WO2025021855A1 - Materials for organic light-emitting devices and organic sensors - Google Patents

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

Materials for organic light-emitting devices and organic sensors

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.

Electronic devices containing organic, organometallic and/or polymer 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 polymer light-emitting diodes (OLEDs or PLEDs) in display devices, or organic photoreceptors in copiers. Organic solar cells (O-SC), organic field-effect transistors (O-FET), organic thin-film transistors (O-TFT), organic switching elements (O-IC), organic optical amplifiers and organic laser diodes (O-lasers) are at an advanced stage of development and may become very important in the future.

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 in terms of service life, but also in terms of the efficiency and operating voltage of the device.

Electronic devices in the sense of this invention are understood to mean organic electronic devices which contain organic semiconductor materials as functional materials. In particular The electronic devices represent electroluminescent devices such as OLEDs or photosensitizers.

The structure of OLEDs in which organic compounds are used as functional materials is known to those skilled in the art. In general, OLEDs are understood to be electronic devices that have one or more layers that comprise organic compounds and emit light when a voltage is applied.

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

Electronic devices usually 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 can 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.

The hole transport layers and electron transport layers, but also the matrix materials of the emitting layer, have a major influence on the performance data of electronic devices.

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, the object of the present invention is 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.

Surprisingly, it has been found that certain compounds described in more detail below solve this problem, are very suitable for use in electronic devices and lead to organic optical detectors or OLEDs which have very good properties, particularly with regard to service life, efficiency and operating voltage. These compounds, as well as electronic devices, particularly organic optical detectors or OLEDs, which contain such compounds, are therefore the subject of the present invention. The type of use depends on the type of substitution.

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

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,

Formula (2-1) Formula (2-2) Formula (2-3) Formula (2-4)

Formula (2-5) Formula (2-6) Formula (2-7) 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 stand for N;

Y is a single bond, BR ^b , C(R ^b )2, Si(R ^b )2, GeR ^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 , O or S;

X ^I stands at each occurrence, the same or different, for N, CR ^C or CZ, with the proviso that not both X ¹ stand for N;

Y ¹ is the same or different at each occurrence and is NR ^C , O, S, Se or Te;

Z is an electron acceptor group; Z can also form a ring system with R ^c ;

R ^a , R ^b is, identically or differently on each occurrence, 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) ₂ R 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 thio- alkoxy group having 3 to 40 C atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group can each be substituted by one or more radicals R ¹ , where one or more non-adjacent CH2 groups can be replaced by R ¹ C=CR ¹ , C=C, Si(R ¹ )2, C=O, C=S, C=Se, C=NR ¹ , C(=O)O, C(=O)NR ¹ , NR ¹ , P(=O)(R ¹ ), Se, Te, BR ¹ , Ge(R ¹ )2, O, S, SO or SO2, or an aromatic aryl or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or an arylthio or heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or an 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 ; two radicals R ^a , R ^b and/or R ^c can also form a ring system with each other or with another group;

R ^c is, identically or differently on each occurrence, 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) ₂ R 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, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group can each be substituted by one or more radicals R ¹ , where one or more non-adjacent CH2 groups can be replaced by R ¹ C=CR ¹ , C=C, Si(R ¹ )2, C=O, C=S, C=Se, C=NR ¹ , C(=O)O, C(=O)NR ¹ , NR ¹ , P(=O)(R ¹ ), 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, which can each be substituted by one or more radicals R ¹ , or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R ¹ , or an arylthio or heteroarylthio group having 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R ¹ , or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R ^1. 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 ; two radicals R ^a , R ^b and/or R ^c can also form a ring system with each other or with another group;

R ¹ is, identically or differently on 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 may be substituted by one or more radicals R ² , where one or more non-adjacent CH2 groups are represented by R ² C=CR ² , C=C, Si(R ² ) 2, C = O, C = S, C = Se, C = NR ² , C ( = O) O, C ( = O) NR ² , NR ² , P ( = O) (R ² ), O, S, SO or SO 2 and where one or more H atoms can be replaced by D, F, CI, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which can be substituted by one or more R ² radicals, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which can be substituted by one or more R ² radicals, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which can be substituted by one or more R ² radicals, or a combination of these systems; two or more, preferably adjacent, radicals R ¹ can form a ring system with one another; one or more radicals R ¹ can form a ring system with another part of the compound;

R ² is selected on each occurrence, identically or differently, 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 can be replaced by D, F, CI, Br, I or CN and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, where two or more, preferably adjacent, substituents R ² can form a ring system with each other;

Electron acceptor groups are generally known to the person skilled in the art. In general, this is a group that is able to accept electrons, i.e. to be reduced. An electron acceptor group in the sense of the present invention is preferably an organic group that has a LUMO of < -2.8 eV, preferably

< -2.9 eV, particularly preferably < -3.0 eV and most preferably

< -3.2 eV. The LUMO of the electron acceptor group in the sense of the present compound is defined as the LUMO of the group Z, which has a hydrogen atom instead of the compound represented by formula (1) and formula (2-1) to (2-7). The LUMO is determined by quantum chemical calculation, as generally described in the examples section below.

An aryl group in the sense of this invention contains 6 to 40 C atoms; a heteroaryl group in the sense 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 aromatic ring systems.

An electron-poor heteroaryl group in the sense of the present invention is a heteroaryl group which has at least one heteroaromatic six-membered ring with 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 poor heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline or quinoxaline.

An aromatic ring system in the sense 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 in the sense 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 in the sense of this invention is to be understood as a system which does not necessarily only contain 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 to be understood as aromatic ring systems in the sense 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.

An electron-rich heteroaromatic ring system is characterized by the fact that it is a heteroaromatic ring system that does not contain any electron-poor heteroaryl groups. An electron-poor heteroaryl group is a six-membered heteroaryl group with at least one nitrogen atom or a five-membered heteroaryl group with at least two heteroatoms, one of which is a nitrogen atom and the other is oxygen, sulfur or a substituted nitrogen atom, where further aryl or heteroaryl groups can be condensed onto these groups. In contrast, electron-rich heteroaryl groups are five-membered 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 can be fused on. Examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene or indenocarbazole. An electron-rich heteroaryl group is also called an electron-rich heteroaromatic residue.

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.

In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which can contain 1 to 20 C atoms and in which individual H atoms or CH2 groups can also be substituted by the abovementioned groups, preferably means 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. An alkoxy group with 1 to 40 carbon atoms is preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, Cycloheptyloxy, n-octyloxy, cyclo-octyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. A thioalkyl group with 1 to 40 C atoms includes in particular methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio,

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

2-Ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, Ethynylthio, propynylthio, butynylthio, pentinylthio, hexynylthio, heptynylthio or octynylthio are understood. general Alkyl, alkoxy or thioalkyl groups according to the present invention can be straight-chain, branched or cyclic, wherein one or more non-adjacent CH2 groups can be replaced by the above-mentioned groups; furthermore, one or more H atoms by D, F, CI, Br, I, CN or NO2, preferably F, CI or CN, more preferably F or CN, particularly preferably CN.

For the purposes of the present invention, the generic term “alkyl group” includes both straight-chain alkyl groups and branched or cyclic alkyl groups. The same applies to alkenyl, alkynyl, alkoxy and thioalkoxy groups.

An aromatic or heteroaromatic ring system with 5 to 60 or 5 to 40 aromatic ring atoms, which can be substituted with the above-mentioned radicals and which can be linked to the aromatic or heteroaromatic ring via any position, is understood to mean in particular groups which are 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-quinoline, phenothiazine, Phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazine-imidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, Hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinazoline, Quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene,

2.3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline,

1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadi- azole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine,

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

In the context of the present description, the phrase "two or more radicals can form a ring" is to be understood to mean, among other things, that the two radicals are linked to one another by a chemical bond with formal elimination of two hydrogen atoms. This is illustrated by the following scheme.

Rin education

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 bound, forming a ring. This is illustrated by the following scheme:

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),

wobei die verwendeten Symbole die oben genannten Bedeutungen auf- weisen.

where the symbols used have the meanings given above.

The structure of formula (2-1 a) is particularly suitable for compounds which are used in organic electroluminescent devices, in which case Y ¹ preferably represents NR ^C , O or S. The structures of formulae (2-1 b) and (2-2a) to (2-7a) are particularly suitable for compounds which are used in photoreceptors, in which case Y ¹ preferably represents S, Se or Te, which are identical or different on each occurrence, particularly preferably S or Se, and very particularly preferably S.

In a preferred embodiment, a maximum of three Xs stand for N, particularly preferably a maximum of two Xs stand for N, very particularly preferably a maximum of one X stands for N and particularly preferably all Xs stand for CR ^a . In a preferred embodiment, at least one R ^c is an electron acceptor group or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , where two adjacent R ^c can also form an electron acceptor group or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ . Compounds having an electron acceptor group are particularly suitable as photosensitizers, while the compounds having an aromatic or heteroaromatic ring system are particularly suitable as materials for OLEDs, in particular as triplet matrix materials. Such compounds preferably do not have an electron acceptor group.

In a preferred embodiment of the invention, at least one group X ¹ , preferably exactly one group X ^{1 ,} is CZ or a group CR ^C , where R ^c is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R ¹ .

In a preferred embodiment, a maximum of one X ¹ stands for CZ.

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

formula (1 -1 ) where the symbols used have the meanings given above.

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),

Formula (3-11) Formula (3-12)

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

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),

Formula (4-1 ) Formula (4-2)

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 stands for a single bond, BR ^b , C(R ^b )2, NR ^b or 0.

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. Particularly preferably, these compounds also have at least one group Z, particularly preferably exactly one group Z.

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

In a preferred embodiment, the compound is particularly suitable for photosensitizers, where Y ¹ is the same or different on each occurrence and is S or Se, preferably S. Particularly preferably, these compounds also have at least one group Z, particularly preferably exactly one group Z.

In a preferred embodiment, the compound is particularly suitable for photosensitizers, where Y ¹ on each occurrence is the same or different and represents S or Se, preferably S, and Y represents a single bond or S. Particularly preferably, these compounds also have at least one group Z, particularly preferably exactly one group Z.

The group Z is an electron acceptor group. 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 with one another, or aromatic or heteroaromatic ring systems substituted by at least two CN groups are particularly suitable for this purpose. These electron acceptor groups are described in more detail below.

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 can form a ring system with R ^c . In particular, it is a terminal alkenyl group which is substituted on the terminal C atom by two CN groups. R is defined analogously to R ^a above.

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 group Z are continuously conjugated with the 5-membered ring to which the group Z is bonded.

The term "conjugation" or "conjugated" is known to those skilled in the art. A continuous conjugation of the at least two CN groups of the Z group is formed as soon as alternating double and single bonds are present between the at least two CN groups or the at least one CN group and at least one substituted carbonyl group of the Z group and the 5-membered ring which comprises the Y ¹ group and to which the Z group is bonded. A further link between the previously mentioned conjugated groups, which occurs, for example, via an S, N or O atom, does not harm a 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 can 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 can form a ring system with the group R ^c .

Z is particularly preferably 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, where the two CN groups or the CN group and the substituted carbonyl group are preferably bonded terminally.

wobei R und R¹ die oben genannten Bedeutungen aufweisen, die gestrichelte Bindung die Anbindungsstelle darstellt und weiterhin gilt: 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 given above, the dashed bond represents the attachment point and furthermore:

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

X ^z is 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 can also optionally be deuterated:

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.

For formula (Z-2) the following applies:

R, which is bonded to the non-cyclic alkenyl group in formula (Z-2), is preferably the same or different on each occurrence and is 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.

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 . Preferably, this R is selected from H, D, methyl, CD3 or CN.

wobei die gestrichelte Bindung die Anbindungsstelle darstellt, R für H, D, optional deuteriertes Methyl oder CN steht und R¹ gleich oder verschieden bei jedem Auftreten für H, D oder optional deuteriertes Methyl, insbeson- dere für optional deuteriertes Methyl steht. 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 . The two groups R ¹ can also form a ring system with one another. Preferably, these groups R ¹ are identical or different on each occurrence and are 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 can also be partially or completely deuterated,

where the dashed bond represents the attachment point, R represents H, D, optionally deuterated methyl or CN and R ¹ , identical or different on each occurrence, represents H, D or optionally deuterated methyl, in particular optionally deuterated methyl.

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

wobei die gestrichelte Bindung die Anbindungsstelle darstellt.

where the dashed bond represents the attachment point.

In a further preferred embodiment of the invention, the group Z is a terminal alkenyl group with 2 to 10 C atoms, preferably with 2 to 4 C atoms and particularly preferably with 2 C atoms, which can be substituted with one or more substituents R and where the terminal C atom is substituted with a group -C(=O)-L-C(=O)-. The two C(=O) groups of the group -C(=O)-L-C(=O)- are each bonded to the terminal C atom of the alkenyl group, so that a cyclic group is formed. The group L is a divalent organic group.

wobei die gestrichelte Bindung die Anknüpfung dieser Gruppe darstellt, R analog zu R^a oben definiert ist und weiterhin gilt: L ist eine optional deuterierte bivalente Aryl- oder Heteroarylgruppe mitA 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 is defined analogously to R ^a above and furthermore: L is an optionally deuterated bivalent aryl or heteroaryl group with

5 to 14 aromatic ring atoms, preferably with 6 to 10 aromatic ring atoms, particularly preferably a phenylene group, which can each 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

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

wobei die gestrichelte Bindung die Anknüpfung dieser Gruppe darstellt und R die oben genannten Bedeutungen aufweist. Preferred embodiments of the formula (Z-3) are thus the structures of the 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.

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 identical 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 identical or different and are H, D or an optionally deuterated alkyl group having 1 to 6 C atoms. The R radicals 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 on each occurrence and are H, D or an optionally deuterated alkyl group having 1 to 6 C atoms, where several R radicals can also form a ring with one another. It is preferred if the R radicals which are bonded to a carbon atom which is adjacent to a carbonyl group are identical or different on each occurrence and are D or an optionally deuterated alkyl group having 1 to 6 C atoms, in particular D or methyl.

wobei die gestrichelte Bindung die Anknüpfung dieser Gruppe darstellt. Particularly preferred embodiments of the structure of formula (Z-3) are the structures of the following formulas (Z-3a) to (Z-3zz), whereby these structures can also be partially or completely deuterated,

where the dashed bond represents the attachment of this group.

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. R is defined analogously to R ^a above. Preference is given to compounds in which at least one CN group and preferably at least two CN groups are continuously conjugated with the 5-membered ring containing Y ¹ to which the aromatic or heteroaromatic ring system is bonded.

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 continuously conjugated with the 5-membered ring which comprises the group Y ¹ and to which the aryl or heteroaryl group is bound.

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 are formed between the CN group of the group Z and the 5-membered ring comprising the group Y ¹ .

wobei die gestrichelte Bindung die Anknüpfung dieser Gruppe darstellt, R analog zu R^a oben definiert ist und weiterhin gilt: 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 is defined analogously to R ^a above and furthermore:

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

wobei die gestrichelte Bindung die Anknüpfung dieser Gruppe darstellt, R wie oben definiert ist und mindestens zwei Gruppen R für CN stehen. In a preferred embodiment of the formula (Z-4), a maximum of two groups X ² stand for N, particularly preferably a maximum of one group X ² stands for N and very particularly preferably all groups X ² stand for CR. A preferred embodiment of the formula (Z-4) is thus the structure of the formula (Z-4-1 ),

where the dashed bond represents the attachment of this group, R is as defined above and at least two R groups represent CN.

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

wobei die gestrichelte Bindung die Verknüpfung der Gruppe andeutet und R die oben genannten Bedeutungen aufweist. Bevorzugt sind maximal zwei Reste R ungleich H oder D, besonders bevorzugt ist maximal ein Rest R ungleich H oder D und ganz besonders bevorzugt stehen alle Reste R für H oder D.

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.

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

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 can be substituted by one or more substituents R and where the terminal C atom is substituted by two groups -SO2R"'. The substituent R"' is preferably an alkyl group having 1 to 6 C atoms, where the two substituents R"' can also form a ring system with one another.

wobei die gestrichelte Bindung die Anknüpfung dieser Gruppe darstellt, R analog zu R^a bis R^e oben definiert ist und weiterhin gilt: 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 is defined analogously to R ^a to R ^e above 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 stand for -CR2-CR2- or -CR2-CR2-CR2-, where R in each case preferably stands for 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.

wobei die verwendeten Symbole die oben genannten Bedeutungen aufweisen und die Gruppe optional deuteriert sein kann. 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.

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 is also given for each of these structures, which is defined according to the invention as the LUMO for the corresponding compound which carries an H instead of the dashed bond, where the LUMO was calculated as described in the example section.

Preferred embodiments for an electron acceptor group or group Z are the formulas (Z-1) to (Z-5) given 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) given 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) given above. The structures (Z-1-1) and (Z-2a) to (Z-2d) are particularly preferred.

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

Particularly preferred are compounds for which:

In addition, the following compounds are preferred for photosensitizers:

Compounds of the formula (5-1 ) for which Y ¹ stands for S or Se, preferably S, and Y stands for a single bond or S.

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

If Y is C(R ^b ) 2 , R ^b is preferably the same or different on each occurrence and is 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 fully deuterated and may be substituted by one or more radicals R ¹ , or an aryl or heteroaryl group having 5 to 12 aromatic ring atoms, preferably a phenyl group, which may be partially or fully deuterated and may be substituted by one or more radicals R ¹ , where the two radicals R ^b of the 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 radicals R ^b is preferably a 5-membered ring or a 6-membered ring. If 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 fully deuterated and where the two R ^b groups may also form a ring with one another, or the two R ^b groups together with the C atom to which they are bound form a cyclopentyl, cyclohexyl or adamantanyl group, which may also be partially or fully deuterated. R ^b particularly preferably represents methyl, which may also be partially or fully deuterated. In a further preferred embodiment of the invention, the radical R ^a is 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, where the alkyl group can be substituted in each case by one or more radicals R ¹ , or an aryl or heteroaryl group having 5 to 12 aromatic ring atoms, preferably a phenyl group, which can be substituted by one or more radicals R ¹ , where the radical R ^a can form a ring together with the radical R ^1. In a particularly preferred embodiment of the invention, the radical R ^a is H, D, optionally deuterated methyl or optionally deuterated phenyl, very particularly preferably H or D.

If two radicals, 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 one another, this can be mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic. The radicals which form a ring system with one another can be adjacent, ie these radicals are bonded to the same carbon atom or to carbon atoms which are directly bonded to one another, or they can be further apart from one another.

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.

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

Preferred substituents R, R ^a , R ^b and R ^c are described below.

In a preferred embodiment of the invention, R, R ^a , R ^b and R ^c are the same or different on each occurrence and are selected from the group consisting of H, D, F, CN, Si(R ¹ )s, B(OR ¹ )2, a straight-chain alkyl or an alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, where the alkyl group may be substituted in each case by one or more radicals R ¹ , or an aromatic or heteroaromatic ring system having 6 to 40 aromatic ring atoms, which may be substituted in each case by one or more radicals R ¹ ; two or more radicals may form a ring system with one another. In a particularly preferred embodiment of the invention, R, R ^a , R ^b and R ^c are the same or different on each occurrence and are 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 can in each case be substituted by one or more radicals R ¹ , 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, which can in each case be substituted by one or more radicals R ¹ ; two or more radicals can form a ring system with one another.

It may be preferred if at least one of the substituents R, R ^a , R ^b , and R ^{c ,} identical or different 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 may in each case be substituted by one or more radicals R ¹ .

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 can be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which can be linked via the 1-, 2-, 3- or 4-position, naphthalene, in particular 1- or 2-linked naphthalene, indole, benzofuran, benzothiophene, Carbazole, which can be linked via the 1-, 2-, 3-, 4- or 9-position, dibenzofuran, which can be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, which can be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which can be substituted by one or more radicals R, R ¹ or R ² .

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

R-58

R-114 R-115 R-116 R-117

wobei R¹ die oben genannten Bedeutungen aufweist, die gestrichelte Bindung die Bindung darstellt und weiterhin gilt:

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

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

A ¹ is, identically or differently at each occurrence, 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 stands for BR ¹ , C=O, NR ¹ , 0 or S;

A ² is, identically or differently on each occurrence, C(R ¹ ) 2, NR ¹ , 0 or S; p is 0 or 1, where p = 0 means that the group Ar ³ is not present and that the corresponding aromatic or heteroaromatic group is bonded directly 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 equal to 1; r is 0 or 1 , where r = 0 means that no group A ¹ is bonded at this position and residues R ¹ are bonded to the corresponding carbon atoms instead.

In a preferred embodiment, Ar ³ comprises divalent 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 are the bond to the aromatic or heteroaromatic group is after R-1 to R-184.

If the above-mentioned groups R-1 to R-184 have several groups A ¹ , all combinations from the definition of A ¹ are possible. Preferred embodiments are then those in which one group A ¹ stands for C(R ¹ )2, NR ¹ , 0 or S and the other group A ¹ stands for C(R ¹ )2, NR ¹ , 0 or S.

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

If A ¹ is C(R ¹ ) 2 , the substituents R ¹ which are bonded to this carbon atom are preferably identical or different on each occurrence and 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 ² . R ¹ is very particularly preferably a methyl group or a phenyl group. The radicals R ¹ can also form a ring system with one another, resulting in a spiro system.

Other suitable groups R, R ^a , R ^b and R ^c are groups of

Formula -Ar ⁴ -N(Ar ² )(Ar ³ ), where Ar ² , Ar ³ and Ar ⁴ , the same or different at each occurrence, represent an aromatic or heteroaromatic ring system with 5 to 24 aromatic ring atoms, which can each be substituted by one or more radicals R ¹ . The total number of aromatic ring atoms of Ar ² , Ar ³ and Ar ⁴ is a maximum of 60 and preferably a maximum of 40.

Ar ⁴ and Ar ² can be connected to one another and/or Ar ² and Ar ³ can also be connected to one another by a group selected from C(R ¹ ) 2, NR ¹ , O or S. Preferably, Ar ⁴ and Ar ² are connected to one another or Ar ² and Ar ³ are connected to one another ortho to the position of the connection to the nitrogen atom. In a further embodiment of the invention, none of the groups Ar ² , Ar ³ or Ar ⁴ are connected to one another.

Ar ⁴ is preferably an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, preferably with 6 to 12 aromatic ring atoms, each of which can be substituted by one or more radicals R ¹ . Ar ⁴ is particularly preferably selected from the group consisting of ortho-, meta- or para-phenylene or ortho-, meta- or para-biphenyl, each of which can be substituted by one or more radicals R ¹ , but is preferably unsubstituted. Ar ⁴ is very particularly preferably an unsubstituted phenylene group.

Preferably, Ar ² and Ar ³ are the same or different on each occurrence and are an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may each be substituted by one or more radicals R ¹ . Particularly preferred groups Ar ² and Ar ³ are the same or different on each occurrence and are 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-

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 -,

4- or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene or triphenylene, each of which may be substituted by one or more radicals R ¹ . Ar ² and Ar ³ are particularly preferably the same or different on each occurrence and are selected from the group consisting of from 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.

In a further preferred embodiment of the invention, R ¹ is the same or different on each occurrence and is 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 may in each case be substituted by one or more radicals R ² , or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R ² ; two or more radicals R ¹ may form a ring system with one another. In a particularly preferred embodiment of the invention, R ¹ is the same or different on each occurrence and is 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 may in each case be substituted by one or more radicals R ² , but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, which may in each case be substituted by one or more radicals R ² , but is preferably unsubstituted; two or more radicals R ¹ can form a ring system with one another.

In a further preferred embodiment of the invention, R ² is the same or different on each occurrence and is 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.

In a further embodiment of the invention, R ^c and, if present, Z, form an aryl or Heteroaryl group with 4 to 14 aromatic ring atoms, which can be substituted with R ¹ .

In compounds according to the invention which are processed by vacuum evaporation, the alkyl groups preferably have no more than five C atoms, particularly preferably no more than 4 C atoms, very particularly preferably no more than 1 C atom. For compounds which are processed from solution, compounds which are substituted with alkyl groups, in particular branched alkyl groups, with up to 10 C atoms or which are substituted with oligoarylene groups, for example ortho-, meta-, para- or branched terphenyl or quaterphenyl groups, are also suitable.

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

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

The compounds according to the invention can in principle be prepared by various methods. However, the methods described below have proven to be particularly suitable.

Therefore, a further subject matter of the invention is 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 according to formula (1) is obtained by intramolecular cyclization. Optionally, further radicals can be introduced by coupling reactions.

The synthesis of the compounds according to the invention can be carried out, among other things, according to the following schemes. First, the parent compound (4) is converted 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 intramolecularly cyclized using palladium-2-phosphine catalysis, see Scheme 1. Analogously, compounds with two or three fused five-membered rings can be used as starting materials.

Der so dargestellte Grundköper (4) kann dann weiter via SeAr-Reaktion, z. B. einer Halogenierung, bevorzugt einer Bromierung mit N-Bromsuccin- imid, einer Formylierung oder Acylierung bzw. Nitrierung, etc., in o-Position zu Y weiter funktionalisiert werden. Die reaktiven Halogen- Intermediate können in C-C-Kupplungen (A) wie einer Suzuki-, Negishi, Grignard-Cross, Sonogashira-Kupplung, etc., bzw. in C-N-Kupplungen (B) wie Buchwald-Hartwig- oder Ullmann-Kupplung, die Carbonyl-Intermediate können mittels Knoevenagel-Kondensation (C), z.B. mit Malonsäuredinitril, weiter zu den weiterne erfindungsgemäßen Verbindungen umgesetzt werden (Schema 2). Scheme 1 :

The basic structure (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 or acylation or nitration, etc. The reactive halogen intermediates can be further converted to the other compounds according to the invention in CC couplings (A) such as a Suzuki, Negishi, Grignard-Cross, Sonogashira coupling, etc., or in CN couplings (B) such as Buchwald-Hartwig or Ullmann coupling, the carbonyl intermediates can be further converted to the other compounds according to the invention by means of Knoevenagel condensation (C), e.g. with malononitrile (Scheme 2).

Scheme 2:

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

The invention also relates to an oligomer, polymer or dendrimer containing one or more compounds according to formula (1) or the preferred embodiments, wherein the bond(s) to the Oligomer, polymer or dendrimer can occur at any position in formula (1).

Of particular interest are compounds according to the invention which are characterized by a high glass transition temperature. In this context, preference is given in particular to compounds according to the invention of the formula (1) or the preferred embodiments which have a glass transition temperature of at least 70 °C, particularly preferably of at least 110 °C, very particularly preferably of at least 125 °C and especially preferably of at least 150 °C, determined according to DIN 51005 (version 2005-08).

For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes, formulations of the compounds according to the invention are required. These formulations can be, for example, solutions, dispersions or emulsions. It may be preferable 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, phenetol, 1,4-diisopropylbenzene, di-benzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, di- ethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetra-ethylene 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. A further subject matter of the present invention is therefore a formulation or a composition containing 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 which 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.

Yet another subject matter of the present invention is therefore a composition containing a compound according to the invention and at least one further organic functional material. Functional materials are generally the organic or inorganic materials which are introduced between the anode and the cathode. The organic functional material is preferably selected from the group consisting of photosensitizers, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocking materials and hole blocking materials, preferably photosensitizers, electron transport materials, electron injection materials or hole blocking materials.

A further subject matter 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.

Yet another subject of the present invention is an electronic device containing at least one compound according to the invention. An electronic device in the sense of the present The invention relates to a device which contains at least one layer which contains at least one organic compound. The component can also contain inorganic materials or layers which are made entirely of inorganic materials.

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” (D. M. 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. Organic optical detectors are particularly preferred.

The organic optical detector contains a cathode, an anode and at least one light-absorbing layer. In addition to these layers, it can 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 can also be introduced between two light-absorbing layers, which, for example, have an exciton-blocking function. It should be noted, however, that not all of these layers necessarily have to be present. The organic optical detector can contain one light-absorbing layer, or it can contain several light-absorbing layers.

The compound according to the invention can be used in different

Layers can be used, depending on the exact structure. Preferably a Organic optical detector containing a compound according to formula (1) or (2) or the preferred embodiments set out 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 which is absorbed by the photosensitizer.

If the compound according to the invention is used as a photosensitizer in a light-absorbing layer, a suitable co-material which is known as such is preferably used. The co-material is used either as a mixture with the photosensitizer or in a layer which is adjacent to the layer containing the photosensitizer.

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-bis-carbazolylbiphenyl) 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. 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. 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. B. according to EP 652273 or WO 2009/062578, diazasilol or tetraazasilol derivatives, e.g. according to WO 2010/054729, diazaphosphol derivatives, e.g. according to WO 2010/054730, bridged carbazole derivatives, e.g. according to WO 2011/042107, WO 2011/060867, WO 2011/088877 and WO 2012/143080, triphenylene- derivatives, e.g. 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.

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, hole blocking materials. Particular preference is given to using subphthalocyanines, subphthalocyanine derivatives, fullerenes or fullerene derivatives, among others. Such compounds are known to the person skilled in the art for use in organic optical detectors.

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.

Preferred subphthalocyanines, subphthalocyanine derivatives, fullerenes or fullerene derivatives which can be used are described, inter alia, in European patent application EP 3848374 A1, which is incorporated by reference for disclosure purposes. These materials are set out in particular on pages 84 to 86 (cf. paragraphs [322] to [332]).

In the further layers of the organic optical detector according to the invention, all materials can be used as are usually used according to the prior art. The person skilled in the art can therefore, without inventive step, 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.

Also preferred is an organic optical detector, characterized in that one or more layers are provided with a sublimation The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10' ⁵ mbar, preferably less than 10' ⁶ mbar. However, it is also possible for the initial pressure to be even lower, for example less than 10' ⁷ mbar.

An organic optical detector is also preferred, characterized in that one or more layers are coated using the OVPD (Organic Vapour Phase Deposition) method or with the aid of carrier gas sublimation. The materials are applied at a pressure between 10' ⁵ mbar and 1 bar. A special case of this method is the OVJP (Organic Vapour Jet Printing) method, in which the materials are applied directly through a nozzle and thus structured.

Also preferred is an organic optical detector, characterized in that one or more layers are produced from solution, such as by spin coating, or using any printing method, such as screen printing, flexographic printing, offset printing, LITI (light induced thermal imaging, thermal transfer printing), ink-jet printing or nozzle printing. Soluble compounds are required for this, which are obtained, for example, by suitable substitution.

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.

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.

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 the European patent application EP 3848374 A1, whereby this document is incorporated by reference for disclosure purposes. In this regard, reference is made in particular to the devices described in EP 3848374 A1. Figures 1 to 10, which are set out, inter alia, on pages 83 to 90 of the document EP 3848374 A1.

The device is also preferably an organic electroluminescent device comprising a cathode, anode and at least one emitting layer, wherein at least one organic layer, which can 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.

In addition to these layers, the organic electroluminescent device can 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 can also be introduced between two emitting layers, which, for example, have an exciton blocking function. It should be noted, however, that not all of these layers necessarily have to be present.

The organic electroluminescent device can contain one emitting layer or it can contain several emitting layers. If several emitting layers are present, these preferably have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, ie 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 showing 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 Electroluminescent device can also be a tandem OLED, especially for white-emitting OLEDs.

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

The organic electroluminescent device can contain one emitting layer, or it can 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.

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.

Suitable phosphorescent compounds (= triplet emitters) are in particular compounds which emit light, preferably in the visible range, when suitably excited and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. All luminescent complexes with transition metals or lanthanides are preferably regarded as phosphorescent compounds, in particular if they contain copper, molybdenum, tungsten, rhenium, Contain ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing indium, platinum or copper. In the context of the present invention, all luminescent indium, platinum or copper complexes are considered to be phosphorescent emitting compounds.

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 in accordance with 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 also possible for the person skilled in the art to use further phosphorescent complexes in combination with the compounds of formula (1) in organic electroluminescent devices without inventive step. Further examples are listed in a table below.

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.

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

An electron transport layer in the sense of the present application is a layer with an electron-transporting function between the cathode and the emitting layer.

In the context of the present application, electron injection layers and hole blocking layers are understood to mean certain 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 directly borders the cathode or is only separated from it 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 directly borders 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).

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, i.e. in a proportion of 100% in the electron transport layer, or it can be used in combination with one or more other compounds.

Hole transport layers or electron blocking layers of the electronic devices according to the invention can additionally comprise one or more p-dopants. p-dopants used according to the present invention are preferably those organic electron acceptor compounds which are 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.

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.

The proportion of matrix material in the emitting layer in this case 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.

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.

An emitting layer of an organic electroluminescent device can also comprise systems that contain a large number of matrix materials (mixed matrix systems) and/or a large number 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 are 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. The compounds of formula (1) are preferably 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 other 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.

The mixed matrix systems can contain one or more emitting compounds, preferably one or more phosphorescent compounds. In general, mixed matrix systems are preferably used in phosphorescent organic electroluminescent devices.

Particularly suitable matrix materials which can be used in combination with the compounds according to the invention as matrix components of a mixed matrix system are selected from the preferred matrix materials for phosphorescent compounds or the preferred matrix materials for fluorescent compounds mentioned below, depending on which type of emitting compound is 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.

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 which contains three substituted or unsubstituted aromatic or heteroaromatic ring systems which are directly bonded to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a condensed ring system, particularly preferably with at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. An aromatic anthraceneamine is understood to mean a compound in which a diarylamino group is directly bonded to an anthracene group, preferably in position 9. An aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably in positions 9, 10. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously, in which the diarylamino groups are preferably bonded to the pyrene 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 -fluorenediamines, for example according to WO 2008/006449, and dibenzoindenofluorenamines or -diamines, for example according to WO 2007/140847, and the indenofluorene derivatives with condensed aryl groups disclosed in WO 2010/012328. Also 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 bound 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.

Useful matrix materials, preferably for fluorescent compounds, include materials from different substance classes. Preferred matrix materials are selected from the classes of oligoaryls (e.g. 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthyl-anthracene), 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 with naphthalene, anthracene, benzanthracene and/or pyrene or atropisomers of these compounds, the oligoarylenevinylenes, the ketones, the phosphine oxides and the sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes which include anthracene, benzanthracene, benzophenanthrene and/or pyrene or atropisomers of these compounds. In the context of the present invention, an oligoarylene is understood to mean a compound in which at least three aryl or arylene groups are connected 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 benzanthracenyl-anthracene compounds disclosed in WO 2015/158409, the indenobenzofurans disclosed in WO 2017/025165 and the pyrene compounds disclosed in WO 2017/036573 disclosed phenanthryl-anthracenes.

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, diazasilol or tetraazasilol derivatives, e.g. according to WO 2010/054729, diazaphosphole derivatives, e.g. according to WO 2010/054730, bridged carbazole derivatives, e.g. according to WO 2011/042107, WO 2011/060867, WO 2011/088877 and WO 2012/143080, triphenylene derivatives, e.g. according to WO 2012/048781, lactams, e.g. according to WO 2011/116865 or WO 2011/137951, or dibenzofuran derivatives, e.g. B. according to WO 2015/169412, WO 2016/015810, WO 2016/023608, WO 2017/148564 or WO 2017/148565. Likewise, a further 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 which 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.

Particularly suitable hole-transporting matrix materials which are advantageously combined with compounds of the formula (1), as described above or preferably described, in a mixed matrix system can be selected from the compounds of the 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 the formula (1) are substituted by at least one electron-deficient heteroaryl group.

Formel (HH-6), wobei für die verwendeten Symbole und Indizes gilt: A further subject matter 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:

A ¹ is C(R ⁷ )2, NR ⁷ , 0 or S;

L is a bond, O, S, C(R ⁷ )2 or NR ⁷ ;

A is, at each occurrence, independently of each other, a group of

Formula (HH-4-1 ) Formula (HH-4-2);

X2 is the same or different at each occurrence and is CH, CR ⁶ or N, where a maximum of 2 symbols X2 N can be used;

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

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

R ⁶ is, identically or differently on each occurrence, 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 may in each case be substituted by one or more radicals R ⁷ and where one or more non-adjacent CH 2 groups may be replaced by Si(R ⁷ ) 2, C=O, NR ⁷ , O, S or CONR ⁷ , or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R ⁷ ; two radicals R ⁶ can also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another; Ars, identical or different at each occurrence, independently represents an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R ⁷ ;

R ⁷ is, identically or differently on 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, where the alkyl, alkenyl or alkynyl group may each be substituted by one or more radicals R ⁸ , where one or more non-adjacent CH2 groups are replaced by Si(R ⁸ )2, C=O, NR ⁸ , O, S or CONR ⁸ , or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, each of which may be substituted by one or more radicals R ⁸ ; two or more radicals R ⁷ can form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another, preferably the radicals R ⁷ do not form such a ring system;

R ⁸ is, identically or differently on 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 on each occurrence

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

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

In compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-5) or (HH-6), s is preferably 0 or 1 if the radical R ⁶ is different from D, or particularly preferably 0.

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 particularly preferably 0.

In compounds of the formulas (HH-1), (HH-2), (HH-3) or (HH-5), u is preferably 0 or 1 if the radical R ⁶ is different from D, or particularly preferably 0.

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.

In compounds of the 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.

In compounds of the 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.

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

In formula (HH-4-2), U ¹ or U ² is preferably a single bond or C(R ⁷ ) ₂ , where R ⁷ has a meaning as previously mentioned, particularly preferably U ¹ or U ² is a single bond. In formula (HH-4-2), q, q1 , q2 are preferably 0 or 1 if the radical R ⁶ is different from D.

In a preferred embodiment of the compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) which are reacted according to the invention with compounds of formula (1) or preferred compounds of Formula (1) can be combined as described above, R ⁶ is the same or different on each occurrence and is 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 may in each case be substituted by one or more radicals R ⁷ , or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, preferably having 5 to 40 ring atoms, which may in each case be substituted by one or more radicals R ⁷ .

In a preferred embodiment of the compounds of the 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 the formula (1) or preferred compounds of the formula (1), as described above, R ⁶ is the same or different on each occurrence and is selected from the group consisting of D or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may be substituted by one or more radicals R ⁷ .

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 can be linked via the 1-, 2-, 3- or 4-position, spirobifluorenyl, which can 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 can be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which can be linked via the 1-, 2-, 3- or 4-position dibenzothiophene, which can be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which can be substituted by one or more radicals R ⁷ . Ars is preferably unsubstituted. If A ¹ in formula (HH-2) or (HH-3) or (HH-6) is 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 may also be substituted by one or more radicals R ⁸ . In a particularly preferred embodiment, this substituent R ⁷ is the same or different on each occurrence and 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, and radicals derived from triazine, pyrimidine and quinazoline, which may be substituted by one or more radicals R ⁸ .

If A ¹ in formula (HH-2) or (HH-3) or (HH-6) is C(R ⁷ ) ₂ , the substituents R ⁷ which are bonded to this carbon atom are preferably identical or different on each occurrence and are 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 ⁷ is very particularly preferably a methyl group or a phenyl group. The radicals R ⁷ can also form a ring system with one another, resulting in a spiro system.

In a preferred embodiment of the compounds of the 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.

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.

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

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

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 with the same basic chemical structure, which differ only in the degree of deuteration.

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%.

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.

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.

Examples of suitable further matrix materials for 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 completely deuterated. Examples of suitable further matrix materials for 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],

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 given in Tables T1 and T2 below.

Table T1 :

Die vorstehend genannten Hostmaterialien der Formel (1 ) sowie deren bevorzugt beschriebene Ausführungsformen können in der erfindungs- gemäßen Vorrichtung beliebig mit den zuvor genannten Matrixmaterialien/ Hostmaterialien, den Matrixmaterialien/Hostmaterialien der Formeln (HH- 1 ), (HH-2), (HH-3), (HH-4), (HH-5) oder (HH-6) sowie deren bevorzugt beschriebenen Ausführungsformen der Tabelle T1 oder den Verbindungen H1 bis H27 kombiniert werden. 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 the 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 the 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.

The concentration of the host material of formula (1), as previously described 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 entire mixture or based on the entire composition of the light-emitting layer.

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.

The present invention also relates to a mixture which, in addition to the above-mentioned host materials of 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.

The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the light-emitting layer contains at least one phosphorescent emitter 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.

Suitable charge transport materials, as 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 as are used in these layers according to the prior art.

All materials that are used as hole transport materials in the hole transport layer according to the state of the art 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 (for example according to WO 06/122630 or WO 06/100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (for example 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.

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 which are 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 which are claimed and disclosed in WO 2012/034627.

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. Other 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 aluminium 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 above-mentioned Compounds as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300.

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

In the further layers of the organic electroluminescent device according to the invention, all materials can be used as are usually used according to the prior art. The person skilled in the art can therefore, without inventive step, 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.

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

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

Also preferred is an organic electroluminescent device, characterized in that one or more layers are deposited from solution, such as by spin coating, or by any printing method, such as screen printing, flexographic printing, offset printing, LITI (Light Induced Thermal Imaging, thermal transfer printing), ink-jet printing or nozzle printing. Soluble compounds are required for this, which can be obtained, for example, by suitable substitution.

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.

These methods 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.

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).

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:

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.

2. Electronic devices, in particular organic optical detectors or organic electroluminescent devices, containing compounds according to 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, containing compounds according to formula (1) or the preferred embodiments described as photosensitizers have excellent efficiency. The compounds according to the invention according to formula (1) or the preferred embodiments described result in a low operating voltage when used in electronic devices.

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.

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

6. Compounds according to formula (1) or the preferred embodiments shown exhibit excellent glass film formation.

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.

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

The invention is explained in more detail by the following examples, without intending to limit it. The person skilled in the art can carry out the invention in the entire disclosed area from the descriptions. and without inventive step, prepare further compounds according to the invention and use them in electronic devices or apply the method according to the invention.

Examples:

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

Literature-known Synthone LS:

Synthesis of synthons:

Example S1 :

Ein gut gerührtes Gemisch aus 33.3 g (100 mmol) S2, Stufe A, 41 .5 g (300 mmol) Kaliumcarbonat, 3, 1 g (30 mmol) Pivalinsäure, 1.16 g (4 mmol) Tri-tert-butylphosphonium-tetrafluoroborat und 449 mg (2 mmol) Palladium(ll)acetat, 100 g Glaskugeln (3 mm Durchmesser) und 300 ml Dimethylacetamid (DMAC) wird 3 h bei 150 °C gerührt. Man lässt auf 80 °C abkühlen, tropft 1000 ml Wasser zu, saugt vom ausgefallenen Roh- produkt ab, wäscht dieses dreimal mit je 100 ml Wasser und dreimal mit je 50 ml Methanol und trocknet im Vakuum. Man löst das Rohprodukt in 500 ml DCM und 50 ml Ethylacetat, filtriert über ein mit DCM vorgeschlämmtes Kieselgelbett ab und entfernt dieses im Vakuum, wobei das abdestillierte DCM gegen Ende durch simultane Zugabe von 200 ml Methanol substi- tuiert wird. Man saugt vom auskristallisierten Produkt ab, wäscht dieses dreimal mit je 50 ml EtOH und trocknet im Vakuum. Ausbeute: 15.3 g (51 mmol), 51 %: Reinheit: ca. 97 % in n. ¹H-NMR. A well-stirred mixture of 25.2 g (100 mmol) 1-chloro-11H-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 mixture is filtered off with suction through a Celite bed pre-slurried with 1,2-dichlorobenzene, the filtrate is concentrated to dryness in a vacuum, the residue is taken up in 500 ml of dichloromethane (DCM), filtered through a silica gel bed pre-slurried with DCM, the filtrate is mixed with 300 ml of methanol and concentrated to approx. 150 ml in a vacuum at 40 °C. The crystallized product is filtered off with suction, washed three times with 50 ml of methanol and dried in a vacuum. Recrystallization from acetonitrile / DCM. Yield: 20.0 g (60 mmol), 60%: Purity: approx. 97% in n. ¹ H-NMR.

A well-stirred mixture of 33.3 g (100 mmol) S2, step A, 41.5 g (300 mmol) potassium carbonate, 3.1 g (30 mmol) pivalic acid, 1.16 g (4 mmol) tri-tert-butylphosphonium tetrafluoroborate and 449 mg (2 mmol) palladium(II) acetate, 100 g glass beads (3 mm diameter) and 300 ml dimethylacetamide (DMAC) is stirred for 3 h at 150 °C. It is allowed to cool to 80 °C, 1000 ml water is added dropwise, the precipitated crude product is filtered off with suction, washed three times with 100 ml water each time and three times with 50 ml methanol each time and dried in vacuo. The crude product is dissolved in 500 ml DCM and 50 ml ethyl acetate, filtered through a silica gel bed pre-slurried with DCM and removed in vacuo, whereby the distilled DCM is replaced towards the end by simultaneous addition of 200 ml methanol. The crystallized product is filtered off with suction, washed three times with 50 ml EtOH each time and dried in vacuo. Yield: 15.3 g (51 mmol), 51%: Purity: approx. 97% in n. ¹ H-NMR.

The following connections can be represented analogously:

Synthesis of the compounds according to the invention:

Example B1 :

Level A:

Carrying out the Vielsmeier-Haak formylation analogously to

US 2021/0234103, page 70, compound 1-1 D. Preparation: 4.6 g (15.5 mmol)

S1. The crude product is purified by chromatography (Torrent column machine from A. Semrau). Yield: 2.8 g (8.5 mmol), 55%: Purity: approx. 98% in n. ¹ H-NMR.

Level B:

Procedure according to Haig et al., Chem. Mat., 2011 , 23(20), 4435, page 4436, verb. 3. Batch: 3.3 g (10.0 mmol) B1 step A. 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) and fractional sublimation or annealing under high vacuum. Yield: 2.6 g (7.0 mmol), 70%: Purity: >99.9% in n. HPLC.

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.

The following connections can be represented analogously:

Example B100:

Level A:

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

Level B:

Preparation analogous to Z. He et al., Tetrahedron (2020), 76(51 ), 131315, General Procedure A. Preparation: 3.8 g (10.0 mmol) B100 stage A. Reaction control via TLC for consumption of B100 stage A, typical reaction time 16 - 24 h. 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) and fractional sublimation or annealing under high vacuum. Yield: 2.7 g (7.3 mmol), 73%: Purity: > 99.9% in n. HPLC.

Example B200: Carry out analogously to example S1. Preparation: 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 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) and fractional sublimation or annealing in a high vacuum. Yield: 2.0 g (5.7 mmol), 57%: Purity: > 99.9% in n. HPLC

Beispiel B300: The following connections can be represented analogously:

Example B300:

Procedure analogous to K. Ogawa et al., Journal of Organic Chemistry (2001 ), 66(26), 9067. Preparation: 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) and fractional sublimation or annealing in a high vacuum. Yield: 2.1 g (4.4 mmol), 44%: Purity: > 99.9% in n. HPLC

Determination of the LUMO of the acceptor groups

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

Invoice as described below. The LUMO the electron acceptor group in the sense of the present compound is defined as the LUMO of the group Z which has a hydrogen atom instead of the group represented by formula (1) and formula (2-1) to (2-7).

The Gaussian16 (Rev. B.01) program package is used in all quantum chemical calculations. The neutral singlet ground state is optimized at the B3LYP/6-31 G(d) level. LUMO calcd 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.

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

Examples of photodiodes:

1) Manufacturing of mono-layer photodiodes (MLPD)

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

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 maximum absorption in the wavelength range 400 - 700 nm at a voltage of 3 V (Table 1).

2) Herstellung der Bi-Layer Photodioden (BLPD) Table 1 :

2) Manufacturing of bi-layer photodiodes (BLPD)

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

Structure of the BLPD:

ITO-substrate-BLPD

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

Hole transport layer 1 (HTL1), see Table 2

Hole transport layer 2 (HTL2), see Table 2

electron donor layer (EDL), see Table 2

electron acceptor layer (EAL), see Table 2

Electron transport layer 1 (ETL1), see Table 2

electron transport layer 2 (ETL2), see Table 2

Electron injection layer 1 (EIL1), 3 nm EIM

Cathode of magnesium:silver (10:90), 100 nm

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).

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

Table 3: Materials used

Example: Production of OLEDs

1) Vacuum-processed devices:

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).

The following examples present the results of various OLEDs. Cleaned glass plates (cleaned in a Miele laboratory dishwasher, Merck Extran cleaner) coated with structured ITO (indium tin oxide) with a thickness of 50 nm 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.

1a) Blue Fluorescence OLED Components - BF:

The compounds according to the invention can be used in the hole injection layer (HIL), hole transport layer (HTL) and in the 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 (dopant, emitter) D, which is mixed into the matrix material or materials by co-evaporation in a certain volume proportion. A specification such as SMB:D (97:3%) means that the SMB material is present in the layer in a volume proportion of 97% and the dopant D in a proportion 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 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 Im/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 characteristic, as well as the service life. The EQE in (%) and the voltage in (V) are specified at a luminance of 1000 cd/m ²

The OLEDs have the following layer structure:

substrate

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

Hole transport layer (HTL), see Table 4

electron blocking layer (EBL), see Table 4

emission layer (EML), see Table 4

electron transport layer (ETL), see Table 4

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

aluminum cathode, 100 nm

Table 4: Structure of blue fluorescent OLED components

Table 5: Results of blue fluorescence OLED devices

1 b) Phosphorescent OLED components:

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 mixed into the matrix material or materials by co-evaporation in a certain volume proportion. A specification such as M1:M2:lr (55%:35%:10%) means that the material M1 is present in the layer in a volume proportion of 55%, M2 in a volume proportion of 35% and Ir in a volume proportion 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 Im/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 characteristic, as well as the service life. The EQE in (%) and the voltage in (V) are given at a luminance of 1000 cd/m ² . The service life is determined at a starting luminance of 1000 cd/m ² .

The OLEDs have the following layer structure:

substrate

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

Hole transport layer (HTL), see Table 6

electron blocking layer (EBL), see Table 6

emission layer (EML), see Table 6

hole blocking layer (HBL), see Table 6

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

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

aluminum cathode, 100 nm

Table 6: Structure of phosphorescent OLED components

Table 7: Results of phosphorescent OLED devices

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 to 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 stand for N; Y is a single bond, BR ^b , C(R ^b )2, Si(R ^b )2, GeR ^b 2, NR ^b , R ^b P(O), O, S, SO, SO2, Se or Te; X ¹ stands at each occurrence, identically or differently, for N, CR ^C or CZ, with the proviso that not both X ¹ stand for N; Y ¹ is the same or different at each occurrence and is NR ^C , O, S, Se or Te; Z is an electron acceptor group; Z can also form a ring system with R ^c ; R ^a , R ^b is, identically or differently on each occurrence, 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) ₂ R 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, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group can each be substituted by one or more radicals R ¹ , where one or more non-adjacent CH2 groups can be replaced by R ¹ C=CR ¹ , C=C, Si(R ¹ ) ₂ , C=O, C=S, C=Se, C=NR ¹ , C(=O)O, C(=O)NR ¹ , NR ¹ , P(=O)(R ¹ ), Se, Te, BR ¹ , Ge(R ¹ )2, O, S, SO or SO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which can each be substituted by one or more radicals R ¹ , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or an arylthio or heteroarylthio group with 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or a diarylamino, arylheteroarylamino, diheteroarylamino group with 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or an aralkyl or heteroarylalkyl group with 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; two radicals R ^a , R ^b and/or R ^c can also form a ring system with each other or with another group; R ^c is, identically or differently on each occurrence, 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) ₂ R 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 with 3 to 40 C atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group can each be substituted by one or more radicals R ¹ , where one or more non-adjacent CH2 groups can be replaced by R ¹ C=CR ¹ , C=C, Si(R ¹ ) ₂ , C=O, C=S, C=Se, C=NR ¹ , C(=O)O, C(=O)NR ¹ , NR ¹ , P(=O)(R ¹ ), 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, which can each be substituted by one or more radicals R ¹ , or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms which may be substituted by one or more radicals R ¹ , or an arylthio or heteroarylthio group with 5 to 60 aromatic ring atoms which may be substituted by one or more radicals R ¹ , or a diarylamino, arylheteroarylamino, diheteroarylamino group with 5 to 60 aromatic ring atoms which may be substituted by one or more radicals R ¹ , or an aralkyl or heteroarylalkyl group with 5 to 60 aromatic ring atoms and 1 to 10 C atoms in the alkyl radical which may be substituted by one or more radicals R ¹ ; two radicals R ^a , R ^b and/or R ^c can also form a ring system with one another or with another group; R ¹ is, identically or differently on 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 having 2 to 40 C atoms, each of which may be substituted by one or more radicals R ² , where one or more non-adjacent CH2 groups may be replaced by R ² C=CR ² , C=C, Si(R ² ) ₂ , C=O, C=S, C=Se, C=NR ² , C(=O)O, C(=O)NR ² , NR ² , P(=O)(R ² ), O, S, SO or SO2 and where one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ² , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ² may be substituted, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ² , or a combination of these systems; two or more, preferably adjacent, radicals R ¹ may form a ring system with one another; one or more radicals R ¹ may form 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 can be replaced by D, F, CI, Br, I or CN and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, where two or more, preferably adjacent, substituents R ² can form a ring system with one another. 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 stands for a single bond, C(R ^b )2, or S. 5. A compound according to one or more of claims 1 to 4, characterized in that Y ¹ on each occurrence, identically or differently, represents S or Se. 6. Compound according to one or more of claims 1 to 5, characterized in that the electron acceptor group Z is an organic group which has 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 where 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 can form a ring system with R ^c ; (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 ^e in claim 1 and where the terminal C atom is substituted by a group -C(=O)-LC(=O)-; 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 defined analogously to R ^a to R ^e 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 the formulas (Z-1), (Z-1 ') and (Z-2),

Formula (Z-1) Formula (Z-1 ') Formula (Z-2) wherein 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)-CR ₂ - or -NR-NR-; or that group Z represents a group according to formula (Z-4),

where the dashed bond represents the attachment of this group, R has the meanings given in claim 4 and furthermore: X ¹ is the same or different on each occurrence and is CR or N, with the proviso that a maximum of three X ^1s stand for N and that a maximum of two N atoms are directly bonded to one another, and further with the proviso that at least two groups X ¹ stand for C-CN; or that the group Z represents a group of the formula (Z-5),

where the dashed bond represents the attachment 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 stand for -CR2-CR2- or -CR2-CR2-CR2-, where R in each case preferably stands for H, D or an optionally deuterated alkyl group having 1 to 6 C atoms and several radicals R can also form a ring with one another. 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 can also be partially or completely deuterated,

where the dashed bond represents the attachment site, R is H, D, optionally deuterated methyl or CN and R ¹ is or differently at each occurrence represents H, D or optionally deuterated methyl; or that group Z is selected from the structures of the formulas (Z-3-1) to (Z-3-9),

(Z-3-9) wherein the dashed bond represents the attachment 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),

where the dashed bond represents the linkage of this group, R has the meanings given in claim 4 and at least two groups R stand for 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. 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 on 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, where the alkyl group can be substituted in each case by one or more radicals R ¹ , or an aromatic or heteroaromatic ring system having 6 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ . 11. A compound according to one or more of claims 1 to 3 or 10, characterized in that Y on each occurrence, identically or differently, represents a single bond, BR ^b , C(R ^b ) 2, NR ^b or O. 12. A compound according to one or more of claims 1 to 3, 10 or 11, characterized in that Y ¹ on each occurrence is identical or different and represents 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. 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, comprising at least one compound according to one or more of claims 1 to 3 and 10 to 12.