003] Electronic devices containing organic, organometallic, and / or polymeric semiconductors are becoming increasingly important and are used in many commercial products. Examples include organic-based charge transport materials (e.g., triarylamine-based hole transporters) in copiers, organic or polymeric light-emitting diodes (OLEDs or PLEDs) in display devices, and organic photoreceptors in copiers. Organic solar cells (O-SCs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic switching elements (O-ICs), organic optical amplifiers, and organic laser diodes (O-lasers) are at an advanced stage of development and have the potential to become highly important in the future.

[0004] Heterocyclic compounds are often used as photosensitizers in organic optical detectors. Heterocyclic compounds that can be used in optical detectors are known from CN 110964007 A, EP 3026722 A1, EP 3243822 A1, EP 3473622 A1, EP 3757108 A1, EP 3770163 A1, US 2019 / 0131541 A1, and EP 3848374 A1. In general, there is still room for improvement with these heterocyclic compounds, for example, for use as photosensitizers, particularly with regard to lifetime, but also with regard to the efficiency and operating voltage of the device.

[0005] Electronic devices within the meaning of this invention are understood to be organic electronic devices that contain organic semiconductor materials as functional materials. In particular, the electronic devices represent electroluminescent devices such as OLEDs or photosensitizers.

[0006] The structure of OLEDs, which use organic compounds as functional materials, is known to those skilled in the art. Generally, OLEDs are electronic devices that have one or more layers comprising organic compounds and emit light when a voltage is applied.

[0007] In electronic devices, especially OLEDs, there is still a need to improve performance, particularly lifetime, efficiency and operating voltage.

[0008] Electronic devices typically comprise a cathode, an anode, and at least one functional layer, with OLEDs having at least one emitting layer. In addition to these layers, they 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.

[0009] The hole transport layers and electron transport layers, as well as the matrix materials of the emitting layer, have a major influence on the performance of electronic devices.

[0010] 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 optical detector or OLEDs, in particular as photosensitizers in an organic optical detector, and which lead to good device properties when used in this device, as well as to provide the corresponding electronic device. In particular, it is the object of the present invention to provide compounds which lead to a long service life, good efficiency and low operating voltage. Furthermore, it is an object of the present invention to provide photosensitizers which are suitable for infrared, red, green or blue optical detectors, preferably for green or red optical detectors.

[0011] Surprisingly, it has been found that certain compounds, described in more detail below, solve this problem, are very well suited for use in electronic devices, and lead to organic optical detectors or OLEDs that exhibit very good properties, particularly with regard to lifetime, efficiency, and operating voltage. These compounds, as well as electronic devices, in particular organic optical detectors or OLEDs, containing such compounds, are therefore the subject of the present invention. The type of use depends on the type of substitution.

[0012] The present invention relates to a compound of formula (1),

[0013] Formula (1 ) wherein a group according to one of the formulas (2-1 ) to (2-7) is condensed to the two positions marked with * to form a heteroaromatic five-membered ring,

[0014] Formula (2-1) Formula (2-2) Formula (2-3) Formula (2-4)

[0015] Formula (2-5) Formula (2-6) Formula (2-7) where the symbols used are:

[0016] X is the same or different at each occurrence and stands for CR a or N, where a maximum of 2 non-adjacent X per cycle represents N;

[0017] Y is a single bond, BR b , C(R b )2, Si(R b )2, Common European Court of Human Rights b 2, NR b , R b P(O), O, S, SO, SO2, Se or Te, preferably a single bond, BR b , C(R b )2, SiR b 2, NR b , 0 or S;

[0018] X I stands for N, CR, the same or different at each occurrence C or CZ, provided that not both X 1 stand for N;

[0019] Y 1 is the same or different for each occurrence NR C , O, S, Se or Te;

[0020] Z is an electron acceptor group; Z can be substituted with R c also form a ring system;

[0021] R a , R b is, at each occurrence, the same or different: H, D, OH, F, CI, Br, I, CN, NO2, N(R 1 )2, C(=0)N(R 1 )2, C(R 1 )3, Si(R 1 )3, Ge(R 1 )3, B(R 1 )2, C(=O)R 1 , P(=0)(R 1 )2, P(R 1 )2, S(=O)R 1 , S(=O)2R 1 , OSO2R 1 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 1 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R 1 C=CR 1 , C=C, Si(R 1)2, C=O, C=S, C=Se, C=NR 1 , C(=O)O, C(=O)NR 1 , NR 1 , P(=O)(R 1 ), Se, Te, BR 1 , Ge(R 1 )2, O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 may be substituted, or an arylthio or heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 may be substituted, or a diarylamino, arylheteroarylamino, diheteroarylamino group with 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R 1may be substituted, or an aralkyl 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 can be substituted; two radicals R a , R b and / or R c also form a ring system with each other or with another group;

[0022] R c is, at each occurrence, the same or different: H, D, OH, F, CI, Br, I, CN, NO2, N(R 1 )2, C(=O)N(R 1 )2, C(R 1 )3, Si(R 1 )3, Ge(R 1 )3, B(R 1 )2, C(=O)R 1 , P(=O)(R 1 )2, P(R 1 )2, S(=O)R 1 , S(=O)2R 1 , OSO2R 1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 1 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R 1 C=CR 1 , C=C, Si(R 1 )2, C=O, C=S, C=Se, C=NR 1 , C(=O)O, C(=O)NR 1 , NR 1 , P(=O)(R 1 ), Se, Te, BR 1 , Ge(R 1 )2, O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each substituted by one or more radicals R 1 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1 may be substituted, or an arylthio or heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 may be substituted, or a diarylamino, arylheteroarylamino, diheteroarylamino group with 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R 1 may be substituted, or an aralkyl 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 can be substituted; two radicals R a , R b and / or R c also form a ring system with each other or with another group;

[0023] R 1 is the same or different at each occurrence: H, D, F, CI, Br, I, CN, NO2, N(R 2 )2, C(=O)R 2 , P(=O)(R 2 )2, P(R 2 )2, B(R 2 )2, C(R 2 )3, Si(R 2 )3, Ge(R 2)3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or an alkenyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, wherein one or more non-adjacent CH2 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 2 ), O, S, SO or SO2 and where one or more H atoms can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which can be replaced 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 2may be substituted, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms which may be substituted with one or more radicals R 2 may be substituted, or a combination of these systems; two or more, preferably adjacent, radicals R 1 form a ring system; one or more radicals R 1 form a ring system with another part of the compound;

[0024] R 2is selected, identically or differently at each occurrence, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, CI, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, where two or more, preferably adjacent, substituents R 2 form a ring system with each other;

[0025] Electron acceptor groups are generally known to those skilled in the art. Generally, they are groups that are capable of accepting electrons, i.e., being reduced. An electron acceptor group within the meaning of the present invention is preferably an organic group that has a LUMO of < -2.8 eV, preferably

[0026] < -2.9 eV, particularly preferably < -3.0 eV and most particularly preferably

[0027] < -3.2 eV. The LUMO of the electron-accepting group in the context of the present compound is defined as the LUMO of group Z, which contains a hydrogen atom instead of the compound represented by formula (1) and formulas (2-1) to (2-7). The LUMO is determined by quantum chemical calculations, as generally described in the examples below.

[0028] 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.

[0029] 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.

[0030] An aromatic ring system within the meaning of this invention contains 6 to 60 C atoms in the ring system, preferably 6 to 40 C atoms in the ring system. A heteroaromatic ring system within the meaning of this invention contains 2 to 60 C atoms, preferably 3 to 40 C atoms, and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system within the meaning of this invention is to be understood as a system which does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be connected by a non-aromatic unit, such as a C, N or O atom. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc.are understood as aromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are linked, for example, by a short alkyl group. The aromatic ring system is preferably selected from fluorene, 9,9'-spirobifluorene, 9,9-diarylamine, or groups in which two or more aryl and / or heteroaryl groups are linked to one another by single bonds.

[0031] An electron-rich heteroaromatic ring system is characterized by the fact that it is a heteroaromatic ring system that contains no electron-deficient heteroaryl groups. An electron-deficient heteroaryl group is a six-membered ring heteroaryl group with at least one nitrogen atom or a five-membered ring heteroaryl group with at least two heteroatoms, one of which is a nitrogen atom and the other oxygen, sulfur, or a substituted nitrogen atom, to which further aryl or heteroaryl groups may be fused. In contrast, electron-rich heteroaryl groups are five-membered ring heteroaryl groups with exactly one heteroatom selected from oxygen, sulfur, or substituted nitrogen, to which further aryl groups and / or further electron-rich five-membered ring heteroaryl groups may be fused.Examples of electron-rich heteroaryl groups include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, and indenocarbazole. An electron-rich heteroaryl group is also called an electron-rich heteroaromatic radical.

[0032] An electron-poor heteroaromatic ring system is characterized in that it contains at least one electron-poor heteroaryl group, and particularly preferably no electron-rich heteroaryl groups.

[0033] In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which may contain 1 to 20 C atoms and in which individual H atoms or CH2 groups may be substituted by the above-mentioned groups, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neo-pentyl, cyclopentyl, n-hexyl, neo-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, Cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentinyl, hexynyl, heptynyl or octynyl.Unter einer Alkoxygruppe mit 1 bis 40 C-Atomen werden bevor- zugt Methoxy, Trifluormethoxy, Ethoxy, n-Propoxy, i-Propoxy, n-Butoxy, i-Butoxy, s-Butoxy, t-Butoxy, n-Pentoxy, s-Pentoxy, 2-Methylbutoxy, n- Hexoxy, Cyclohexyloxy, n-Heptoxy, Cycloheptyloxy, n-Octyloxy, Cyclo- octyloxy, 2-Ethylhexyloxy, Pentafluorethoxy und 2,2,2-Trifluorethoxy ver- standen. Unter einer Thioalkylgruppe mit 1 bis 40 C-Atomen werden ins- besondere Methylthio, Ethylthio, n-Propylthio, i-Propylthio, n-Butylthio,.

[0034] 1-Butylthio, s-Butylthio, t-Butylthio, n-Pentylthio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclooctylthio,

[0035] 2-Ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio, or octynylthio. In general, alkyl, alkoxy, or thioalkyl groups according to the present invention can be straight-chain, branched, or cyclic, where one or more non-adjacent CH2 groups can be replaced by the above-mentioned groups; Furthermore, one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, preferably F, Cl or CN, more preferably F or CN, particularly preferably CN.

[0036] For the purposes of the present invention, the generic term "alkyl group" encompasses both straight-chain alkyl groups and branched or cyclic alkyl groups. The same applies to alkenyl, alkynyl, alkoxy, and thioalkoxy groups.

[0037] An aromatic or heteroaromatic ring system with 5 to 60 or 5 to 40 aromatic ring atoms, which may each be substituted with the above-mentioned radicals and which may be linked to the aromatic or heteroaromatic ring via any position, is understood to mean, in particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, iso- benzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, iso-quinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-chinolin, Phenothiazin, Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazin- imidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1 ,2-Thiazol, 1 ,3-Thiazol, Benzo- thiazol, Pyridazin, Hexaazatriphenylen, Benzopyridazin, Pyrimidin, Benz- pyrimidin, Chinazolin, Chinoxalin, 1 ,5-Diazaanthracen, 2,7-Diazapyren,

[0038] 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,

[0039] 1 .2.3-Triazol, 1 ,2,4-Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1 ,2,4-Oxadi- azol, 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,

[0040] 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole or groups derived from combinations of these systems.

[0041] 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.

[0042] In education

[0043] 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:

[0044] In a preferred embodiment, the groups of formulas (2-1) to (2-7) are represented by the following formulas (2-1 a) to (2-7a),

[0045] where the symbols used have the meanings given above.

[0046] The structure of formula (2-1 a) is particularly suitable for compounds used in organic electroluminescent devices, where in this case Y 1 preferred for NR C , 0 or S. The structures of formulas (2-1 b) and (2-2a) to (2-7a) are particularly suitable for compounds used in photoreceptors, where in this case Y 1 preferably identically or differently on each occurrence represent S, Se or Te, particularly preferably identically or differently on each occurrence represent S or Se and very particularly preferably represent S.

[0047] In a preferred embodiment, a maximum of three Xs represent N, particularly preferably a maximum of two Xs represent N, very particularly preferably a maximum of one X represents N and particularly preferably all Xs represent CR a . In a preferred embodiment, at least one R c for an electron acceptor group or for an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 can be substituted, whereby two adjacent R c an electron acceptor group or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1Compounds with an electron-acceptor group are particularly suitable as photosensitizers, while compounds with an aromatic or heteroaromatic ring system are particularly suitable as materials for OLEDs, especially as triplet matrix materials. Such compounds preferably do not have an electron-acceptor group.

[0048] In a preferred embodiment of the invention, at least one group X 1 , prefers exactly one group X 1 for CZ or for a group CR C , where R c represents an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 can be substituted.

[0049] In a preferred embodiment, a maximum of one X 1 for CZ.

[0050] In a preferred embodiment of the invention, the structure of formula (1 ) is a structure of the following formula (1 -1 ),

[0051] Formula (1 -1 ) where the symbols used have the meanings given above.

[0052] In a preferred embodiment of the invention, the compounds of formula (1) are selected from the compounds of the following formulas (3-1) to (3-14),

[0053]

[0054] Formula (3-11) Formula (3-12)

[0055]

[0056] Formula (3-13) Formula (3-14) where the symbols used have the meanings given above.

[0057] In a preferred embodiment of the invention, the compounds of formula (1) are selected from the compounds of the following formulas (4-1) to (4-14),

[0058] Formula (4-1) Formula (4-2)

[0059]

[0060]

[0061]

[0062] Formula (4-13) Formula (4-14) where the symbols used have the meanings given above. In a preferred embodiment, the compound is particularly suitable for OLEDs, where Y is a single bond, BR b , C(R b )2, NR b or 0.

[0063] In a further preferred embodiment, the compound is particularly suitable for photosensitizers, where Y is a single bond, C(R b )2 or S, particularly preferably a single bond or S. These compounds particularly preferably also have at least one group Z, particularly preferably exactly one group Z.

[0064] In a preferred embodiment, the compound is particularly suitable for OLEDs, where Y 1 at each occurrence, the same or different, represents a single bond, NR C, 0 or S.

[0065] In a preferred embodiment, the compound is particularly suitable for photosensitizers, where Y 1 at each occurrence, identically or differently, represents S or Se, preferably S. These compounds particularly preferably also have at least one group Z, particularly preferably exactly one group Z.

[0066] In a preferred embodiment, the compound is particularly suitable for photosensitizers, wherein Y 1 at each occurrence, identically or differently, represents S or Se, preferably S, and Y represents a single bond or S. These compounds particularly preferably also contain at least one group Z, particularly preferably exactly one group Z.

[0067] The Z group is an electron acceptor group. Particularly suitable for this purpose are alkenyl groups substituted by at least two CN groups, alkenyl groups substituted by at least one CN group and at least one substituted carbonyl group, alkenyl groups substituted by two substituted carbonyl groups, where the substituents on the carbonyl groups form a ring system, or aromatic or heteroaromatic ring systems substituted by at least two CN groups. These electron acceptor groups are described in more detail below.

[0068] In a preferred embodiment of the invention, the group Z is an alkenyl group having 2 to 20 C atoms, where the alkenyl group may be substituted by one or more radicals R, where one or more non-adjacent CH2 groups may be replaced by O, S, Se or Si(R)2, with the proviso that the group Z has at least two CN groups or is substituted by at least one CN group and at least one substituted carbonyl group; the group Z may be substituted with R c form a ring system. In particular, it is a terminal alkenyl group substituted at the terminal C atom with two CN groups. R is analogous to R a defined above.

[0069] The alkenyl group can be straight-chain, cyclic, or branched, with the branched groups having at least 3 carbon atoms and the cyclic groups having at least 4 carbon atoms. The cyclic groups can also have one or more heteroatoms. The alkenyl group has at least two CN groups or at least one CN group and at least one substituted carbonyl group, which are preferably bonded to the same carbon atom. It is preferred if the at least two CN groups or at least one CN group and at least one substituted carbonyl group of the Z group are continuously conjugated with the 5-membered ring to which the Z group is bonded.

[0070] The term "conjugation" or "conjugated" is known to those skilled in the art. A continuous conjugation of the at least two CN groups of group Z is formed as soon as alternating double and single bonds are formed between the at least two CN groups or the at least one CN group and at least one substituted carbonyl group of group Z and the 5-membered ring containing the group Y. 1and to which the group Z is bonded. A further linkage between the aforementioned conjugated groups, which occurs, for example, via an S, N or O atom, does not harm the conjugation. In a preferred embodiment of the invention, Z is an alkenyl group having 2 to 10 C atoms, preferably having 2 to 6 C atoms, particularly preferably having 2 to 4 C atoms, which may be substituted by one or more radicals R, where at least two CN groups or at least one CN group and at least one substituted carbonyl group are bonded to the alkenyl group, preferably terminally; the alkenyl group may be bonded to the group R c form a ring system.

[0071] Particularly preferably, Z is an alkenyl group having 2 C atoms which is substituted by a radical R and two CN groups or one CN group and one substituted carbonyl group, wherein the two CN groups or the CN group and the substituted carbonyl group are preferably bonded terminally.

[0072] Preferred embodiments of the group Z are the structures of the formulas (Z-1), (Z-1 ') and (Z-2), where R and R 1 have the meanings mentioned above, the dashed bond represents the connection point and furthermore:

[0073] R' stands for CN or for C(=O)R", where R" stands for OH, OD, an alkyl group having 1 to 6 C atoms or an alkoxy group having 1 to 6 C atoms; preferably R' = CN;

[0074] X zis 0, S or Se, preferably 0 or S and particularly preferably 0; p is 0, 1 or 2, preferably 0 or 1 and particularly preferably 1. Preferably, R in formula (Z-1) and (Z-1') is H or D, so that the groups (Z-1) and (Z-1') are a group of the formula (Z-1-1), (Z-1-2) or (Z-1-3), which may also optionally be deuterated:

[0075] Formula (Z-1-1) Formula (Z-1-2) Formula (Z-1-3) where the dashed bond represents the attachment point and R" has the meanings given above. Formula (Z-1-1) is particularly preferred.

[0076] For formula (Z-2) the following applies:

[0077] R, which is bonded to the non-cyclic alkenyl group in formula (Z-2), is preferably, identically or differently on each occurrence, H, D or an optionally deuterated alkyl group having 1 to 5 C atoms, particularly preferably H, D or optionally deuterated methyl and very particularly preferably H or D.

[0078] R, which is bonded to the five-membered ring in formula (Z-2), is preferably H, D, CN, F, an optionally deuterated alkyl group having 1 to 5 C atoms or an optionally deuterated phenyl group, which can also be substituted by one or more preferably non-aromatic radicals R 1 may be substituted. Preferably, this R is selected from H, D, methyl, CD3 or CN.

[0079] The groups R 1 which are bonded to the five-membered ring in formula (Z-2) are preferably identical or different on each occurrence and are H, D, an optionally deuterated alkyl group having 1 to 5 C atoms or an optionally deuterated phenyl group, which can also be substituted by one or more preferably non-aromatic radicals R 1 can be substituted. The two groups R 1 also form a ring system with each other. These groups R 1identically or differently on each occurrence, an optionally deuterated alkyl group having 1 to 4 C atoms, in particular an optionally deuterated methyl group. Preferred embodiments of the formula (Z-2) are the structures of the following formulas (Z-2-1), (Z-2-2), (Z-2-3) and (Z-2-4), where these groups may also be partially or fully deuterated, where the dashed bond represents the attachment site, R represents H, D, optionally deuterated methyl or CN and R 1 identical or different at each occurrence represents H, D or optionally deuterated methyl, in particular optionally deuterated methyl.

[0080] Particularly preferred embodiments of formula (Z-2) are the structures of the following formulas (Z-2a) to (Z-2d), where these groups may also be partially or completely deuterated,

[0081] where the dashed bond represents the attachment point.

[0082] In a further preferred embodiment of the invention, the group Z is a terminal alkenyl group having 2 to 10 C atoms, preferably having 2 to 4 C atoms, and particularly preferably having 2 C atoms, which may be substituted by one or more substituents R and wherein the terminal C atom is substituted by a group -C(=O)-LC(=O)-. The two C(=O) groups of the group -C(=O)-LC(=O)- are each bonded to the terminal C atom of the alkenyl group, forming a cyclic group. The group L is a bivalent organic group.

[0083] A preferred embodiment of this group Z is a group of the following formula (Z-3), where the dashed bond represents the attachment of this group, R analogous to R a is defined above and furthermore: L is an optionally deuterated bivalent aryl or heteroaryl group with

[0084] 5 to 14 aromatic ring atoms, preferably with 6 to 10 aromatic ring atoms, particularly preferably a phenylene group, each of which may be substituted by one or more radicals R, or a group according to one of the formulas -NR-C(=O)-NR-, -NR-C(=S)-NR or -NR-C(=C(CN)2)-NR, where R preferably represents H, D or an optionally deuterated alkyl group having 1 to 6 C atoms, in particular an optionally deuterated methyl group, or a group according to one of the formulas -CR2-CR2-, -CR2-CR2-CR2-, -CR2-C(=O)-CR2-, -O-CR2-O- or -NR-NR-, where R each preferably represents H, D or an optionally deuterated alkyl group having 1 to

[0085] 6 C atoms and several R residues can also form a ring with each other.

[0086] Preferred embodiments of formula (Z-3) are thus the structures of formulas (Z-3-1) to (Z-3-9), where the dashed bond represents the attachment of this group and R has the meanings given above.

[0087] The radical R which is bonded to the double bond in formula (Z-3) or (Z-3-1) to (Z-3-9) is preferably H or D. The radicals R which are bonded to the benzo group in formula (Z-3-1) are preferably the same or different on each occurrence and are H, D, F or CN. The radicals R which are bonded to the nitrogen atoms in formula (Z-3-2) to (Z-3-4) and (Z-3-8) are preferably the same or different and are H, D or an optionally deuterated alkyl group having 1 to 6 C atoms. The radicals R which are bonded to the carbon atoms of the aliphatic cycle in formula (Z-3-5) to (Z-3-7) and (Z-3-9) are preferably identical or different at each occurrence and represent H, D or an optionally deuterated alkyl group having 1 to 6 C atoms, where several radicals R can also form a ring with one another.It is preferred if the radicals R which are bonded to a carbon atom which is adjacent to a carbonyl group, identically or differently on each occurrence, represent D or an optionally deuterated alkyl group having 1 to 6 C atoms, in particular D or methyl.

[0088] Particularly preferred embodiments of the structure of formula (Z-3) are the structures of the following formulas (Z-3a) to (Z-3zz), wherein these structures may also be partially or completely deuterated, where the dashed bond represents the attachment of this group.

[0089] In a further embodiment of the invention, the group Z is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R, with the proviso that the group Z has at least two CN groups. Here, R is analogous to R adefined above. Preference is given to compounds in which at least one CN group and preferably at least two CN groups are bonded to the 5-membered ring containing Y 1 to which the aromatic or heteroaromatic ring system is bound, is continuously conjugated.

[0090] The term "conjugated" is known to the person skilled in the art. A continuous conjugation of the at least one CN group is formed, for example, by this group binding directly to an aryl or heteroaryl group, wherein this aryl or heteroaryl group is bonded to the 5-membered ring containing the group Y. 1 and to which the aryl or heteroaryl group is bonded, is continuously conjugated.

[0091] Furthermore, a continuous conjugation of the at least one CN group of the group Z is formed as soon as alternating double and single bonds between the CN group of the group Z and the 5-membered ring, which the group Y 1 includes, are formed.

[0092] In a preferred embodiment of the invention, this group Z is a group according to the following formula (Z-4), where the dashed bond represents the attachment of this group, R analogous to R a is defined above and continues to apply:

[0093] X 2 is the same or different on each occurrence CR or N, with the proviso that a maximum of three X 2 represent N and that a maximum of two N atoms are directly bonded to each other, and further with the proviso that at least two groups X 2 stand for C-CN.

[0094] In a preferred embodiment of the formula (Z-4), a maximum of two groups X 2 for N, particularly preferably a maximum of one group X 2 for N and most preferably all groups X 2 for CR. A preferred embodiment of formula (Z-4) is thus the structure of formula (Z-4-1 ), where the dashed bond represents the attachment of this group, R is as defined above and at least two groups R represent CN.

[0095] Particularly preferably, the group Z can represent a partial structure of the formulas (Z-4a) to (Z-4i),

[0096] where the dashed bond indicates the linkage of the group and R has the meanings given above. Preferably, a maximum of two R radicals are not H or D, particularly preferably a maximum of one R radical is not H or D, and very particularly preferably all R radicals are H or D.

[0097] The groups of formulas (Z-4a), (Z-4e), (Z-4f) and (Z-4g) are preferred.

[0098] In a further preferred embodiment of the invention, the group Z is a terminal alkenyl group having 2 to 10 C atoms, preferably having 2 to 4 C atoms and particularly preferably having 2 C atoms, which may be substituted by one or more substituents R and wherein the terminal C atom is substituted by two groups -SO2R"'. The substituent R"' is preferably an alkyl group having 1 to 6 C atoms, wherein the two substituents R"' may also form a ring system with one another.

[0099] A preferred embodiment of this group Z is a group of the following formula (Z-5), where the dashed bond represents the attachment of this group, R analogous to R a to R e is defined above and continues to apply:

[0100] R"' is an optionally deuterated alkyl group having 1 to 6 C atoms; or the two groups R"' together form a ring and represent -CR2-CR2- or -CR2-CR2-CR2-, where R in each case preferably represents H, D or an optionally deuterated alkyl group having 1 to 6 C atoms and several radicals R can also form a ring with each other.

[0101] A preferred embodiment of this group is the group of formulas (Z-5-1 ), where the symbols used have the meanings given above and the group can optionally be deuterated.

[0102] Examples of suitable acceptor groups Z are the structures shown in the table below, where these structures are linked via the dashed bond. The LUMO for each of these structures is also given, which is defined according to the invention as the LUMO for the corresponding compound that bears an H instead of the dashed bond, with the LUMO being calculated as described in the examples section.

[0103] Preferred embodiments for an electron acceptor group or group Z are the formulas (Z-1) to (Z-5) shown above, and particularly preferred structures are the formulas (Z-1-1) to (Z-1-3), (Z-2-1) to (Z-2-4), (Z-3-1) to (Z-3-8), (Z-4-1) and (Z-5-1) shown above, and very particularly preferred structures are the formulas (Z-1-1), (Z-1-2), (Z-1-3), (Z-2a) to (Z-2d), (Z-3a) to (Z-3zz) and (Z-4a) to (Z-4i) shown above. The structures (Z-1-1) and (Z-2a) to (Z-2d) are particularly preferred.

[0104] In the case of use as photosensitizers, compounds are preferred in which a group X 1 stands for CZ and for which applies:

[0105] Particularly preferred compounds are those for which:

[0106] In addition, the following compounds are preferred for photosensitizers:

[0107] Compounds of formula (5-1 ) for which Y 1 is S or Se, preferably S, and Y is a single bond or S.

[0108] Very particular preference is given to compounds of formula (5-1 ) in which Y 1 is S and Z is a structure of the formula (Z-1 ), preferably R c and R is D or H, particularly preferably H.

[0109] If Y for C(R b )2, R b preferably identically or differently on each occurrence represents a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 12 C atoms, where the alkyl group may in each case be partially or completely deuterated and with one or more radicals R 1may be substituted, or for an aryl or heteroaryl group having 5 to 12 aromatic ring atoms, preferably a phenyl group, which may be partially or completely deuterated and by one or more radicals R 1 may be substituted, where the two radicals R b of group Y together can form a ring. If two radicals R b together form a ring, a spiro system is formed, where the ring formed by the two residues R b The ring formed is preferably a 5-membered ring or a 6-membered ring. When Y is C(R e )2, R b particularly preferably represents F, methyl, ethyl, neo-pentyl or phenyl, where these groups may also be partially or completely deuterated and where the two groups R b can also form a ring with each other, or the two groups R btogether with the C atom to which they bind, form a cyclopentyl, cyclohexyl or adamantanyl group, which may also be partially or fully deuterated. Particularly preferably, R b represents methyl, which may also be partially or completely deuterated. In a further preferred embodiment of the invention, the radical R a for H, D, a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 12 C atoms, wherein the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, or an aryl or heteroaryl group having 5 to 12 aromatic ring atoms, preferably a phenyl group, which may be substituted by one or more radicals R 1 may be substituted, where the radical R a with the remainder R 1 together can form a ring. In a particularly preferred embodiment of the invention, the radical R arepresents H, D, optionally deuterated methyl or optionally deuterated phenyl, most preferably H or D.

[0110] When two residues, which can be selected in particular from R, R a , R b , R c , R 1 and / or R 2 , form a ring system with each other, this can be mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic. The radicals forming a ring system can be adjacent, meaning that these radicals are bonded to the same carbon atom or to carbon atoms that are directly bonded to each other, or they can be further apart.

[0111] The compounds according to the invention preferably have a molecular weight of less than or equal to 5000 g / mol, preferably less than or equal to 4000 g / mol, particularly preferably less than or equal to 3000 g / mol, very particularly preferably less than or equal to 2000 g / mol and particularly preferably less than or equal to 1200 g / mol.

[0112] Furthermore, preferred compounds according to the invention are characterized in that they are sublimable.

[0113] Preferred substituents R, R a , R b and R c described.

[0114] In a preferred embodiment of the invention, R, R a , R b and R c identically or differently at each occurrence selected from the group consisting of H, D, F, CN, Si(R 1 )s, B(OR 1)2, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, wherein the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system having 6 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 may be substituted; two or more radicals may form a ring system with each other. In a particularly preferred embodiment of the invention, R, R a , R b and R c identically or differently on each occurrence selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms, preferably having 1 to 4 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, preferably having 3 to 6 C atoms, where the alkyl group is in each case substituted with one or more radicals R 1may be substituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, particularly preferably having 6 to 18 aromatic ring atoms, very particularly preferably having 6 to 13 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted; two or more residues can form a ring system.

[0115] It may be preferred if at least one of the substituents R, R a , R b , and R c identically or differently on each occurrence represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, particularly preferably having 6 to 18 aromatic ring atoms, very particularly preferably having 6 to 13 aromatic ring atoms, which in each case is substituted by one or more radicals R 1 can be substituted.

[0116] Preferred aromatic or heteroaromatic ring systems R, R a, R b and / or R c are selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which may be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which may be linked via the 1-, 2-, 3- or 4-position, naphthalene, in particular 1- or 2-linked naphthalene, indole, benzofuran, benzothiophene, carbazole, which may be linked via the 1-, 2-, 3-, 4- or 9-position, dibenzofuran, which may be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, which may be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, Indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which is substituted with one or more radicals R, R 1 or R2 can be substituted.

[0117] If R, R a , R b and / or R c represent an aromatic or heteroaromatic ring system, these are preferably selected, identically or differently at each occurrence, from the groups of the following formulas R-1 to R-184,

[0118]

[0119] R-58

[0120]

[0121]

[0122] R-114 R-115 R-116 R-117

[0123] where R 1 has the meanings given above, the dashed bond represents the bond and furthermore:

[0124] Ar 3is at each occurrence, identically or differently, a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, each of which is substituted by one or more radicals R 1 can be substituted;

[0125] A 1 is the same or different each time it occurs BR 1 , C(R 1 )2, C=O, NR 1 , 0 or S, where A 1 in the formulas R-150, R-151 and R-152 for BR 1 , C=O, NR 1 , 0 or S;

[0126] A 2 is the same or different at each occurrence C(R 1 )2, NR 1 , 0 or S; p is 0 or 1 , where p = 0 means that the group Ar 3is not present and that the corresponding aromatic or heteroaromatic group is directly bonded to the associated atom, for example a carbon atom or to a heteroatom such as a nitrogen, where, in the case of bonding to a heteroatom, for the formulas R-44, R-49, R-53, R-57, R-58, R-62, R-66, R-70, R-71, R-112, R-152 to R-160, R-167, R-172, R-177, R-182 p is 1; r is 0 or 1, where r = 0 means that no group A is present at this position. 1 and the corresponding carbon atoms are instead bound to residues R 1 are bound.

[0127] In a preferred embodiment, Ar comprises 3 bivalent aromatic or heteroaromatic ring systems based on the groups R-1 to R-184, where p is 0 and the dashed bond and an R 1 represents the bond to the aromatic or heteroaromatic group according to R-1 to R-184.

[0128] If the above groups R-1 to R-184 contain several groups A 1 all combinations from the definition of A 1 Preferred embodiments are then those in which a group A 1 for C(R 1 )2, NR 1 , 0 or S and the other group A 1 for C(R 1 )2, NR 1 , 0 or S.

[0129] If A 1 for NR 1 the substituent R 1 which is bonded to the nitrogen atom, preferably represents an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 2 In a particularly preferred embodiment, this substituent R 1identical or different on each occurrence represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, and which in each case can also be substituted by one or more radicals R 2 Particularly preferred are phenyl, biphenyl, terphenyl and quaterphenyl with linkage patterns as listed above for R-1 to R-35, where these structures are substituted by one or more radicals R 1 may be substituted, but are preferably unsubstituted.

[0130] If A 1 for C(R 1 )2, the substituents R 1which are bonded to this carbon atom, preferably identically or differently on each occurrence, represent a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 2 R is particularly preferably 1 represents a methyl group or a phenyl group. The radicals R 1 also form a ring system with each other, which leads to a spiro system.

[0131] Other suitable groups R, R a , R b and R c are groups of

[0132] Formula -Ar 4 -N(Ar 2 )(Ar 3 ), where Ar 2 , Ar 3 and Ar 4identically or differently on each occurrence represent an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which is substituted by one or more radicals R 1 The total number of aromatic ring atoms of Ar 2 , Ar 3 and Ar 4 maximum 60 and preferably maximum 40.

[0133] Ar 4 and Ar 2 with each other and / or Ar 2 and Ar 3 with each other also by a group selected from C(R 1 )2, NR 1 , O or S. Preferably, the linking of Ar 4 and Ar 2 with each other or from Ar 2 and Ar 3 are ortho to the position of the linkage to the nitrogen atom. In a further embodiment of the invention, none of the groups Ar 2 , Ar 3 or Ar 4 connected to each other.

[0134] Ar is preferred 4 an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted. Particularly preferred is Ar 4 selected from the group consisting of ortho-, meta- or para-phenylene or ortho-, meta- or para-biphenyl, each of which is substituted by one or more radicals R 1 may be substituted, but are preferably unsubstituted. Ar is particularly preferred 4 an unsubstituted phenylene group.

[0135] Preference is given to Ar 2 and Ar 3 identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 1 Particularly preferred groups Ar 2 or Ar 3are, identically or differently at each occurrence, selected from the group consisting of benzene, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spiro-bifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene, 1-, 2-

[0136] 3- or 4-carbazole, 1-, 2-, 3- or 4-dibenzofuran, 1-, 2-, 3- or 4-di-benzothiophene, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2-,

[0137] 4- or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene or triphenylene, each of which is substituted with one or more radicals R 1 may be substituted. Particularly preferred are Ar 2 and Ar 3identically or differently on each occurrence selected from the group consisting of benzene, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, in particular 1-, 2-, 3- or 4-fluorene, or spirobifluorene, in particular 1-, 2-, 3- or 4-spirobifluorene.

[0138] In a further preferred embodiment of the invention, R 1 identically or differently on each occurrence selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl group is in each case substituted with one or more radicals R 2 may be substituted, or an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, each substituted by one or more radicals R2 may be substituted; two or more radicals R 1 form a ring system with each other. In a particularly preferred embodiment of the invention, R 1 identically or differently on each occurrence selected from the group consisting of H, a straight-chain alkyl group having 1 to 6 C atoms, in particular having 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group having 3 to 6 C atoms, where the alkyl group is in each case substituted with one or more radicals R 2 may be substituted, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, each substituted by one or more radicals R 2 may be substituted, but is preferably unsubstituted; two or more radicals R 1 form a ring system with each other.

[0139] In a further preferred embodiment of the invention, R 2identical or different on each occurrence H, D, 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.

[0140] In a further embodiment of the invention, R c and if present Z, an aryl or heteroaryl group fused to the last five-membered ring with 4 to 14 aromatic ring atoms, which can also be substituted with R 1 can be substituted.

[0141] In compounds according to the invention that are processed by vacuum evaporation, the alkyl groups preferably have no more than five carbon atoms, particularly preferably no more than 4 carbon atoms, and most preferably no more than 1 carbon atom. Also suitable for compounds that are processed from solution are compounds that are substituted by alkyl groups, particularly branched alkyl groups, with up to 10 carbon atoms, or that are substituted by oligoarylene groups, for example ortho-, meta-, para-, or branched terphenyl or quaterphenyl groups.

[0142] 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.

[0143] Examples of preferred compounds according to the embodiments listed above are the compounds listed in the following table:

[0144]

[0145] The compounds of the invention can, in principle, be prepared by various methods. However, the methods described below have proven particularly suitable.

[0146] Therefore, the invention further provides a process for preparing the compounds according to the invention, in which a benzo[a]carbazole is provided and coupled at the nitrogen atom with a corresponding heteroaryl group, and the compound of formula (1) is obtained by intramolecular cyclization. Optionally, further radicals can be introduced by coupling reactions.

[0147] The synthesis of the compounds according to the invention can be carried out, inter alia, according to the following schemes. First, the parent compound (4) is prepared by reacting a benzo[a]carbazole (1) with a 2-bromo- or 2-iodo-substituted 5-membered-ring heterocycle (2) in a copper-catalyzed Ullmann coupling to give the intermediate (3), which is then subjected to intramolecular cyclization under palladium-phosphine catalysis (see Scheme 1). Analogously, compounds with two or three fused pentagons can be used as starting materials.

[0148] Scheme 1 : The parent compound (4) thus prepared can then be further functionalized in the o-position to Y via SeAr reaction, e.g., a halogenation, preferably a bromination with N-bromosuccinimide, a formylation, acylation, or nitration, etc. The reactive halogen intermediates can be converted into the other compounds according to the invention by means of a C-C coupling (A) such as a Suzuki, Negishi, Grignard-Cross, Sonogashira coupling, etc., or into C-N coupling (B) such as a Buchwald-Hartwig or Ullmann coupling. The carbonyl intermediates can be converted into the other compounds according to the invention by means of a Knoevenagel condensation (C), e.g., with malononitrile (Scheme 2).

[0149] Scheme 2:

[0150] The compounds of the invention can also be mixed with a polymer. It is also possible to incorporate these compounds covalently into a polymer.

[0151] The invention also relates to an oligomer, polymer or dendrimer comprising one or more compounds according to formula (1) or the preferred embodiments, wherein the bond(s) to the oligomer, polymer or dendrimer can be made at any position in formula (1).

[0152] Of particular interest are 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 of formula (1) or the preferred embodiments that 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).

[0153] For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, Cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP,p-Cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butylmethyl ether, triethylene glycol butylmethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyloctanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents. The present invention therefore further provides a formulation or composition comprising at least one compound according to the invention and at least one further compound. The further compound can be, for example, a solvent,in particular one of the above-mentioned solvents or a mixture of these solvents. However, the further compound can also be at least one further organic or inorganic compound that is also used in the electronic device, for example a comaterial, whereby these compounds differ from the compounds according to the invention. Suitable comaterials are listed below in connection with the organic electronic device. The further compound can also be polymeric.

[0154] The present invention therefore further provides a composition comprising a compound according to the invention and at least one further organic functional material. Functional materials are generally the organic or inorganic materials introduced between the anode and cathode. The organic functional material is preferably selected from the group consisting of photosensitizers, electron-transport materials, electron-injection materials, hole-conducting materials, hole-injection materials, electron-blocking materials, and hole-blocking materials, preferably photosensitizers, electron-transport materials, electron-injection materials, or hole-blocking materials.

[0155] A further object of the present invention is the use of a compound according to the invention in an electronic device, preferably an organic, photoelectric device, in particular in an organic optical detector, preferably as a photosensitizer, particularly preferably as a green, red, infrared or blue photosensitizer, especially preferably as a green photosensitizer.

[0156] The present invention further relates to an electronic device containing at least one compound according to the invention. An electronic device within the meaning of the present invention is a device that contains at least one layer containing at least one organic compound. The component may also contain inorganic materials or layers composed entirely of inorganic materials.

[0157] The electronic device is preferably selected from the group consisting of organic photoelectric devices, organic electroluminescent devices (OLEDs, sOLEDs, PLEDs, LECs, etc.), 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 photodiodes (OPDs), organic field quench devices (O-FQDs), and organic electrical sensors, preferably organic optical detectors, organic photoreceptors, and organic electronic sensors. Particular preference is given to organic optical detectors.

[0158] The organic optical detector contains a cathode, an anode, and at least one light-absorbing 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 light-absorbing layers. It should be noted, however, that not all of these layers are necessarily present. The organic optical detector may contain one light-absorbing layer, or it may contain multiple light-absorbing layers.

[0159] The compound according to the invention can be used in different

[0160] Layers can be used, depending on the precise structure. Preference is given to an organic optical detector comprising a compound according to formula (1) or (2) or the preferred embodiments described above in a light-absorbing layer as a photosensitizer, preferably an infrared, red, green, or blue photosensitizer, particularly preferably as a green photosensitizer, the color in each case indicating the color of the light absorbed by the photosensitizer.

[0161] When the compound of the invention is used as a photosensitizer in a light-absorbing layer, a suitable co-material known per se is preferably used. The co-material is used either as a mixture with the photosensitizer or in a layer adjacent to the layer containing the photosensitizer.

[0162] Suitable co-materials which can be used in combination, i.e. as a mixture with the compounds according to the invention or in a layer adjacent to the layer containing 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. B. 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. according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, e.g. according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776, azacarbazole derivatives, e.g. B. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar comaterials, e.g. B. according to WO 2007 / 137725, silanes, e.g. B. according to WO 2005 / 111172, azaboroles or boron 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. according to WO 2012 / 048781, dibenzofuran derivatives, e.g. according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565 or biscarbazoles, e.g. according to JP 3139321 B2.

[0163] In a preferred embodiment of the invention, one or more compounds according to the invention according to formula (1) or the preferred embodiments are used in combination with electron-transport materials, electron-injection materials, or hole-blocking materials. Particular preference is given to using, among others, subphthalocyanines, subphthalocyanine derivatives, fullerenes, or fullerene derivatives. Such compounds are known to those skilled in the art for use in organic optical detectors.

[0164] This embodiment is particularly preferred in the case that the compound according to the invention can be used as hole conductor materials, hole injection materials and / or electron blocking materials.

[0165] Preferred subphthalocyanines, subphthalocyanine derivatives, fullerenes, or fullerene derivatives are described, inter alia, in European patent application EP 3848374 A1, which is incorporated herein by reference for disclosure purposes. These materials are set forth in particular on pages 84 to 86 (see paragraphs

[0322] to

[0332] ).

[0166] In the further layers of the organic optical detector according to the invention, all materials commonly used in the prior art can be used. Therefore, without inventive effort, the person skilled in the art can use all materials known for organic optical detectors in combination with the compounds according to the invention according to formula (1) or the preferred embodiments described above.

[0167] Also preferred is an organic optical detector characterized in that one or more layers are coated using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10' 5 mbar, preferably less than 10' 6 mbar. However, it is also possible that the initial pressure is even lower, for example less than 10' 7 mbar.

[0168] Also preferred is an organic optical detector, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are sublimated at a pressure between 10' 5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured.

[0169] Also preferred is an organic optical detector 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 can be obtained, for example, by suitable substitution.

[0170] Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are vapor-deposited.

[0171] These methods are generally known to the person skilled in the art and can be applied by him without inventive step to organic optical detectors containing the compounds according to the invention.

[0172] Further details of preferred electronic devices, in particular organic optical detectors, as well as their manufacture, are known from the prior art. These are described, inter alia, in European patent application EP 3848374 A1, which is incorporated herein by reference for disclosure purposes. Reference is made in particular to Figures 1 to 10 described in EP 3848374 A1, which are set forth, inter alia, on pages 83 to 90 of EP 3848374 A1.

[0173] The device is also preferably an organic electroluminescent device comprising a cathode, an anode, and at least one emitting layer, wherein at least one organic layer, which may be an emitting layer, hole-transport layer, electron-transport layer, hole-blocking layer, electron-blocking layer, or another functional layer, comprises at least one compound according to the invention. The layer depends on the substitution of the compound.

[0174] In addition to these layers, the organic electroluminescent device 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, charge generation layers, and / or organic or inorganic p / n junctions. Interlayers, which, for example, have an exciton-blocking function, may also be inserted between two emitting layers. It should be noted, however, that not every one of these layers is necessarily required.

[0175] The organic electroluminescent device can contain one emitting layer or it can contain multiple emitting layers. If multiple emitting layers are present, they preferably have a total of multiple emission maxima between 380 nm and 750 nm, resulting in overall white emission, i.e., 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 basic structure is described, for example, in WO 2005 / 011013). The organic electroluminescent device according to the invention can also be a tandem OLED, in particular for white-emitting OLEDs.

[0176] The compound of formula (1) is preferably used in an organic electroluminescent device comprising one or more phosphorescent emitters. The compound of the invention according to the embodiments listed above can be used in different layers, depending on the precise structure.

[0177] The organic electroluminescent device may contain one emitting layer, or it may contain several emitting layers, with at least one layer containing at least one compound according to the invention. Furthermore, the compound according to the invention can also be used in an electron-transport layer and / or in a hole-blocking layer and / or in a hole-transport layer and / or in an exciton-blocking layer and / or as a matrix material. The compound according to the invention is particularly preferably used as a matrix material in an emitting layer and / or as an electron-transport material in an electron-transport or hole-blocking layer, in particular as a matrix material in a phosphorescent layer.

[0178] The term "phosphorescent compound" typically refers to compounds in which the emission of light occurs through a spin-forbidden transition, e.g., a transition from an excited triplet state or a state with a higher spin quantum number, e.g., a quintet state.

[0179] Suitable phosphorescent compounds (= triplet emitters) are, in particular, compounds which, upon suitable excitation, emit light, preferably in the visible range, and which 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. All luminescent complexes with transition metals or lanthanides are preferably regarded as phosphorescent compounds, particularly if they contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, in particular compounds containing indium, platinum, or copper. For the purposes of the present invention, all luminescent indium, platinum, or copper complexes are regarded as phosphorescent emitting compounds.

[0180] 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 / 041769, WO 2019 / 020538, WO 2018 / 178001, WO 2019 / 115423, and WO 2019 / 158453. In general, all phosphorescent complexes as used according to the prior art for phosphorescent OLEDs 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.It is possible for the skilled person, even without inventive step, to use other phosphorescent complexes in combination with the compounds of formula (1) in organic electroluminescent devices. Further examples are listed in the table below.

[0181] According to the invention, it is also possible to use the compound of formula (1) in an electronic device containing one or more fluorescent emitting compounds.

[0182] In a preferred embodiment of the invention, the compounds of formula (1) are used as electron-transporting materials. In this case, the compounds are preferably contained in an electron-transport layer or a hole-blocking layer or an electron-conducting or bipolar host material. Use in an electron-transport layer or host material is particularly preferred.

[0183] An electron transport layer within the meaning of the present application is a layer with an electron-transporting function between the cathode and the emitting layer.

[0184] In the context of the present application, electron injection layers and hole blocking layers are understood to mean specific embodiments of electron transport layers. In the case of a plurality of electron transport layers between the cathode and the emitting layer, an electron injection layer is an electron transport layer that is directly adjacent to the cathode or is separated from it only by a single coating of the cathode. In the case of several electron transport layers between the cathode and the emitting layer, a hole blocking layer is the electron transport layer that is directly adjacent to the emitting layer on the cathode side. The OLED according to the invention preferably comprises two, three or four electron-transporting layers between the cathode and the emitting layer, of which preferably at least one, particularly preferably exactly one or two, contains compounds of the formula (1).

[0185] If the compound of formula (1) is used as an electron transport material in an electron transport layer, an electron injection layer or a hole blocking layer, the compound can be used as a pure material, ie in a proportion of 100% in the electron transport layer, or it can be used in combination with one or more other compounds.

[0186] Hole-transport layers or electron-blocking layers of the electronic devices according to the invention may additionally comprise one or more p-dopants. P-dopants used according to the present invention are preferably organic electron-accepting compounds capable of oxidizing one or more of the other compounds in the mixture. Particularly preferred embodiments of p-dopants are the compounds disclosed in WO 2011 / 073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US 8057712, WO 2009 / 003455, WO 2010 / 094378, WO 2011 / 120709, US 2010 / 0096600, WO 2012 / 095143 and DE 102012209523.

[0187] In a further embodiment of the present invention, the compound of formula (1) is used in an emitting layer as a matrix material in combination with one or more emitting compounds, preferably phosphorescent compounds.

[0188] In this case, the proportion of matrix material in the emitting layer is between 50.0 and 99.9 vol.%, preferably between 80.0 and 99.5 vol.%, particularly preferably between 92.0 and 99.5 vol.% for fluorescent emitting layers and between 85.0 and 97.0 vol.% for phosphorescent emitting layers.

[0189] Accordingly, the proportion of the emitting compound is between 0.1 and 50.0 vol.%, preferably between 0.5 and 20.0 vol.%, particularly preferably between 0.5 and 8.0 vol.% for fluorescent emitting layers and between 3.0 and 15.0 vol.% for phosphorescent emitting layers.

[0190] An emitting layer of an organic electroluminescent device can also comprise systems that contain a plurality of matrix materials (mixed matrix systems) and / or a plurality of emitting compounds. In this case, too, the emitting compounds are generally those that have the smaller proportion in the system and the matrix materials those that have the larger proportion in the system. In individual cases, however, the proportion of an individual matrix material in the system can be lower than the proportion of an individual emitting compound. Preferably, the compounds of formula (1) are used as a component of mixed matrix systems. The mixed matrix systems preferably consist of two or three different matrix materials, particularly preferably of two different matrix materials.In this case, one of the two materials is preferably a material with hole-transporting properties and the other material is a material with electron-transporting properties. The compound of formula (1) is, depending on the substitution, the matrix material with electron-transporting properties or the matrix material with hole-transporting properties. However, the desired electron-transporting and hole-transporting properties of the mixed matrix components can also be predominantly or completely combined in a single mixed matrix component, with the further mixed matrix component(s) fulfilling other functions. The two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, even more preferably 1:10 to 1:1, and most preferably 1:4 to 1:1.Mixed matrix systems are preferably used in phosphorescent organic electroluminescent devices. A source for more detailed information on mixed matrix systems is the application WO 2010 / 108579.

[0191] The mixed matrix systems can contain one or more emitting compounds, preferably one or more phosphorescent compounds. Mixed matrix systems are generally preferred for use in phosphorescent organic electroluminescent devices.

[0192] Particularly suitable matrix materials that can be used in combination with the compounds of the invention as matrix components of a mixed matrix system are selected from the preferred matrix materials for phosphorescent compounds listed below or the preferred matrix materials for fluorescent compounds, depending on the type of emitting compound used in the mixed matrix system. Preferred phosphorescent compounds for use in mixed matrix systems are the same as those described above as generally preferred phosphorescent emitter materials.

[0193]

[0194] Preferred fluorescent-emitting compounds are selected from the class of arylamines. In the context of the present invention, an arylamine or an aromatic amine is understood to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems that are bonded directly to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, particularly preferably having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in position 9.An aromatic anthracene diamine is understood to be a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably in positions 9, 10. Analogously, aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined, in which the diarylamino groups are bonded to the pyrene preferably in the 1-position or 1,6-position. Further preferred emitting compounds are indenofluorenamines or fluorenediamines, for example according to WO 2006 / 108497 or WO 2006 / 122630, benzoindenofluorenamines or benzofluorenediamines, for example according to WO 2008 / 006449, and dibenzoindenofluorenamines or diamines, for example according to WO 2007 / 140847, as well as the indenofluorene derivatives with fused aryl groups disclosed in WO 2010 / 012328. Likewise preferred are the pyrenearylamines disclosed in WO 2012 / 048780 and WO 2013 / 185871.Also preferred are the benzoindenofluorenamines disclosed in WO 2014 / 037077, the benzofluorenamines disclosed in WO 2014 / 106522, the extended benzoindenofluorenes disclosed in WO 2014 / 111269 and WO 2017 / 036574, the phenoxazines disclosed in WO 2017 / 028940 and WO 2017 / 028941, and the fluorine derivatives bonded to furan units or to thiophene units disclosed in WO 2016 / 150544. Furthermore, boron compounds according to W02020208051, W02015102118, WO2016152418, WO2018095397, WO201 9004248, WO2019132040, US20200161552, WO2021089450 can be used.

[0195] Useful matrix materials, preferably for fluorescent compounds, include materials from various substance classes. Preferred matrix materials are selected from the classes of oligoaryls (e.g. 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthylanthracene), in particular oligoaryls with fused aromatic groups, oligoarylenevinylenes (e.g. DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (e.g. according to WO 2004 / 081017), hole-conducting compounds (e.g. according to WO 2004 / 058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (for example according to WO 2005 / 084081 and WO 2005 / 084082), atropisomers (for example according to WO 2006 / 048268), boronic acid derivatives (for example according to WO 2006 / 117052) or the benzanthracenes (for example according to WO 2008 / 145239).Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene, and / or pyrene, or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides, and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzophenanthrene, and / or pyrene, or atropisomers of these compounds. For the purposes of the present invention, an oligoarylene is understood to mean a compound in which at least three aryl or arylene groups are bonded to one another.Further preferred are the anthracene derivatives disclosed in WO 2006 / 097208, WO 2006 / 131192, WO 2007 / 065550, WO 2007 / 110129, WO 2007 / 065678, WO 2008 / 145239, WO 2009 / 100925, WO 2011 / 054442 and EP 1553154, the pyrene compounds disclosed in EP 1749809, EP 1905754 and US 2012 / 0187826, the benzanthracenylanthracene compounds disclosed in WO 2015 / 158409, the indenobenzofurans disclosed in WO 2017 / 025165 and the compounds disclosed in WO 2017 / 036573 disclosed phenanthryl-anthracenes.

[0196] Preferred matrix materials for phosphorescent compounds are, as well as compounds according to formula (1), 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 WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176, indolocarbazole derivatives, e.g. B. according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, e.g. according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776, azacarbazole derivatives, e.g. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, e.g. according to WO 2007 / 137725, silanes, e.g. according to WO 2005 / 111172, azaboroles or boronic esters, e.g. according to WO 2006 / 117052, triazine derivatives, e.g. B.according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, diazasilole or tetraazasilole derivatives, e.g. according to WO 2010 / 054729, diazaphosphole derivatives, e.g. according to WO 2010 / 054730, bridged carbazole derivatives, e.g. B. according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080, triphenylene derivatives, e.g. according to WO 2012 / 048781, lactams, e.g. according to WO 2011 / 116865 or WO 2011 / 137951, or dibenzofuran derivatives, e.g. according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565. Likewise, another phosphorescent emitter, which emits at a shorter wavelength than the actual emitter, can be present in the mixture as a co-host, or a compound that does not participate, or does not participate to a significant extent, in charge transport, as described, for example, in WO 2010 / 108579.Since the compounds according to the invention are electron-transporting compounds, they are preferably combined with a hole-transporting matrix material.

[0197] Particularly suitable hole-transporting matrix materials, which are advantageously combined with compounds of formula (1), as described above or preferably described, in a mixed-matrix system, can be selected from the compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), as described below. This applies in particular when the compounds of formula (1) are substituted by at least one electron-deficient heteroaryl group.

[0198] A further subject of the invention is therefore an organic electronic device comprising an anode, a cathode and at least one organic layer containing at least one light-emitting layer, wherein the at least one light-emitting layer contains at least one compound of the formula (1) as matrix material 1, as described above or described as preferred, and at least one compound of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) as matrix material 2, Formula (HH-6), where the symbols and indices used are:

[0199] A 1 is C(R 7 )2, NR 7 , 0 or S;

[0200] L is a bond, 0, S, C(R 7 )2 or NR 7 ;

[0201] A is, at each occurrence, independently of each other, a group of

[0202] Formula (HH-4-1 ) Formula (HH-4-2);

[0203] X2 is the same or different at each occurrence CH, CR 6 or N, where a maximum of 2 symbols X2 can mean N;

[0204] * indicates the binding site to the formula (HH-4);

[0205] U 1 , U 2 are when a bond occurs, 0, S, C(R 7 )2 or NR 7 ;

[0206] R 6 is at each occurrence, identically or differently, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , 0, S or CONR 7may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; two radicals R 6 also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ars, identical or different at each occurrence, independently represents an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which with one or more radicals R 7 can be substituted;

[0207] R 7 is the same or different at each occurrence D, F, CI, Br, I, N(R 8 )2, CN, NO2, OR 8 , SR 8 , Si(R 8 )3, B(OR 8 )2, C(=O)R 8 , P(=O)(R 8 )2, S(=O)R 8 , S(=O)2R 8 , OSO2R 8, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 8 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted; two or more radicals R 7 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R 7 no such ring system;

[0208] R 8is, identically or differently at each occurrence, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may be replaced by F; c, c1, c2 each independently of one another at each occurrence

[0209] Occurrence 0 or 1 , where the sum of the indices at each occurrence c+c1 +c2 = 1; d, d1 , d2 each independently at each occurrence

[0210] Occurrence 0 or 1 , where the sum of the indices at each occurrence is d + d1 + d2 = 1; q, q1 , q2 each independently mean 0, 1, 2, 3 or 4 at each occurrence; s is the same or different at each occurrence: 0, 1, 2, 3 or 4; t is the same or different at each occurrence: 0, 1, 2, or 3; u is the same or different at each occurrence: 0, 1 or 2; u1 , u2 each independently mean 0 or 1 at each occurrence, where the sum u1 + u2 = 1; and v is 0, 1, 2 or 3.

[0211] In compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-5) or (HH-6), s is preferably 0 or 1 when the radical R 6 is different from D, or more preferably 0.

[0212] In compounds of the formulas (HH-1), (HH-2) or (HH-3), t is preferably 0 or 1 if the radical R 6 is different from D, or more preferably 0.

[0213] In compounds of the formulas (HH-1), (HH-2), (HH-3) or (HH-5), u is preferably 0 or 1 when the radical R 6 is different from D, or more preferably 0.

[0214] The sum of the indices s, t and u in compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-5) or (HH-6) is preferably at most 6, particularly preferably at most 4 and particularly preferably at most 2. This preferably applies when R 6 is different from D.

[0215] In compounds of formula (HH-4), c, c1, c2 each independently represent 0 or 1 at each occurrence, where the sum of the indices c+c1+c2 represents 1 at each occurrence. Preferably, c2 represents 1.

[0216] In compounds of formula (HH-4), L is preferably a single bond or C(R 7 )2, where R 7 has a meaning mentioned above, particularly preferably L is a single bond.

[0217] In formula (HH-4-1 ) v is preferably 0 or 1 when the radical R 6 is different from D.

[0218] In formula (HH-4-2) U 1 or U 2 when occurring, preferably a single bond or C(R 7 )2, where R 7 has a meaning mentioned above, particularly preferred are U 1 or U 2 a single bond when occurring. In formula (HH-4-2), q, q1 , q2 are preferably 0 or 1 when the radical R 6 is different from D.

[0219] In a preferred embodiment of the compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), which can be combined according to the invention with compounds of formula (1) or preferred compounds of formula (1), as described above, R 6identically or differently on each occurrence selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl group is in each case substituted with one or more radicals R 7 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, preferably having 5 to 40 ring atoms, each substituted by one or more radicals R 7 can be substituted.

[0220] In a preferred embodiment of the compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), which can be combined according to the invention with compounds of formula (1) or preferred compounds of formula (1), as described above, R 6identically or differently on each occurrence selected from the group consisting of D or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which is reacted with one or more radicals R 7 can be substituted.

[0221] Preferably, Ars in compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-5) or (HH-6) is 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, fluorenyl, which may be linked via the 1-, 2-, 3- or 4-position, spirobifluorenyl, which may be linked via the 1-, 2-, 3- or 4-position, naphthyl, in particular 1- or 2-linked naphthyl, or residues derived from 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 may be linked, dibenzothiophene, which may be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene,which are each substituted with one or more radicals R, 7 may be substituted. Preferably, Ars is not substituted. If A 1 in formula (HH-2) or (HH-3) or (HH-6) for NR 7 the substituent R 7 which is bonded to the nitrogen atom, preferably represents an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 8 In a particularly preferred embodiment, this substituent R 7 identical or different on each occurrence, represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 18 aromatic ring atoms. Preferred embodiments for R 7 are phenyl, biphenyl, terphenyl and quaterphenyl, which are preferably unsubstituted, as well as radicals derived from triazine, pyrimidine and quinazoline, which are substituted by one or more radicals R 8can be substituted.

[0222] If A 1 in formula (HH-2) or (HH-3) or (HH-6) for C(R 7 )2, the substituents R 7 which are bonded to this carbon atom, preferably identically or differently on each occurrence, represent a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more radicals R 8 R is particularly preferably 7 represents a methyl group or a phenyl group. The radicals R 7 also form a ring system with each other, which leads to a spiro system.

[0223] In a preferred embodiment of the compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), these compounds are partially or completely deuterated, particularly preferably completely deuterated.

[0224] The preparation of the compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6) are generally known and some of the compounds are commercially available.

[0225] Compounds of formula (HH-4) are disclosed, for example, in WO2021 / 180614, on pages 110 to 119, particularly as examples on pages 120 to 127. Their preparation is disclosed in WO2021 / 180614 A1 on page 128 and in the synthesis examples on pages 214 to 218.

[0226] The preparation of the triarylamines of formula (HH-6) is known to the person skilled in the art and some of the compounds are commercially available.

[0227] If the at least one further matrix material is a deuterated compound, it is possible that this at least one matrix material is a mixture of deuterated compounds of the same basic chemical structure, which differ only in the degree of deuteration.

[0228] In a preferred embodiment of the at least one further matrix material, this is a mixture of deuterated compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), as described above, wherein the degree of deuteration of these compounds is at least 50% to 90%, preferably 70% to 100%.

[0229] Corresponding deuteration methods are known to the person skilled in the art and are described, for example, in KR2016041014 A, WO2017 / 122988 A1, KR2020052820 A, KR101978651 B1 and WO2018 / 110887 A1 or in Bulletin of the Chemical Society of Japan, 2021, 94(2), 600-605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071.

[0230] Examples of suitable further matrix materials for a combination with compounds of formula (1 ), as previously described or preferably described, are the compounds described in WO2019 / 229011 A1 , Table 3, pages 137 to 203, which may also be partially or completely deuterated.

[0231] Examples of suitable further matrix materials for a combination with compounds of formula (1) or preferred compounds of formula (1), as previously described or preferably described, are the compounds described in WO2021 / 180625 A1, Table 3, pages 131 to 127 and in Table 4, pages 137 to 139, which may also be partially or fully deuterated. Examples of suitable further matrix materials for a combination with compounds of formula (1) or preferred compounds of formula (1), as previously described or preferably described, are the compounds described in KR20230034896 A, on pages 42 to 47, compounds [2-1] to [2-110], or on pages 49 to 51, compounds [3-1] to [3-26].

[0232] Further examples of suitable host materials of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6) for combination with compounds of the formula (1) or preferred embodiments are the structures listed in Tables T1 and T2 below.

[0233] Table T1 :

[0234]

[0235] Particularly suitable compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), which are selected according to the invention and are preferably used in combination with at least one compound of the formula (1) in the electroluminescent device according to the invention, are the compounds of Table T2. The above-mentioned host materials of formula (1) and their preferred embodiments can be combined as desired in the device according to the invention with the previously mentioned matrix materials / host materials, the matrix materials / host materials of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) and their preferred embodiments of Table T1 or the compounds H1 to H27.

[0236] The concentration of the host material of formula (1), as described above or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 5 wt.% to 90 wt.%, preferably in the range from 10 wt.% to 85 wt.%, more preferably in the range from 20 wt.% to 85 wt.%, even more preferably in the range from 30 wt.% to 80 wt.%, very particularly preferably in the range from 20 wt.% to 60 wt.% and most preferably in the range from 30 wt.% to 50 wt.%, based on the total mixture or based on the total composition of the light-emitting layer.

[0237] The concentration of the sum of all host materials of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), as described above or described as preferred, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 10 wt.% to 95 wt.%, preferably in the range from 15 wt.% to 90 wt.%, more preferably in the range from 15 wt.% to 80 wt.%, even more preferably in the range from 20 wt.% to 70 wt.%, very particularly preferably in the range from 40 wt.% to 80 wt.% and most preferably in the range from 50 wt.% to 70 wt.%, based on the entire mixture or based on the entire composition of the light-emitting layer.

[0238] The present invention also relates to a mixture which, in addition to the above-mentioned host materials of the formula (1), hereinafter referred to as host material 1, and the host material of at least one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), hereinafter referred to as host material 2, as previously described or preferably described, contains at least one phosphorescent emitter.

[0239] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the light-emitting layer contains, in addition to the above-mentioned host materials of the formulas (1) and at least one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), as described above, at least one phosphorescent emitter.

[0240] Suitable charge transport materials which can be used in the hole injection or hole transport layer or in the electron barrier layer or in the electron transport layer of the electronic component according to the invention are, in addition to the compounds of formula (1), for example those mentioned in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials which are used in these layers according to the prior art.

[0241] Any materials that are currently used as hole-transport materials in the hole-transport layer can be used as materials for the hole-transport layer. Aromatic amine compounds can be used. Further compounds which are preferably used in hole-transporting layers of the OLEDs according to the invention are, in particular, indenofluorenamine derivatives (e.g. according to WO 06 / 122630 or WO 06 / 100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (e.g. according to WO 01 / 049806), amine derivatives with fused aromatics (for example according to US 5,061,569), the amine derivatives disclosed in WO 95 / 09147, monobenzoindenofluorenamines (for example according to WO 08 / 006449), dibenzoindenofluorenamines (for example according to WO 07 / 140847), spirobifluorenamines (for example according to WO 2012 / 034627 or WO 2013 / 120577), fluorenamines (for example according to WO 2014 / 015937, WO 2014 / 015938, WO 2014 / 015935 and WO 2015 / 082056),Spirodibenzopyranamines (for example according to WO 2013 / 083216), dihydroacridine derivatives (for example according to WO 2012 / 150001), spirodibenzofurans and spirodibenzothiophenes (for example according to WO 2015 / 022051, WO 2016 / 102048 and WO 2016 / 131521), phenanthrenediarylamines (for example according to WO 2015 / 131976), spirotribenzotropolones (for example according to WO 2016 / 087017), spirobifluorenes with meta-phenyldiamine groups (for example according to WO 2016 / 078738), spirobisacridines (for example according to WO 2015 / 158411), xanthenediarylamines (for example according to WO 2014 / 072017), and 9,10-dihydroanthracene spiro compounds with diarylamino groups according to WO 2015 / 086108.,

[0242] Very particular preference is given to the use of spirobifluorenes substituted by diarylamino groups in the 4-position as hole-transporting compounds, in particular the use of those compounds claimed and disclosed in WO 2013 / 120577, and the use of spirobifluorenes substituted by diarylamino groups in the 2-position as hole-transporting compounds, in particular the use of those compounds claimed and disclosed in WO 2012 / 034627.

[0243] The OLED according to the invention preferably comprises two or more different electron-transporting layers. The compound of formula (1) can be used in one or more or in all electron-transporting layers. In a preferred embodiment, the compound of formula (1) is used in exactly one or exactly two electron-transporting layers, and other compounds are used in the other electron-transporting layers present. Further compounds that can be used in addition to the compounds of formula (1) are all materials that are used according to the prior art as electron-transport materials in the electron-transport layer. Particularly suitable are aluminum complexes, e.g. Alq3, zirconium complexes, e.g. Zrq4, lithium complexes, e.g.Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives. Other suitable materials are derivatives of the aforementioned compounds as disclosed in JP 2000 / 053957, WO 2003 / 060956, WO 2004 / 028217, WO 2004 / 080975, and WO 2010 / 072300.

[0244] The device is structured, contacted and finally sealed accordingly (depending on the application) to exclude harmful influences from water and air.

[0245] 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, without inventive effort, the skilled person can use all materials known for organic electroluminescent devices in combination with the compounds according to the invention according to formula (1) or the preferred embodiments described above.

[0246] Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10' 5 mbar, preferably less than 10' 6 mbar. However, it is also possible that the initial pressure is even lower, for example less than 10' 7 mbar.

[0247] Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are sublimated at a pressure between 10' 5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured.

[0248] 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.

[0249] Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are vapor-deposited.

[0250] 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.

[0251] According to the invention, the electronic devices containing one or more compounds of formula (1) can be used in displays, as light sources in lighting applications and as light sources in medical and / or cosmetic applications (e.g. light therapy).

[0252] The electronic devices according to the invention, in particular organic optical detectors and organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art:

[0253] 1 . The compounds according to formula (1) or the preferred embodiments described, which contain a group Z, have a very high extinction coefficient. This is a significant advantage for the use of the materials in organic optical detectors.

[0254] 2. Electronic devices, in particular organic optical detectors or organic electroluminescent devices, comprising compounds of formula (1) or the preferred embodiments described, in particular as photosensitizers or OLEDs, have a very good lifetime. 3. Electronic devices, in particular organic optical detectors, comprising compounds of formula (1) or the preferred embodiments described as photosensitizers, have excellent efficiency. The inventive compounds of formula (1) or the preferred embodiments described result in a low operating voltage when used in electronic devices.

[0255] 4. The compounds according to the invention according to formula (1) or the preferred embodiments shown show high stability, in particular thermal stability and low vapor deposition temperatures.

[0256] 5. Using compounds according to formula (1) or the preferred embodiments described above, the formation of optical loss channels can be avoided in electronic devices, particularly organic optical detectors. As a result, these devices are characterized by high photocurrent efficiency of photosensitizers and excellent energy transfer.

[0257] 6. Compounds according to formula (1) or the preferred embodiments described have excellent glass film formation.

[0258] 7. Compounds of formula (1) or the preferred embodiments lead to good device results when used as matrix materials for phosphorescent dopants, in particular for red, orange or yellow phosphorescent dopants.

[0259] These advantages mentioned above are not accompanied by a deterioration of the other electronic properties.

[0260] 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.

[0261] Examples:

[0262] Unless otherwise stated, the following syntheses were carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be obtained, for example, from Sigma-ALDRICH or ABCR. The respective information in square brackets or the numbers given for individual compounds refer to the CAS numbers of the compounds known from the literature. For compounds that can exhibit multiple enantiomeric, diastereomeric, or tautomeric forms, one form is shown as a representative.

[0263] Literature-known Synthone LS:

[0264]

[0265] Synthesis of synthons:

[0266] Example S1 :

[0267] A well-stirred mixture of 25.2 g (100 mmol) 1-chloro-11 H-benzo[a]-carbazole [111960-32-8], 31.5 g (150 mmol) 2-iodothiophene [3437-95-4], 20.7 g (150 mmol) potassium carbonate, 35.5 g (250 mmol) sodium sulfate, 1.3 g (20 mmol) copper powder, 100 g glass beads (3 mmol diameter) and 600 ml 1,2-dichlorobenzene is heated under reflux for 48 h. While still hot, the filtrate is filtered with suction through a bed of Celite pre-slurried with 1,2-dichlorobenzene, the filtrate is concentrated to dryness in vacuo, the residue is taken up in 500 ml of dichloromethane (DCM), filtered through a bed of silica gel pre-slurried with DCM, 300 ml of methanol are added to the filtrate, and the mixture is concentrated to approximately 150 ml in vacuo at 40 °C. The crystallized product is filtered off with suction, washed three times with 50 ml of methanol, and dried in vacuo. Recrystallization from acetonitrile / DCM. Yield: 20.0 g (60 mmol), 60%; Purity: approximately 97% in n. 1 H-NMR. A well-stirred mixture of 33.3 g (100 mmol) of S2, step A, 41.5 g (300 mmol) of potassium carbonate, 3.1 g (30 mmol) of pivalic acid, 1.16 g (4 mmol) of tri-tert-butylphosphonium tetrafluoroborate, 449 mg (2 mmol) of palladium(II) acetate, 100 g of glass beads (3 mm diameter), and 300 ml of dimethylacetamide (DMAC) is stirred at 150 °C for 3 h. The mixture is allowed to cool to 80 °C, 1000 ml of water is added dropwise, and the precipitated crude product is filtered off with suction, washed three times with 100 ml of water each time and three times with 50 ml of methanol each time, and dried in vacuo. The crude product is dissolved in 500 ml of DCM and 50 ml of ethyl acetate, filtered through a silica gel bed pre-slurried with DCM, and removed in vacuo, replacing the distilled DCM towards the end with simultaneous addition of 200 ml of methanol. The crystallized product is filtered off with suction, washed three times with 50 ml of EtOH each time, and dried in vacuo. Yield: 15.3 g (51 mmol), 51%; Purity: approx. 97% in n. 1 H-NMR.

[0268] The following connections can be represented analogously:

[0269]

[0270] Synthesis of the compounds according to the invention:

[0271] Example B1:

[0272] Level A:

[0273] Carrying out the Vielsmeier-Haak formylation analogously to

[0274] US 2021 / 0234103, page 70, compound 1-1 D. Batch: 4.6 g (15.5 mmol)

[0275] S1. The crude product was purified by chromatography (Torrent column chromatography from A. Semrau). Yield: 2.8 g (8.5 mmol), 55%; Purity: approximately 98% by weight. 1 H-NMR.

[0276] Level B:

[0277] Procedure according to Haig et al., Chem. Mat., 2011, 23(20), 4435, page 4436, compound 3. Batch: 3.3 g (10.0 mmol) B1, step A. The crude product is purified by chromatography (Torrent column chromatography from A. Semrau) and / or repeated hot extraction crystallization (common organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) as well as fractional sublimation or annealing under high vacuum. Yield: 2.6 g (7.0 mmol), 70%; Purity: >99.9% by HPLC.

[0278] Instead of malononitrile, other CH-acidic compounds such as 1,3-indandione, barbituric acids and thiobarbituric acids, 2-(4,5,5-trimethyl-2(5 / - / )-furanylidene)-propanedinitrile and 2-(4,5,5-trimethyl-2(5 / - / )-thiophenylidene)-propanedinitrile and their derivatives can be reacted, see US 2021 / 0234103, page 71, Compound 1 and following.

[0279] The following connections can be represented analogously:

[0280]

[0281] Example B100:

[0282] Level A:

[0283] Preparation analogous to VG Nenajdenko, Russian Chemical Bulletin (2012), 61 (7), 1463. Batch: 3.0 g (10.0 mmol) S1. Yield: 3.3 g (8.7 mmol), 87%. Purity: approx. 98% in n. 1 H-NMR.

[0284] Level B:

[0285] Preparation analogous to Z. He et al., Tetrahedron (2020), 76(51), 131315, General Procedure A. Batch: 3.8 g (10.0 mmol) B100 stage A. Reaction monitored via TLC for consumption of B100 stage A, typical reaction time 16 - 24 h. The crude product is purified by chromatography (Torrent column automat from A. Semrau) and / or repeated hot extraction crystallization (common organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) as well as fractional sublimation or annealing under high vacuum. Yield: 2.7 g (7.3 mmol), 73%; Purity: > 99.9% by HPLC.

[0286] Example B200: Procedure analogous to Example S1. Batch: 2.5 g (10 mmol) LS1, 2.6 g (10 mmol) 2-iodobenzothiophene [36748-89-7]. The crude product is purified by chromatography (Torrent column automaton from A. Semrau) and / or repeated hot extraction crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) as well as fractional sublimation or annealing under high vacuum. Yield: 2.0 g (5.7 mmol), 57%. Purity: > 99.9% by HPLC.

[0287] The following connections can be represented analogously: Example B300:

[0288] Procedure analogous to K. Ogawa et al., Journal of Organic Chemistry (2001), 66(26), 9067. Batch: 3.8 g (10 mmol) S1, 1.7 g (10 mmol) diphenylamine [122-39-4]. The crude product is purified by chromatography (Torrent column machine from A. Semrau) and / or repeated hot extraction crystallization (usual organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) as well as fractional sublimation or annealing under high vacuum. Yield: 2.1 g (4.4 mmol), 44%; Purity: > 99.9% by HPLC.

[0289]

[0290] Determination of the LUMO of the acceptor groups

[0291] The LUMO value of the acceptor groups Z is determined by quantum chemical

[0292] Calculation as described below. The LUMO of the electron-accepting group in the context of the present compound is defined as the LUMO of the group Z, which contains a hydrogen atom instead of the group represented by formula (1) and formulas (2-1) to (2-7).

[0293] The Gaussian16 program package (Rev. B.01) is used for all quantum chemical calculations. The neutral singlet ground state is optimized at the B3LYP / 6-31 G(d) level. LUMO calc. values ​​are determined at the B3LYP / 6-31 G(d) level for the ground state energy optimized with B3LYP / 6-31 G(d). The default settings for SCF and gradient convergence are used.

[0294] The LUMO calc. value in eV derived from the quantum chemical calculation is additionally scaled with the following factors: LUMO = 0.99687 * LUMO calc. - 0.72445.

[0295] Examples of photodiodes:

[0296] 1) Manufacturing of mono-layer photodiodes (MLPD)

[0297] Cleaned quartz substrates (15 min. ultrasound in an acetone / isopropanol / water bath (1:1:1 v:v:v), followed by UV-ozone) are sputtered with a 150 nm thick indium tin oxide (ITO) anode. A 30 nm thick layer of HTM2 (see Table 3) is deposited on top of this under high vacuum, followed by an 80 nm thick layer of the inventive compounds B and Ceo in a 1:1 volume ratio. A 1.5 nm thick ytterbium layer is then deposited.

[0298] Finally, a 10 nm thick ITO cathode is applied by sputtering. The IPCE (Incident Photon to Charge Carrier Efficiency) of the initial devices is then determined using a PTS-2-QE from Photonic Solutions (UK) at the absorption peak in the wavelength range 400–700 nm at a voltage of 3 V (Table 1).

[0299] Table 1 : 2) Manufacturing of bi-layer photodiodes (BLPD)

[0300] Cleaned quartz substrates (15 min. ultrasound in an acetone / isopropanol / water bath (1:1:1 v:v:v), followed by UV ozone) are sputtered with a 150 nm thick indium tin oxide (ITO) anode. All other materials are thermally deposited in a vacuum chamber. The materials used to fabricate the BLPDs are shown in Table 3. The electron transport layer 2 (ETL2) can be fabricated by co-evaporation of two materials. A designation such as ETM1:EIL (50:50) means that the co-evaporated layer contains 50% by volume of each of the individual materials.

[0301] Structure of the BLPD:

[0302] ITO substrate BLPD

[0303] Hole injection layer (HIL) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 10 nm

[0304] Hole transport layer 1 (HTL1), see Table 2

[0305] Hole transport layer 2 (HTL2), see Table 2

[0306] Electron donor layer (EDL), see Table 2

[0307] Electron acceptor layer (EAL), see Table 2

[0308] Electron transport layer 1 (ETL1), see Table 2

[0309] Electron transport layer 2 (ETL2), see Table 2

[0310] Electron injection layer 1 (EIL1), 3 nm EIM

[0311] Cathode made of magnesium:silver (10:90), 100 nm

[0312] Subsequently, the IPCE (Incident Photon to Charge Carrier Efficiency) of the initial devices is determined using a PTS-2-QE, Photonic Solutions (UK) at the maximum absorption in the wavelength range 400-700 nm at a voltage of 9 V (Table 2).

[0313] Table 2: Structure of bi-layer photodiodes (BLPD)

[0314] Table 3: Materials used

[0315]

[0316] Example: Production of OLEDs

[0317] 1) Vacuum-processed devices:

[0318] 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).

[0319] 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). These coated glass plates form the substrates onto which the OLEDs are applied.

[0320] 1a) Blue Fluorescence OLED Components - BF:

[0321] The compounds according to the invention can be used in the hole injection layer (HIL), hole transport layer (HTL), and electron blocking layer (EBL). 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 4) and an emitting dopant (emitter) D, which is admixed to the matrix material(s) by co-evaporation in a specific volume fraction. A value such as SMB:D (97:3%) means that the SMB material is present in the layer in a volume fraction of 97% and the dopant D in a volume fraction of 3%. Analogously, the electron transport layer can also consist of a mixture of two materials, see Table 4. The results are summarized in Table 5. The materials used to produce the OLEDs are shown in Table 8.

[0322] 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 characteristics (IUL characteristics) assuming a Lambertian radiation pattern, as well as the lifetime. The EQE is specified in (%) and the voltage in (V) at a luminance of 1000 cd / m². 2

[0323] The OLEDs have the following layer structure:

[0324] Substrat

[0325] Hole injection layer (HIL) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0326] Hole transport layer (HTL), see Table 4

[0327] Electron blocking layer (EBL), see Table 4

[0328] Emission layer (EML), see Table 4

[0329] Electron transport layer (ETL), see Table 4

[0330] Electron injection layer (EIL) made of ETM2, 1 nm

[0331] Cathode made of aluminum, 100 nm

[0332] Table 4: Structure of blue fluorescent OLED components

[0333] Table 5: Results of blue fluorescent OLED devices

[0334] 1 b) Phosphorescent OLED components:

[0335] The compounds A according to the invention can be used in the hole injection layer (HIL), the hole transport layer (HTL), the electron blocking layer (EBL), and in the emission layer (EML) as matrix material (host material) M (see Table 8) or A (see materials according to the invention). For this purpose, all materials are thermally vapor-deposited in a vacuum chamber. The emission layer always consists of at least one or more matrix materials M and a phosphorescent dopant Ir, which is admixed 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 in a volume fraction of 55%, M2 in a volume fraction of 35%, and Ir in 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 6. The results are summarized in Table 7. The materials used to manufacture the OLEDs are shown in Table 8. The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd / A), the power efficiency (measured in λm / W), and the external quantum efficiency (EQE, measured in percent) are determined as a function of the luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming a Lambertian radiation pattern, as well as the lifetime. The EQE is given in (%) and the voltage in (V) at a luminance of 1000 cd / m². 2 The lifetime is determined at a starting luminance of 1000 cd / m 2 certainly.

[0336] The OLEDs have the following layer structure:

[0337] Substrat

[0338] Hole injection layer (HIL) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0339] Hole transport layer (HTL), see Table 6

[0340] Electron blocking layer (EBL), see Table 6

[0341] Emission layer (EML), see Table 6

[0342] Hole blocking layer (HBL), see Table 6

[0343] Electron transport layer (ETL), made of ETM1:ETM2 (50%:50%), 30 nm

[0344] Electron injection layer (EIL) made of ETM2, 1 nm

[0345] Cathode made of aluminum, 100 nm

[0346] Table 6: Structure of phosphorescent OLED components

[0347] Table 7: Results of phosphorescent OLED devices

[0348] Table 8: Structural formulas of the materials used

Claims

Patent claims 1 . Compound of formula (1 ), Formula (1 ) wherein a group according to one of the formulas (2-1 ) to (2-7) is condensed onto the two positions marked with * to form a heteroaromatic five-membered ring, where the symbols used are: X is the same or different at each occurrence and stands for CR a or N, where a maximum of 2 non-adjacent X per cycle represents N; Y is a single bond, BR b , C(R b )2, Si(R b )2, Common European Court of Human Rights b 2, NR b , R b P(O), 0, S, SO, SO2, Se or Te; X 1 stands for N, CR, the same or different at each occurrence C or CZ, provided that not both X 1 stand for N; Y 1 is the same or different for each occurrence NR C , O, S, Se or Te; Z is an electron acceptor group; Z can be substituted with R c also form a ring system; R a , R b is, at each occurrence, the same or different: H, D, OH, F, CI, Br, I, CN, NO2, N(R 1 )2, C(=O)N(R 1 )2, C(R 1 )3, Si(R 1 )3, Ge(R 1 )3, B(R 1 )2, C(=O)R 1 , P(=O)(R 1 )2, P(R 1 )2, S(=O)R 1 , S(=O)2R 1 , OSO2R 1 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 1 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R 1 C=CR 1 , C=C, Si(R 1 )2, C=O, C=S, C=Se, C=NR1 , C(=O)O, C(=O)NR 1 , NR 1 , P(=O)(R 1 ), Se, Te, BR 1 , Ge(R 1 )2, O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 may be substituted, or an arylthio or heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 may be substituted, or a diarylamino, aryl-heteroarylamino, diheteroarylamino group with 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R 1 may be substituted, or an aralkyl 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 R1 be substituted can; two radicals R a , R b and / or R c also form a ring system with each other or with another group; R c is, at each occurrence, the same or different: H, D, OH, F, CI, Br, I, CN, NO2, N(R 1 )2, C(=O)N(R 1 )2, C(R 1 )3, Si(R 1 )3, Ge(R 1 )3, B(R 1 )2, C(=O)R 1 , P(=O)(R 1 )2, P(R 1 )2, S(=O)R 1 , S(=O)2R 1 , OSO2R 1 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 1 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R1 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 ), Se, Te, BR 1 , Ge(R 1 )2, O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 may be substituted, or an arylthio or heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 may be substituted, or a diarylamino, aryl-heteroarylamino, diheteroarylamino group with 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R 1may be substituted, or an aralkyl 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 can be substituted; two radicals R a , R b and / or R c also form a ring system with each other or with another group; R 1 is the same or different at each occurrence: H, D, F, CI, Br, I, CN, NO2, N(R 2 )2, C(=O)R 2 , P(=O)(R 2 )2, P(R 2 )2, B(R 2 )2, C(R 2 )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 a Alkenyl group with 2 to 40 C atoms, each with one or more radicals R 2 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R 2C=CR 2 , C=C, Si(R 2 )2, C=O, C=S, C=Se, C=NR 2 , C(=O)O, C(=O)NR 2 , NR 2 , P(=O)(R 2 ), O, S, SO or SO2 and where one or more H atoms can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2 may be substituted, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms which may be substituted with one or more radicals R 2 may be substituted, or a combination of these systems; two or more, preferably adjacent, radicals R 1 form a ring system; one or more radicals R 1form a ring system with another part of the compound; R 2 is selected, identically or differently at each occurrence, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, CI, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, where two or more, preferably adjacent, substituents R 2 form a ring system with each other.

2. A compound according to claim 1, selected from the compounds of formulas (3-1) to (3-14), Formula (3-13) Formula (3-14) wherein the symbols used have the meanings given in claim 1.

3. A compound according to claim 1 or 2, selected from the compounds of formulas (4-1) to (4-14), Formula (4-3) Formula (4-4) Formula (4-13) Formula (4-14) wherein the symbols used have the meanings given in claim 1.

4. A compound according to one or more of claims 1 to 3, characterized in that Y is a single bond, C(R b )2, or S stands.

5. Compound according to one or more of claims 1 to 4, characterized in that Y 1 stands for S or Se, the same or different at each occurrence.

6. Compound according to one or more of claims 1 to 5, characterized in that the electron acceptor group Z is an organic group having a LUMO of < -2.8 eV, preferably < -2.9 eV.

7. A compound according to one or more of claims 1 to 6, characterized in that the group Z is selected from: (A) an alkenyl group having 2 to 20 C atoms, which may be substituted by one or more radicals R, where R has the same meanings as R a to R e in claim 1 and wherein one or more non-adjacent CH2 groups may be replaced by O, S, Se or Si(R)2, with the proviso that the alkenyl group has at least two CN groups or at least one CN group and one substituted carbonyl group; the alkenyl group may be substituted with R c form a ring system; (B) a terminal alkenyl group having 2 to 10 C atoms, which may be substituted by one or more substituents R, where R has the same meanings as R a to R ein claim 1 and wherein the terminal C atom is substituted with a group -C(=O)-LC(=O)-; wherein the group L is a divalent organic group; (C) an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R, with the proviso that the group has at least two CN groups; R is analogous to R a to R e defined in claim 1.

8. A compound according to one or more of claims 1 to 7, characterized in that group Z is selected from the structures of formulas (Z-1), (Z-1 ') and (Z-2), Formula (Z-1) Formula (Z-1 ') Formula (Z-2) where R and R 1 have the meanings given in claims 1 and 4, the dashed bond represents the attachment point and furthermore: R' stands for CN or for C(=O)R", where R" stands for OH, OD, an alkyl group with 1 to 6 C atoms or an alkoxy group with 1 to 6 C atoms X is 0, S or Se; p is 0, 1 or 2; or that the group Z represents a group of formula (Z-3), where the dashed bond represents the linkage of this group, R has the meanings given in claim 4 and furthermore: L is a bivalent aryl or heteroaryl group having 5 to 14 aromatic ring atoms, each of which may be substituted by one or more radicals R, or a group according to one of the formulas -NR-C(=O)-NR-, -NR-C(=S)-NR, -NR-C(=C(CN)2)-NR, -CR2-CR2-, -CR2-CR2-CR2-, -CR2-C(=O)-CR2- or -NR-NR-; or that group Z represents a group according to formula (Z-4), where the dashed bond represents the linkage of this group, R has the meanings given in claim 4 and furthermore: X 1is the same or different on each occurrence CR or N, with the proviso that a maximum of three X 1 represent N and that a maximum of two N atoms are directly bonded to each other, and further with the proviso that at least two groups X 1 represent C-CN; or that the group Z represents a group of formula (Z-5), where the dashed bond represents the linkage of this group, R has the meanings given in claim 4 and furthermore: R"' is an optionally deuterated alkyl group having 1 to 6 C atoms; or the two groups R"' together form a ring and represent -CR2-CR2- or -CR2-CR2-CR2-, where R in each case preferably represents H, D or an optionally deuterated alkyl group having 1 to 6 C atoms and several radicals R can also form a ring with each other.

9. Compound according to one or more of claims 1 to 8, characterized in that the group Z is selected from the structures of the formulas (Z-1-1), (Z-1-2), (Z-1-3), (Z-2-1), (Z-2-2), (Z-2-3) and (Z-2-4), where these groups may also be partially or completely deuterated, where the dashed bond represents the attachment site, R represents H, D, optionally deuterated methyl or CN and R 1 equal or differently at each occurrence represents H, D or optionally deuterated methyl; or that group Z is selected from the structures of formulas (Z-3-1) to (Z-3-9), (Z-3-9) wherein the dashed bond represents the linkage of this group and R has the meanings given in claim 4; or that the group Z represents a structure of the formula (Z-4-1), wherein the dashed bond represents the linkage of this group, R has the meanings given in claim 4 and at least two groups R represent CN; or that the group represents a structure of the formula (Z-5-1), (Z-5-1) wherein the dashed bond represents the attachment of this group and R"' has the meanings given in claim 5 and the group can optionally be deuterated.

10. A compound according to one or more of claims 1 to 9, characterized in that the substituents R, R a , R b , R c are selected, identically or differently at each occurrence, from the group consisting of H, D, F, CN, Si(R 1 )s, B(OR 1 )2, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl group is in each case substituted with one or more radicals R 1may be substituted, or an aromatic or heteroaromatic ring system with 6 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 1 can be substituted.

11. A compound according to one or more of claims 1 to 3 or 10, characterized in that Y at each occurrence, identically or differently, represents a single bond, BR b , C(R b )2, NR b or O.

12. Compound according to one or more of claims 1 to 3, 10 or 11, characterized in that Y 1 same or different for each occurrence for NR C , O or S.

13. Composition comprising at least one compound according to one or more of claims 1 to 12 and at least one further organic functional material.

14. Use of a compound according to one or more of claims 1 to 12 or a composition according to claim 13 in an electronic device.

15. An electronic device comprising at least one compound according to one or more of claims 1 to 12 and / or a composition according to claim 13.

16. Electronic device according to claim 15, which is an organic optical detector, an organic photoreceptor and an organic electronic sensor, characterized in that the compound according to one or more of claims 1 to 10 is used as a photosensitizer in a light-absorbing layer.

17. Electronic device according to claim 15, which is an organic electroluminescent device, characterized in that the device comprises an anode, a cathode and at least one emitting layer, wherein at least one organic layer which is an emitting layer, hole transport layer, Electron transport layer, hole blocking layer, electron blocking layer or another functional layer, comprises at least one compound according to one or more of claims 1 to 3 and 10 to 12.

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