WO2024256357A1 - Organic heterocycles for photoelectric devices - Google Patents

Abstract

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

Description

Organic Heterocycles for Photoelectric Devices

The present invention relates to organic heterocycles for use in electronic devices, in particular in organic, photoelectric devices, and to electronic devices, in particular organic, photoelectric devices, containing these heterocyclic compounds.

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.

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, in particular as a photosensitizer 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 was found that certain compounds, described in more detail below, solve this problem, are very well suited for use in electronic devices and lead to organic optical detectors that are particularly suitable for use in food duration, efficiency and operating voltage. These compounds, as well as electronic devices, in particular organic optical detectors, which contain such compounds, are therefore the subject of the present invention.

The present invention relates to a compound of the formula

(1 ) or formula (2),

Formula (1 ) Formula (2) where the symbols and indices used are:

Ar® is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ^a ;

Ar ^b is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms which may be substituted by one or more R ^b radicals;

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

Y ¹ is, identically or differently at each occurrence, S, Se or Te, preferably S or Se and particularly preferably S;

Y ² is a bond, C(R ^d ) ₂ , O, S, Se, NR ^d ,C(=O), Si(R ^d ) ₂ , Ge(R ^d ) ₂ , C=NR ^d , C=C(R ^d ) ₂ , CR ^d =CR ^d or an aromatic or heteroaromatic ring system with 5 to 10, preferably with 5 or 6 aromatic ring atoms, which may be substituted by one or more radicals R ^d , preferably a bond, C(R ^d )2, O, S or NR ^d and particularly preferably C(R ^d )2;

Y ³ is a bond, C(R ^e ) ₂ , O, S, Se, NR ^e , C(=O), Si(R ^e ) ₂ , Ge(R ^e ) ₂ , C=NR ^e , C=C(R ^e )2, CR ^e =CR ^e or an aromatic or heteroaromatic ring system having 5 to 10, preferably 5 or 6 aromatic ring atoms, which may be substituted by one or more radicals R ^e , preferably a bond, C(R ^e )2, O, S or NR ^e ;

R ^a , R ^b , R ^c , R ^d , R ^e is, identically or differently on each occurrence, H, D, OH, F, CI, Br, I, CN, NO ₂ , N(R ¹ ) ₂ , C(=O)N(R ¹ ) ₂ , C(R ¹ ) ₃ , Si(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 ; two radicals R, R ^a , R ^b , R ^c , R ^d , R ^e can also form a ring system with each other or with another group;

oder SO2 ersetzt sein können und wobei ein oder mehrere H-Atome durch D, F, CI, Br, I, CN oder NO2 ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 60 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R² substi- tuiert sein kann, oder eine Aryloxy- oder Heteroaryloxygruppe mit 5 bis 60 aromatischen Ringatomen, die durch einen oder mehrere Reste R² substituiert sein kann, oder eine Aralkyl- oder Hetero- aralkylgruppe mit 5 bis 60 aromatischen Ringatomen, die mit einem oder mehreren Resten R² substituiert sein kann, oder eine Kombi- nation dieser Systeme; dabei können zwei oder mehrere, vorzugs- weise benachbarte Reste R¹ miteinander ein Ringsystem bilden; dabei können ein oder mehrere Reste R¹ mit einem weiteren Teil der Verbindung ein Ringsystem bilden; 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 ) _3I Si(R ² ) ₃ , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or an alkenyl group having 2 to 40 C atoms, each of which may be substituted by one or more radicals R ² , where one or more non-adjacent CH ₂ groups are substituted by , C=Se, C=NR ² , C(=O)O, C(

or SO2 and where one or more H atoms can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which can be substituted by one or more R ² radicals, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which can be substituted by one or more R ² radicals, or an aralkyl or heteroaralkyl group with 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 R ¹ radicals can form a ring system with one another; one or more R ¹ radicals 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 one another; q is 1 or 2, preferably 1 .

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 thienothiophene substituent. 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 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.

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 is understood to mean 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, pentynylthio, hexynylthio, heptynylthio or octynylthio. In general, alkyl, alkoxy or thioalkyl groups according to the present invention can be straight-chain, branched or cyclic, where one or more non-adjacent CH2 groups can be replaced by the above-mentioned groups; Furthermore, one or more H atoms can be replaced by D, F, 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 umbrella 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, isoquinoline, 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-oxadiazole, 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:

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 to R ^e 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 the at least one CN group and at least one substituted carbonyl group of the Group Z is completely conjugated with the 5-membered ring to which group Z is attached.

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 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 ) is H or D, so that the group (Z-1 ) is 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.

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 several preferably non-aromatic radicals R ¹ can be substituted.

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

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 optionally deuterated methyl groups.

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. Preferred embodiments of the formula (Z-2) are the structures of the following formulas (Z-2-1) and (Z-2-2), whereby 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 bivalent organic group.

wobei die gestrichelte Bindung die Anknüpfung dieser Gruppe darstellt, R analog zu R^a bis R^e 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 to R ^e 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 radicals R which are bonded to the carbon atoms of the aliphatic cycle in formula (Z-3-5) to (Z-3-7) and (Z-3-9) are preferably identical or different on each occurrence and represent H, D or an optionally deuterated alkyl group having 1 to 6 C atoms, where several radicals R can also form a ring with one another. It is preferred if the radicals R which are bonded to a carbon atom adjacent to a carbonyl group, identically or differently on each occurrence, represent D or an optionally deuterated alkyl group having 1 to 6 C atoms, in particular D or methyl.

Particularly preferred embodiments of the structure of formula (Z-3) are the structures of the following formulas (Z-3a) to (Z-3v), whereby these structures can also be partially or completely deuterated,

wobei die gestrichelte Bindung die Anknüpfung dieser Gruppe darstellt.

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 to R ^e 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 bis R^e 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 to R ^e above 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.

In a preferred embodiment of the formula (Z-4), a maximum of two groups X ¹ stand for N, particularly preferably a maximum of one group X ¹ stands for N and very particularly preferably all groups X ¹ stand for CR.

wobei die gestrichelte Bindung die Anknüpfung dieser Gruppe darstellt, R wie oben definiert ist und mindestens zwei Gruppen R für CN stehen. 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 radicals R are not H or D, particularly preferably a maximum of one The radical R is not H or D and most preferably all radicals R are H or D.

The groups of the formulas (Z-4a), (Z-4e), (Z-4f), (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.

Preference is given to compounds for which:

Particularly preferred are compounds for which:

In a preferred embodiment of the invention, Ar ^a and Ar ^b are the same or different on each occurrence and are an aryl or heteroaryl group having 6 to 14 aromatic ring atoms, preferably having 6 to 13 aromatic ring atoms, which may be substituted by one or more radicals R ^a or R ^b . In a particularly preferred embodiment of the invention, Ar ^a and Ar ^b are the same or different on each occurrence and are benzene, naphthalene, phenanthrene, dibenzofuran, dibenzothiophene or carbazole, which may each be substituted by one or more radicals R ^a or R ^b . Preferably, at least one of the groups Ar ^a and/or Ar ^b is benzene.

In a preferred embodiment of the invention, the compounds of formulas (1) or (2) are selected from the compounds of the following formulas (3) or (4),

Formula (3) Formula (4) where the symbols used have the meanings given above, where q in formula (3) is preferably = 1, and furthermore:

X ^a stands on each occurrence, identically or differently, for CR ^a or N, preferably for CR ^a , with the proviso that not more than two of the groups X ^a in a cycle stand for N; or two adjacent X ^a together stand for a group of the following formula (X ^a -1 ) or (X ^a -2),

(X ^a -1) (X ^a -2) where the dashed bonds represent the linkage of the group and A stands for 0, S or NR ^a ;

X ^b stands on each occurrence, identically or differently, for CR ^b or N, preferably for CR ^b , with the proviso that not more than two of the groups X ^b in a cycle stand for N; or two adjacent X ^b together stand for a group of the following formula (X ^b -1 ) or (X ^b -2),

(X ^b -1) (X ^b -2) where the dashed bonds represent the linkage of the group and A stands for 0, S or NR ^b .

Preferred embodiments for the group Z in formula (3) and (4) are the formulae (Z-1) to (Z-5) given above, and particularly preferred structures are the formulae (Z-1-1) to (Z-1-3), (Z-2-1), (Z-2-2), (Z-3-1) to (Z-3-8), (Z-4-1), (Z-5-1) given above, and very particularly preferred structures are the formulae (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 a preferred embodiment of the invention, in formula (3) or (4) a total of not more than two groups X ^a and X ^b stand for N. Particularly preferably, all groups X ^a and X ^b stand for CR ^a or CR ^b or for the fused (X ^a -1 ), (X ^a -2 ), (X ^b -1 ) or (X ^b -2) described above.

In a particularly preferred embodiment of the invention, the compounds according to the invention are selected from the compounds of the formula (5) or (5a) to (5f), or (6) or (6a) to (6f),

formula (5)

formula (6)

Formula (6e) Formula (6f) where the compounds can also be partially or completely deuterated, Z stands for a group of the formula (Z-1), (Z-2), (Z-3), (Z-4) or (Z-5), the other symbols have the meanings given above and furthermore: m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, particularly preferably 0 or 1; n is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1.

The following embodiments are therefore suitable:

Preferably, the groups of Z in the formulas (5), (5a) to (5f), (6) and (6a) to (6f) are selected from the groups of the formulas (Z-1-1), (Z-1-2), (Z-1-3), (Z-2-1), (Z-2-2), (Z-3-1) to (Z-3-8), (Z-4-1) and (Z-5-1) and particularly preferably from the groups of the formulas (Z-1'), (Z-2a) to (Z-2d), (Z-3a) to (Z-3zz) and (Z-4a) to (Z~4i). The structures of the formulas (Z-1-1) and (Z-2a) to (Z-2d) are very particularly preferred.

Furthermore, Y ¹ in the formulas (1), (2), (3), (4), (5), (5a) to (5f), (6) and (6a) to (6f) preferably represents S.

In a further preferred embodiment of the invention, Y ³ in formulas (1) and (2) and the preferred embodiments is a bond, C(R)2, O, S or NR ^d , and at the same time the group Y ² is C(R ^e )2, and at the same time the group Y ¹ is S or Se, preferably S. In a particularly preferred embodiment of the invention, Y ³ is a bond or C(R ³ )2, in particular a bond, and Y ² is C(R ^d )2, and Y ¹ is S. In the compounds of the formulas (5a) to (5f) and (6a) to (6f), the group Y ² is preferably C(R ^e )2, and the group Y ¹ is S.

If Y ² is C(R ^e ) 2 , R ^e preferably represents, identically or differently on each occurrence, 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 ^e of the group Y ² together form a ring can form. If two radicals R ^e together form a ring, a spiro system is formed, the ring formed by the two radicals R ^e preferably being a 5-membered ring or a 6-membered ring. If Y ² is C(R ^e )2, R ^e particularly preferably represents F, methyl, ethyl, neo-pentyl or phenyl, where these groups can each also be partially or fully deuterated and where the two groups R ^e can also form a ring with each other, or the two groups R ^e together with the C atom to which they are bound form a cyclopentyl, cyclohexyl or adamantanyl group, which can also be partially or fully deuterated. R ^e particularly preferably represents methyl, which can also be partially or fully deuterated.

In a further preferred embodiment of the invention, the radical R ^c 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 ^c can form a ring with the radical R. In a particularly preferred embodiment of the invention, the radical R ^c is H, D, optionally deuterated methyl or optionally deuterated phenyl, very particularly preferably H or D.

In a further preferred embodiment of the invention, the radical R ^d stands for H, D, for a straight-chain alkyl group having 1 to 10 C atoms, for 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 for 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 .

In a particularly preferred embodiment of the invention, the compounds according to the invention are selected from the compounds of the following formulas (7-1) to (7-8) and (8-1) to (8-3),

wobei die Symbole und Indizes oben genannten Bedeutungen aufweisen und Z für eine Gruppe der Formel (Z-1 ), (Z-2), (Z-3), (Z-4) oder (Z-5) oder insbesondere deren bevorzugte Ausführungsformen steht. Besonders bevorzugt steht Z für eine Gruppe der Formel (Z-1 ) oder (Z-2a) bis (Z-2d) und ganz besonders bevorzugt für eine Gruppe der Formel (Z-1 -1 ). Hierbei sind. Verbindungen der Formeln (7-2), (7-5) und (7-6) bevorzugt, und Verbindungen der Formel (7-6) sind besonders bevorzugt. formula (8-1 )

where the symbols and indices have the meanings given above and Z stands for a group of the formula (Z-1), (Z-2), (Z-3), (Z-4) or (Z-5) or in particular preferred embodiments thereof. Z particularly preferably stands for a group of the formula (Z-1) or (Z-2a) to (Z-2d) and very particularly preferably for a group of the formula (Z-1 -1). Here, compounds of formulas (7-2), (7-5) and (7-6) are preferred, and compounds of formula (7-6) are particularly preferred.

Furthermore, for the formulas set out above, it is preferred if the sum of the indices m and n is at most 10, preferably at most 8, particularly preferably at most 6, particularly preferably at most 4, and most preferably at most 2.

If two radicals, which can be selected in particular from R, R ^a , R ^b , R ^c , R ^d , R ^e , 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 , R ^c , R ^d and R ^e are described below.

In a preferred embodiment of the invention, R, R ^a , R ^b , R ^c , R ^d and R ^e 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 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 can be substituted in each case by one or more radicals R ¹ , or an aromatic or heteroaromatic ring system with 6 to 40 aromatic ring atoms, each of which may be substituted 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 , R ^c , R ^d and R ^e 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 , R ^c , R ^d , R ^e , 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 , R ^c , R ^d and/or R ^e 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 may be substituted by one or more radicals R, R ¹ or R ² .

If R, R ^a , R ^b , R ^c , R ^d and/or R ^e 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-23 R-24

R-22

R-152

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 at each occurrence, identically or differently, a bivalent aromatic or heteroaromatic ring system with 6 to 18 aromatic tic ring atoms, each of which may 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 represent the bond to the aromatic or heteroaromatic group 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 can also be represented by one or more radicals R ² can be substituted. In a particularly preferred embodiment, this substituent R ¹ is the same or different on each occurrence and represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, and which can each also be substituted by one or more radicals R ^2. Particularly preferred are phenyl, biphenyl, terphenyl and quaterphenyl with linkage patterns as listed above for R-1 to R-35, where these structures can 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 , R ^c , R ^d and R ^e are groups of the formula -Ar ⁴ -N(Ar ² )(Ar ³ ), where Ar ² , Ar ³ and Ar ^{4 ,} identical or different on each occurrence, represent an aromatic or heteroaromatic ring system with 5 to 24 aromatic ring atoms, which may 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, which may each be substituted by one or more radicals R ¹ . Ar ² and Ar ³ are very particularly preferably selected, identically or differently on each occurrence, from the group consisting of benzene, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, in particular 1-, 2-, 3- or 4-fluorene, or spirobifluorene, in particular 1-, 2-, 3- or 4-spirobifluorene.

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 tic ring system with 6 to 24 aromatic ring atoms, which can each be substituted by one or more radicals R ² ; two or more radicals R ¹ can 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 with 1 to 6 C atoms, in particular with 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group with 3 to 6 C atoms, where the alkyl group can be substituted in each case by one or more radicals R ² , but is preferably unsubstituted, or an aromatic or heteroaromatic ring system with 6 to 13 aromatic ring atoms, which can each be substituted by one or more radicals R ² , but is preferably unsubstituted; Two or more radicals R ¹ can form a ring system.

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 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 basic structure with an aromatic amino group is synthesized and at least one heterocyclic radical is introduced, preferably by means of a nucleophilic aromatic substitution reaction or a coupling reaction.

The invention further relates to a process for preparing the compounds according to the invention, in which the basic structure of the compound is synthesized, which has a hydrogen atom instead of the group Z, followed by the introduction of the group Z, for example by formylation or acylation of the position at which the group Z is to be introduced, followed by a Knoevenagel condensation. The synthesis of the compounds according to the invention can be carried out, inter alia, according to Scheme 1 below. In a first step, a compound with an aromatic amino group (1) can be reacted with a 5-5 ring heterocycle (2) (thienothiophene, selenolothiophene, selenoloselenophene) in a Ullmann coupling. The compound (3) thus obtained can be reacted in a hydroxyalkylation reaction with a carbonyl compound (4) to form a nitrogen-containing hydroxy compound (5), which is shown as step 2 in Scheme 1. In step 3, this hydroxy compound (5) is cyclized and subsequently derivatized in step 4 by formylation or acylation to form a carbonyl compound (8). In step 5, the carbonyl compound (8) can be reacted in a Knoevenagel condensation with a CH-acidic compound H2CZ' (9), such as, for example, B. malononitrile, 1,3-indandione, barbituric acids, thiobarbituric acids, 2-(4,5,5-trimethyl-2(5/-/)-furanylidene)-propanedinitriles and 2-(4,5,5-trimethyl-2(5/-/)-thiophenylidene)-propanedinitriles and their derivatives (9) are converted to a compound (10) according to the invention. The Knoevenagel condensation is described, among others, in S. Haig et al., Chem. Mat., 2011, 23(20), 4435.

Scheme 1 :

Step 1 : Ullmann coupling

CR ₂ , SiR ₂ , NR, O, S, Se, etc.

Schritt 3: Cyclisierung

Step 2: Hydroxyalkylation

Step 3: Cyclization

Step 5: Knoevenagel condensation

The synthesis of the compounds according to the invention can further be carried out according to the following scheme 2, by means of which in particular compounds with further groups Y ² can be obtained, such as, for example, O, S, Se, NR ^d , Ge(R ^d )2, Si(R ^d )2, C=O, -CR ^d =CR ^d - or C=NR ^d . In the first step, a compound with an aromatic amino group (11) can be reacted with a 2,3-bishalo-functionalized 5-5-ring heterocycle (12) by double Ullmann coupling. The resulting compound (13) can be prepared by formylation or

Acylation into a carbonyl compound (14). In step 3, the carbonyl compound (14) can be converted into a compound (15) according to the invention in a Knoevenagel condensation. Scheme 2:

Step 1 : Ullmann coupling

Step 2: Formylation or acylation

Step 3: Knoevenagel condensation

The synthesis of the compounds according to the invention can also be carried out according to the following scheme 3, by means of which in particular compounds with further groups Y ² can be obtained, such as a bond. Starting from (16) and (12), the intermediates (17) can be obtained according to D. Bader et al., J. Org. Chem., 2020, 85(5), 3865. The intermediates (17) can then be converted into the corresponding compounds (19) according to the invention by means of steps 2 and 3. Scheme 3:

Step 1 : Ullmann coupling

The meaning of the symbols used in Schemes 1, 2 and 3 essentially corresponds to those defined for formula (1) or preferred embodiments of these structures, whereby for reasons of clarity, numbering and a complete representation of all symbols and substituents have been omitted and for reasons of clarity, the substituents shown have all been designated with R. In addition, for reasons of clarity, the use of symbols to represent possible nitrogen atoms in the heteroaromatic rings has been omitted in many cases. as shown, for example, in formula (3) and (4) by the symbols X ^a and X ^b . These details are therefore to be understood as examples, whereby the person skilled in the art is able to transfer the syntheses set out above and below, in particular in the examples, to compounds in which one or more of the symbols X ^a and X ^b stand for nitrogen or which contain other aromatic groups, such as naphthalene, instead of the benzene groups in the basic structure.

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

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.

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 (2) 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-methyl- naphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, Decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenetol, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, Tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, Pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents.

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, 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 invention is 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 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 also 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, depending on the precise structure. Preference is given to an organic optical detector containing a compound according to formula (1) or (2) or the preferred embodiments described above in a light-absorbing layer as a photosensitizer, preferably an infrared, red, green or blue photosensitizer, particularly preferably as a green photosensitizer, the color in each case indicating the color of the light that 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. CBP (N,N-biscarbazolylbiphenyl) or those in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527, WO 2008/086851 or WO 2013/041176, indolocarbazole derivatives, e.g. according to WO 2007/063754 or WO 2008/056746, indenocarbazole derivatives, e.g. according to WO 2010/136109, WO 2011/000455, WO 2013/041176 or WO 2013/056776, azacarbazole derivatives, e.g. according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar comaterials, e.g. B. according to WO 2007/137725, silanes, e.g. according to WO 2005/111172, azaboroles or boronates, 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. according to EP 652273 or WO 2009/062578, diazasilole or tetraazasilole derivatives, e.g. according to WO 2010/054729, diazaphosphole derivatives, e.g. B. 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 (2) 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 are described, inter alia, in European patent application EP 3848374 A1, which document is incorporated by reference for disclosure purposes. These materials are set out in particular on pages 84 to 86 (see 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 (2) or the preferred embodiments described above.

Also preferred is an organic optical detector, 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.

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, and 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 Figures 1 to 10 described in EP 3848374 A1, which are set out, inter alia, on pages 83 to 90 of the document EP 3848374 A1.

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

1 . In particular, compounds according to formula (1) and (2) and the preferred embodiments described which contain thienothiophene structures, in which X ¹ stands for S, have the advantage that they are less toxic than compounds in which one or more X ¹ stands for Se.

2. The compounds according to formula (1) and (2) or the preferred embodiments described have a very high extinction coefficient. This is a significant advantage for the use of the materials in organic optical detectors.

3. Electronic devices, in particular organic optical detectors containing compounds according to formula (1) or (2) or The preferred embodiments described, in particular as photosensitizers, have a very good service life.

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

5. The compounds according to the invention according to formula (1) or (2) or the preferred embodiments shown show high stability, in particular thermal stability and low vapor deposition temperatures.

6. Using compounds according to formula (1) or (2) 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.

7. Compounds according to formula (1) or (2) or the preferred embodiments described have excellent glass film formation.

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 thereby. The person skilled in the art can carry out the invention in the entire disclosed area from the descriptions and can, without inventive step, produce further compounds according to the invention and use them in electronic devices or apply the method according to the invention.

Description of the characters

Figure 1 shows the absorption spectra of two compounds according to the invention (compounds B1 and B500) in a concentration of approx. 10 ^-5 M in degassed dichloromethane. Figure 2 shows the absorption spectra of a further eight compounds according to the invention (compounds B301, B400, B700, B800, B801, B900, B907 and B1002) in a concentration of approx. 10 ^-5 M in degassed dichloromethane.

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.

Procedure analogous to K. Mazzio et al, Appl. Mat. & Interfaces, 2011 , 3, 2, 271 . A solution of 3.46 g (10 mmol) (6) (step 3 with X = single bond & Y = S) and 1.59 g (10 mmol) 4-methyl-3-cyclo-hexen-1-carbonyl chloride [16695-95-7] in 150 ml DCM cooled to 0 °C is added dropwise over 10 min. with a solution of 1 .73 g (13 mmol) aluminum chloride, anhydrous, and stirred for 1 h. The mixture is quenched by carefully adding 50 g of ice, the organic phase is separated off and washed twice with 50 ml each of water, once with 50 ml of saturated sodium chloride solution and dried over magnesium sulfate: sodium carbonate (1:1). The drying agent is filtered off, the filtrate is concentrated in a vacuum, the orange oil is mixed with 30 g of polyphosphoric acid (85%), the mixture is homogenized at 50 °C and then the temperature is increased to 100 °C. After 30 min., cool to 50 °C and then add 200 ml of water dropwise while cooling (caution: exothermic, induction period, maximum temperature 80 °C). The precipitated solid is filtered off with suction, taken up in 150 ml of DCM, washed once with 50 ml of saturated sodium hydrogen carbonate solution, twice with 50 ml of water, once with 50 ml of saturated sodium chloride solution and dried over magnesium sulfate. The drying agent is filtered off and the filtrate is concentrated to dryness in a vacuum. Further purification of the crude product is carried out by chromatography (Torrent column machine from A. Semrau). Yield: 937 mg (2.0 mmol) 20%; Purity: approx. 97% according to ¹ H-NMR.

Synthesis of the compounds according to the invention:

The aldehydes (8) can be prepared analogously to US 2021/0234103 page 70, by using the corresponding starting materials listed below, an o-bromoamine (1 ), a 5-5-ring heterocycle (2) (thienothiophene, selenolothiophene, selenoloselenophene), a ketone (4), and subsequent formylation of the compounds (6) with a formamide (7) or acylation, see Scheme 1 , steps 1 to 4. In the last step 5, the carbonyl compounds (8) are condensed in a Knoevenagel condensation (e.g. S. Haig et al., Chem. Mat., 2011 , 23(20), 4435 and US2021/0234103, p. 71 , Compound 1 and following) with malononitrile, 1 ,3-indandione, barbituric acids, thiobarbituric acids, 2-(4,5,5-trimethyl-2(5/-/)-furanylidene)-propanedinitrile and 2-(4,5,5-trimethyl-2(5/-/)-thiophenylidene)-propanedinitrile and their derivatives (9) to give the compounds (10) according to the invention.

Scheme 1 :

Step 1 : Ullmann coupling

X: single bond,

CR ₂ , NR, O, S, Se, Te

Step 2: Hydroxyalkylation

Step 4: Formylation or acylation

Step 5: Knoevenagel condensation

Alternative procedure to step 2: Suzuki clutch

A well-stirred mixture of 100 mmol (3), 120 mmol of the alkenyl-BFsK salt, 250 mmol of cesium carbonate, 3 mmol of palladium(II) acetate, 9 mmol of triphenylphosphine, 1000 ml of THF and 200 ml of water is heated under reflux for 16 h. After cooling, 500 ml of ethyl acetate (EA) is added, the aqueous phase is separated off, the organic phase is washed three times with 300 ml of water each time and once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. The drying agent is filtered off through a silica gel bed pre-slurried with EA and the solvent is removed in vacuo. The residue is reacted further without further purification.

Alternative procedure to step 3: cyclization

A well-stirred mixture of 100 mmol (11 ) and 400 g polyphosphoric acid is heated to 90 °C for 1 h. Allow to cool to 60 °C, pour the reaction mixture into 5 l ice water with vigorous stirring, stir for 30 min., filter off the precipitated solid or work extractively with EA or dichloromethane (DCM). The crude product is recrystallized from DCM/acetonitrile or chromatographed.

Alternative procedure to step 5: Knoevenagel condensation,

A well-stirred mixture of 100 mmol (8), 110 mmol (9) or the other acceptors, in particular the 1,3-diones, 105 mmol piperidine and 500 ml acetonitrile is heated under reflux for 20 hours. After cooling, the precipitated product is filtered off with suction, washed three times with a little acetonitrile and dried in a vacuum. Products that do not precipitate can be isolated by extraction in the water/dichloromethane system. 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.

Alternative method for introducing BR, SiRz, GeRz, NR, S bridges:

Example B1 :

Procedure analogous to S. Haig et al., Chem. Mat., 2011 , 23(20), 4435. A mixture of 37.4 g (100 mmol) (8 with X = single bond & Y = S), 14.6 g (220 mmol) malononitrile [109-77-3], 446 mg (5 mmol) ß-alanine [107-95-9], 300 ml ethanol and 200 ml dichloromethane (DCM) is stirred in a stirred autoclave for 3 h at 80 °C. The mixture is allowed to cool with stirring, the precipitated product is filtered off with suction, the residue is washed three times with 30 ml of cold ethanol each time and the residue is dried in vacuo. Further purification is carried out by chromatography (Torrent column machine from A. Semrau) or hot extraction crystallization (usual organic solvents, preferably acetonitrile or acetonitrile-DCM mixtures (4:1 - 1:2 vv) and by fractional sublimation under high vacuum (p approx. 10' ⁵ mbar).

Yield: 29.8 g (71 mmol) 71%; Purity: approx. 99.9% according to HPLC.

Instead of malononitrile, other CH-active compounds such as 1,3-indandione, barbituric acids and thiobarbituric acids (see US 2021/0234103, p. 71, Compound 1 and following) and 2-(4,5,5-trimethyl-2(5H)-furanylidene)-propanedinitrile and 2-(4,5,5-trimethyl-2(5/-/)-thiophenylidene)-propanedinitrile and their derivatives can be used.

Analogously, the following compounds can be prepared via the 5 steps, in yields of typically 10-40%:

Determination of the LUMO of the acceptor groups

The LUMO value of the acceptor groups Z is determined by quantum chemical calculation as described below. 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 thienothiophene substituent.

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.

absorption spectra

The absorption spectra of the compounds B1 and B500 according to the invention in degassed dichloromethane at a concentration of about 10 ^-5 M are shown in Figure 1. The absorption spectra of the compounds B301, B400, B700, B800, B801, B900, B907 and B1002 according to the invention in degassed dichloromethane at a concentration of about 10 ^-5 M are shown in Figure 2.

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. 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 1).

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 made 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)

Claims

patent claims 1 . Compound of formula (1 ) or formula (2),

Formula (1 ) Formula (2) where the symbols and indices used are: Ar ^a is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms which may be substituted by one or more radicals R ^a ; Ar ^b is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms which may be substituted by one or more R ^b radicals; Z is an electron acceptor group; Z can also form a ring system with R ^c ; Y ¹ is, at each occurrence, the same or different, S, Se or Te; Y ² is a bond, C(R ^d ) ₂ , O, S, Se, NR ^d ,C(=O), Si(R ^d ) ₂ , Ge(R ^d ) ₂ , C=NR ^d , C=C(R ^d ) ₂ , CR ^d =CR ^d or an aromatic or heteroaromatic ring system having 5 to 10 aromatic ring atoms, which may be substituted by one or more radicals R ^d ; Y ³ is a bond, C(R ^e ) ₂ , O, S, Se, NR ^e , C(=O), Si(R ^e ) ₂ , Ge(R ^e ) ₂ , C=NR ^e , C=C(R ^e ) ₂ , CR ^e =CR ^e or an aromatic or hetero- aromatic ring system with 5 to 10 aromatic ring atoms, which may be substituted by one or more radicals R ^e ; R ^a , R ^b , R ^c , R ^d , R ^e is the same or different on each occurrence and is 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 , 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 , OSO ₂ R ¹ , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic Alkyl, alkoxy or thioalkoxy group 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 CH ₂ groups can be replaced by R ¹ C=CR ¹ , C^C, Si(R ¹ ) ₂ , C=O, C=S, C=Se, C=NR ¹ , C(=O)O, C(=O)NR ¹ , NR ¹ , P(=O)(R ¹ ), Se, Te, BR ¹ , Ge(R ¹ ) ₂ , O, S, SO or SO ₂ , 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 a Aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or an arythio 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, R ^a , R ^b , R ^c , R ^d , R ^e can also form a ring system with one another or with another group; R ¹ is, identically or differently at each occurrence, H, D, F, CI, Br, I, CN, NO ₂ , 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 )s, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 C atoms or an alkenyl group with 2 to 40 C atoms, each 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 with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ² , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ² , 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 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 substituents R ² can form a ring system with one another; q is 1 or 2. 2. A compound according to claim 1, characterized in that the electron acceptor group Z is an organic group having a LUMO of < -2.8 eV, preferably < -2.9 eV. 3. A compound according to claim 1 or 2, characterized in that for Y ¹ , Y ² and Y ³ : Y ¹ is S or Se; Y ² is a bond, C(R ^d )2, O, S or NR ^d ; Y ³ is a bond, C(R ^e )2, 0, S or NR ^e . 4. A compound according to one or more of claims 1 to 3, 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. 5. A compound according to one or more of claims 1 to 4, 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 preferably stands for H, D or an optionally deuterated alkyl group having 1 to 6 C atoms and several R radicals can also form a ring with one another. 6. Compound according to one or more of claims 1 to 5, 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) and (Z-2-2), 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 the same or different on each occurrence and 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),

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),

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. 7. Compound according to one or more of claims 1 to 6, characterized in that the group Z is selected from the structures (Z-1a), (Z-2a) to (Z-2d), (Z-3a) to (Z-3zz) and (Z-4a) to (Z-4i), where these groups can also be partially or completely deuterated,

- -

- - wherein the dashed bond represents the attachment point and R has the meanings given in claim 4. 8. A compound according to one or more of claims 1 to 7, characterized in that Ar ^a and Ar ^b , identical or different on each occurrence, each represent an aryl or heteroaryl group having 6 to 13 aromatic ring atoms, which may be substituted by one or more radicals R ^a or R ^b . 9. A compound according to one or more of claims 1 to 8, selected from the compounds of formula (3) or formula (4),

where the symbols have the meanings given in claim 1 and furthermore: X ^a stands on each occurrence, identically or differently, for CR ^a or N, with the proviso that no more than two of the groups X ^a stand for N; or two adjacent X ^a together stand for a group of the following formula (X ^a -1 ) or (X ^a -2),

(X--1) (X ^a -2) where the dashed bonds represent the linkage of the group and A stands for 0, S or NR ^a ; X ^b represents, identically or differently on each occurrence, CR ^b or N, with the proviso that no more than two of the groups X ^b represent N; or two adjacent X ^b together represent a group of the following formula (X ^b -1 ) or (X ^b -2),

where the dashed bonds represent the linkage of the group and A stands for 0, S or NR ^b . 10. A compound according to one or more of claims 1 to 9, selected from the compounds of formulas (5), (5a) to (5f), (6) or (6a) to (6f),

formula (5)

formula (6)

where the compounds can also be partially or completely deuterated, Z stands for a group according to claim 5, the other symbols have the meanings given in claim 1 and furthermore: m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3. 11. A compound according to one or more of claims 1 to 10, selected from the compounds of formulas (7-1) to (7-8) and (8-1) to (8-3),

wherein the symbols and indices have the meanings given in claim 1 and Z stands for a group according to claim 5. 12. A compound according to one or more of claims 1 to 11, characterized in that the substituents R, R ^a , R ^b , R ^c , R ^d , R ^e are selected identically or differently on each occurrence are from the group consisting of H, D, F, CN, Si(R ¹ )3, B(OR ¹ )2, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl group may in each case be substituted by one or more radicals R ¹ , or an aromatic or heteroaromatic ring system having 6 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R ¹ . 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 in an electronic device. 15. Electronic device comprising at least one compound according to one or more of claims 1 to 12. 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.