Organic heterocycles for photoelectric devices

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

[0001] Organic heterocycles for photoelectric devices

[0002] 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.

[0003] Heterocyclic compounds are often used as photosensitizers in organic optical detectors. Heterocyclic compounds that can be used in optical detectors are known from CN 110964007 A, EP 3026722 A1, EP 3243822 A1, EP 3473622 A1, EP 3757108 A1, EP 3770163 A1, US 2019 / 0131541 A1, and EP 3848374 A1. In general, there is still room for improvement with these heterocyclic compounds, for example for use as photosensitizers, particularly with regard to lifetime, but also with regard to the efficiency and operating voltage of the device.

[0004] 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 photosensitizers in an organic optical detector, and which, when used in this device, lead to good device properties, as well as to provide the corresponding electronic device. In particular, it is the object of the present invention to provide compounds which lead to a long service life, good efficiency and low operating voltage. Furthermore, it is an object of the present invention to provide photosensitizers which are suitable for infrared, red, green or blue optical detectors, preferably for green or red optical detectors.

[0005] Surprisingly, it has been found that certain compounds, described in more detail below, solve this problem, are highly suitable for use in electronic devices, and lead to organic optical detectors that exhibit very good properties, particularly with regard to lifetime, efficiency, and operating voltage. These compounds, as well as electronic devices, in particular organic optical detectors, containing such compounds, are therefore the subject of the present invention.

[0006] The present invention relates to a compound of the formula

[0007] (1 ) or formula (2),

[0008] Formula (1 ) Formula (2) where the following applies to the symbols and indices used:

[0009] Ar® is an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is linked to one or more radicals R acan be substituted;

[0010] Ar b is an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is linked to one or more radicals R b can be substituted;

[0011] Z is an electron acceptor group; Z can be substituted with R c also form a ring system;

[0012] Y 1 is, identically or differently at each occurrence, S, Se or Te, preferably S or Se and particularly preferably S;

[0013] 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 is substituted by one or more radicals R d may be substituted, preferably a bond, C(R d )2, 0, S or NR dand particularly preferably C(R d )2;

[0014] Y 3 is a bond, C(R e )2, 0, 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 with 5 to 10, preferably with 5 or 6 aromatic ring atoms, which is substituted by one or more radicals R e may be substituted, preferably a bond, C(R e )2, 0, S or NR e ;

[0015] R a , R b , R c , R d , R e is, at each occurrence, the same or different: H, D, OH, F, CI, Br, I, CN, NO2, N(R 1 )2, C(=O)N(R 1 )2, C(R 1 )3, Si(R 1 )3, B(R 1 )2, C(=O)R 1 , P(=O)(R 1 )2, P(R 1 )2, S(=O)R 1 , S(=O)2R 1 , OSO2R 1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 1 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R 1 C=CR 1 , C=C, Si(R 1 )2, C=O, C=S, C=Se, C=NR 1 , C(=O)O, C(=O)NR 1 , NR 1 , P(=O)(R 1 ), Se, Te, BR 1 , Ge(R 1 )2, O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1may be substituted, or an arylthio or heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 may be substituted, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 may be substituted, or an aralkyl or heteroarylalkyl group having 5 to 60 aromatic ring atoms and 1 to 10 C atoms in the alkyl radical, which may be substituted by one or more radicals R 1 can be substituted; two radicals R, R a , R b , R c , R d , R e also form a ring system with each other or with another group;

[0016] R 1 is the same or different at each occurrence: H, D, F, CI, Br, I, CN, NO2, N(R 2 )2, C(=O)R 2 , P(=O)(R 2 )2, P(R 2 )2, B(R 2 )2, C(R 2 ) 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 is substituted by one or more radicals R 2 may be substituted, where one or more non-adjacent CH2 groups are substituted by , C=Se, C=NR 2 , C(=O)O, C( or SO2 and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2 may be substituted, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms which may be substituted with one or more radicals R 2may be substituted, or a combination of these systems; two or more, preferably adjacent, radicals R 1 form a ring system; one or more radicals R 1 form a ring system with another part of the compound;

[0017] R 2 is selected, identically or differently at each occurrence, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, CI, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, where two or more, preferably adjacent, substituents R 2 form a ring system with each other; q is 1 or 2, preferably 1.

[0018] Electron acceptor groups are generally known to those skilled in the art. Generally, they are groups that are capable of accepting electrons, i.e., being reduced. An electron acceptor group within the meaning of the present invention is preferably an organic group that has a LUMO of < -2.8 eV, preferably

[0019] < -2.9 eV, particularly preferably < -3.0 eV and most particularly preferably

[0020] < -3.2 eV. The LUMO of the electron-accepting group in the context of this compound is defined as the LUMO of group Z, which has a hydrogen atom instead of the thienothiophene substituent. The LUMO is determined by quantum chemical calculations, as generally described in the examples below.

[0021] An aryl group within the meaning of this invention contains 6 to 40 C atoms; a heteroaryl group within the meaning of this invention contains 2 to 40 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e. benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc., or a condensed (fused) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatics linked to one another by a single bond, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as an aromatic ring system.

[0022] An electron-deficient heteroaryl group within the meaning of the present invention is a heteroaryl group that 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-deficient heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, or quinoxaline. An aromatic ring system within the meaning of this invention contains 6 to 60 C atoms in the ring system, preferably 6 to 40 C atoms in the ring system. A heteroaromatic ring system within the meaning of this invention contains 2 to 60 C atoms, preferably 3 to 40 C atoms, and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O, and / or S.An aromatic or heteroaromatic ring system within the meaning of this invention is to be understood as a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be linked by a non-aromatic unit, such as a C, N, or O atom. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are to be understood as aromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are linked, for example, by a short alkyl group. The aromatic ring system is preferably selected from fluorene, 9,9'-spirobifluorene, 9,9-diarylamine, or groups in which two or more aryl and / or heteroaryl groups are linked by single bonds.

[0023] In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which may contain 1 to 20 C atoms and in which individual H atoms or CH2 groups may be substituted by the above-mentioned groups, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neo-pentyl, cyclopentyl, n-hexyl, neo-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, Cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentinyl, hexynyl, heptynyl or octynyl.Unter einer Alkoxygruppe mit 1 bis 40 C-Atomen werden bevor- zugt Methoxy, Trifluormethoxy, Ethoxy, n-Propoxy, i-Propoxy, n-Butoxy, i-Butoxy, s-Butoxy, t-Butoxy, n-Pentoxy, s-Pentoxy, 2-Methylbutoxy, n- Hexoxy, Cyclohexyloxy, n-Heptoxy, Cycloheptyloxy, n-Octyloxy, Cyclo- octyloxy, 2-Ethylhexyloxy, Pentafluorethoxy und 2,2,2-Trifluorethoxy ver- standen. Unter einer Thioalkylgruppe mit 1 bis 40 C-Atomen werden ins- besondere Methylthio, Ethylthio, n-Propylthio, i-Propylthio, n-Butylthio,.

[0024] 1-Butylthio, s-Butylthio, t-Butylthio, n-Pentylthio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclooctylthio,

[0025] 2-Ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio, or octynylthio. In general, alkyl, alkoxy, or thioalkyl groups according to the present invention can be straight-chain, branched, or cyclic, where one or more non-adjacent CH2 groups can be replaced by the above-mentioned groups; Furthermore, one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, preferably F, Cl or CN, more preferably F or CN, particularly preferably CN.

[0026] For the purposes of the present invention, the term "alkyl group" encompasses both straight-chain alkyl groups and branched or cyclic alkyl groups. The same applies to alkenyl, alkynyl, alkoxy, and thioalkoxy groups.

[0027] An aromatic or heteroaromatic ring system with 5 to 60 or 5 to 40 aromatic ring atoms, which may each be substituted with the above-mentioned radicals and which may be linked to the aromatic or heteroaromatic ring via any position, is understood to mean, in particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, iso- benzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, iso-quinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-chinolin, Phenothiazin, Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazin- imidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1 ,2-Thiazol, 1 ,3-Thiazol, Benzo- thiazol, Pyridazin, Hexaazatriphenylen, Benzopyridazin, Pyrimidin, Benz- pyrimidin, Chinazolin, Chinoxalin, 1 ,5-Diazaanthracen, 2,7-Diazapyren,

[0028] 2.3-Diazapyren, 1 ,6-Diazapyren, 1 ,8-Diazapyren, 4,5-Diazapyren, 4,5,9, 10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin,

[0029] 1 .2.3-Triazol, 1 ,2,4-Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1 ,2,4-Oxadi- azol, 1 ,2,5-Oxadiazol, 1 ,3,4-Oxadiazol, 1 ,2,3-Thiadiazol, 1 ,2,4-Thiadiazol, 1 ,2,5-Thiadiazol, 1 ,3,4-Thiadiazol, 1 ,3,5-Triazin, 1 ,2,4-Triazin,

[0030] 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.

[0031] For the purposes of this description, the phrase "two or more residues can form a ring" is understood to mean, among other things, that the two residues are linked by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme.

[0032] In education

[0033] Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring. This is illustrated by the following scheme:

[0034] The Z group is an electron acceptor group. Particularly suitable for this purpose are alkenyl groups substituted by at least two CN groups, alkenyl groups substituted by at least one CN group and at least one substituted carbonyl group, alkenyl groups substituted by two substituted carbonyl groups, where the substituents on the carbonyl groups form a ring system, or aromatic or heteroaromatic ring systems substituted by at least two CN groups. These electron acceptor groups are described in more detail below.

[0035] In a preferred embodiment of the invention, the group Z is an alkenyl group having 2 to 20 C atoms, where the alkenyl group may be substituted by one or more radicals R, where one or more non-adjacent CH2 groups may be replaced by O, S, Se or Si(R)2, with the proviso that the group Z has at least two CN groups or is substituted by at least one CN group and at least one substituted carbonyl group; the group Z may be substituted with R c form a ring system. In particular, it is a terminal alkenyl group substituted at the terminal C atom with two CN groups. R is analogous to R a to R e defined above.

[0036] 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 Z group are continuously conjugated with the 5-membered ring to which the Z group is bonded.

[0037] The term "conjugation" or "conjugated" is known to those skilled in the art. A continuous conjugation of the at least two CN groups of group Z is formed as soon as alternating double and single bonds are formed between the at least two CN groups or the at least one CN group and at least one substituted carbonyl group of group Z and the 5-membered ring containing the group Y. 1 and to which the group Z is bonded. A further link between the previously mentioned conjugated groups, for example via an S, N, or O atom, does not harm the conjugation.

[0038] In a preferred embodiment of the invention, Z is an alkenyl group having 2 to 10 C atoms, preferably having 2 to 6 C atoms, particularly preferably having 2 to 4 C atoms, which may be substituted by one or more radicals R, where at least two CN groups or at least one CN group and at least one substituted carbonyl group are bonded to the alkenyl group, preferably terminally; the alkenyl group may be bonded to the group R c form a ring system.

[0039] Particularly preferably, Z is an alkenyl group having 2 C atoms which is substituted by a radical R and two CN groups or one CN group and one substituted carbonyl group, wherein the two CN groups or the CN group and the substituted carbonyl group are preferably bonded terminally.

[0040] Preferred embodiments of the group Z are the structures of the formulas (Z-1), (Z-1 ') and (Z-2), where R and R 1have the meanings mentioned above, the dashed bond represents the connection point and furthermore:

[0041] R' stands for CN or for C(=O)R", where R" stands for OH, OD, an alkyl group having 1 to 6 C atoms or an alkoxy group having 1 to 6 C atoms; preferably R' = CN;

[0042] 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.

[0043] 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 may also optionally be deuterated:

[0044] 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.

[0045] For formula (Z-2) the following applies:

[0046] R, which is bonded to the non-cyclic alkenyl group in formula (Z-2), is preferably, identically or differently on each occurrence, H, D or an optionally deuterated alkyl group having 1 to 5 C atoms, particularly preferably H, D or optionally deuterated methyl and very particularly preferably H or D.

[0047] R, which is bonded to the five-membered ring in formula (Z-2), is preferably H, D, CN, F, an optionally deuterated alkyl group having 1 to 5 C atoms or an optionally deuterated phenyl group, which can also be substituted by one or more preferably non-aromatic radicals R 1 can be substituted.

[0048] Preferably, this R is selected from H, D, methyl, CD3 or CN.

[0049] The groups R 1which are bonded to the five-membered ring in formula (Z-2) are preferably identical or different on each occurrence and are H, D, an optionally deuterated alkyl group having 1 to 5 C atoms or an optionally deuterated phenyl group, which can also be substituted by one or more preferably non-aromatic radicals R 1 can be substituted. The two groups R 1 also form a ring system with each other. These groups R 1 identical or different on each occurrence, an optionally deuterated alkyl group having 1 to 4 C atoms, in particular optionally deuterated methyl groups.

[0050] Preferred embodiments of formula (Z-2) are the structures of the following formulas (Z-2-1) and (Z-2-2), where these groups may also be partially or completely deuterated, where the dashed bond represents the attachment site, R represents H, D, optionally deuterated methyl or CN and R 1identical or different at each occurrence represents H, D or optionally deuterated methyl, in particular optionally deuterated methyl.

[0051] Particularly preferred embodiments of formula (Z-2) are the structures of the following formulas (Z-2a) to (Z-2d), where these groups may also be partially or completely deuterated,

[0052] where the dashed bond represents the attachment point.

[0053] In a further preferred embodiment of the invention, the group Z is a terminal alkenyl group having 2 to 10 C atoms, preferably having 2 to 4 C atoms, and particularly preferably having 2 C atoms, which may be substituted by one or more substituents R and wherein the terminal C atom is substituted by a group -C(=O)-LC(=O)-. The two C(=O) groups of the group -C(=O)-LC(=O)- are each bonded to the terminal C atom of the alkenyl group, forming a cyclic group. The group L is a bivalent organic group.

[0054] A preferred embodiment of this group Z is a group of the following formula (Z-3), where the dashed bond represents the attachment of this group, R analogous to R a to R e is defined above and furthermore: L is an optionally deuterated bivalent aryl or heteroaryl group with

[0055] 5 to 14 aromatic ring atoms, preferably with 6 to 10 aromatic ring atoms, particularly preferably a phenylene group, each of which may be substituted by one or more radicals R, or a group according to one of the formulas -NR-C(=O)-NR-, -NR-C(=S)-NR or -NR-C(=C(CN)2)-NR, where R preferably represents H, D or an optionally deuterated alkyl group having 1 to 6 C atoms, in particular an optionally deuterated methyl group, or a group according to one of the formulas -CR2-CR2-, -CR2-CR2-CR2-, -CR2-C(=O)-CR2-, -O-CR2-O- or -NR-NR-, where R each preferably represents H, D or an optionally deuterated alkyl group having 1 to

[0056] 6 C atoms and several R residues can also form a ring with each other.

[0057] Preferred embodiments of formula (Z-3) are thus the structures of formulas (Z-3-1) to (Z-3-9), where the dashed bond represents the attachment of this group and R has the meanings given above.

[0058] The radical R which is bonded to the double bond in formula (Z-3) or (Z-3-1) to (Z-3-9) is preferably H or D. The radicals R which are bonded to the benzo group in formula (Z-3-1) are preferably the same or different on each occurrence and are H, D, F or CN. The radicals R which are bonded to the nitrogen atoms in formula (Z-3-2) to (Z-3-4) and (Z-3-8) are the same or different and are preferably H, D or an optionally deuterated alkyl group having 1 to 6 C atoms. The radicals R which are bonded to the carbon atoms of the aliphatic cycle in formula (Z-3-5) to (Z-3-7) and (Z-3-9) are preferably identical or different at each occurrence and represent H, D or an optionally deuterated alkyl group having 1 to 6 C atoms, where several radicals R can also form a ring with one another.It is preferred if the radicals R which are bonded to a carbon atom which is adjacent to a carbonyl group, identically or differently on each occurrence, represent D or an optionally deuterated alkyl group having 1 to 6 C atoms, in particular D or methyl.

[0059] Particularly preferred embodiments of the structure of formula (Z-3) are the structures of the following formulas (Z-3a) to (Z-3v), wherein these structures may also be partially or completely deuterated,

[0060] where the dashed bond represents the attachment of this group.

[0061] In a further embodiment of the invention, the group Z is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R, with the proviso that the group Z has at least two CN groups. Here, R is analogous to R a to R e defined above.

[0062] Preferred compounds are those in which at least one CN group and preferably at least two CN groups are bonded to the 5-membered ring containing Y 1 to which the aromatic or heteroaromatic ring system is bound, is continuously conjugated.

[0063] The term "conjugated" is known to the person skilled in the art. A continuous conjugation of the at least one CN group is formed, for example, by this group binding directly to an aryl or heteroaryl group, wherein this aryl or heteroaryl group is bonded to the 5-membered ring containing the group Y. 1and to which the aryl or heteroaryl group is bonded, is continuously conjugated.

[0064] Furthermore, a continuous conjugation of the at least one CN group of the group Z is formed as soon as alternating double and single bonds between the CN group of the group Z and the 5-membered ring, which the group Y 1 includes, are formed.

[0065] In a preferred embodiment of the invention, this group Z is a group according to the following formula (Z-4), where the dashed bond represents the attachment of this group, R analogous to R a to R e is defined above and continues to apply:

[0066] X 1 is the same or different on each occurrence CR or N, with the proviso that a maximum of three X 1 represent N and that a maximum of two N atoms are directly bonded to each other, and further with the proviso that at least two groups X 1stand for C-CN.

[0067] In a preferred embodiment of the formula (Z-4), a maximum of two groups X 1 for N, particularly preferably a maximum of one group X 1 for N and most preferably all groups X 1 for CR.

[0068] A preferred embodiment of formula (Z-4) is thus the structure of formula (Z-4-1 ), where the dashed bond represents the attachment of this group, R is as defined above and at least two groups R represent CN.

[0069] Particularly preferably, the group Z can represent a partial structure of the formulas (Z-4a) to (Z-4i),

[0070] where the dashed bond indicates the linkage of the group and R has the meanings given above. Preferably, a maximum of two R radicals are not H or D, particularly preferably a maximum of one R radical is not H or D, and very particularly preferably all R radicals are H or D.

[0071] The groups of formulas (Z-4a), (Z-4e), (Z-4f), (Z-4g) are preferred.

[0072] In a further preferred embodiment of the invention, the group Z is a terminal alkenyl group having 2 to 10 C atoms, preferably having 2 to 4 C atoms and particularly preferably having 2 C atoms, which may be substituted by one or more substituents R and wherein the terminal C atom is substituted by two groups -SO2R"'. The substituent R"' is preferably an alkyl group having 1 to 6 C atoms, wherein the two substituents R"' may also form a ring system with one another.

[0073] A preferred embodiment of this group Z is a group of the following formula (Z-5), where the dashed bond represents the attachment of this group, R analogous to R a to R e is defined above and continues to apply:

[0074] R"' is an optionally deuterated alkyl group having 1 to 6 C atoms; or the two groups R"' together form a ring and represent -CR2-CR2- or -CR2-CR2-CR2-, where R in each case preferably represents H, D or an optionally deuterated alkyl group having 1 to 6 C atoms and several radicals R can also form a ring with each other.

[0075] 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.

[0076] Examples of suitable acceptor groups Z are the structures shown in the table below, where these structures are linked via the dashed bond. The LUMO for each of these structures is also given, which is defined according to the invention as the LUMO for the corresponding compound that bears an H instead of the dashed bond, with the LUMO being calculated as described in the examples section.

[0077]

[0078] Preferred compounds are those for which:

[0079] Particularly preferred compounds are those for which:

[0080] In a preferred embodiment of the invention, Ar a and Ar bidentically or differently on each occurrence represents an aryl or heteroaryl group having 6 to 14 aromatic ring atoms, preferably having 6 to 13 aromatic ring atoms, which are substituted with one or more radicals R a or R b In a particularly preferred embodiment of the invention, Ar a and Ar b identical or different at each occurrence for benzene, naphthalene, phenanthrene, dibenzofuran, dibenzothiophene or carbazole, which in each case is substituted with one or more radicals R a or R b Preferably at least one of the groups Ar a and / or Ar b for benzene.

[0081] In a preferred embodiment of the invention, the compounds of formulas (1) and (2) are selected from the compounds of the following formulas (3) and (4),

[0082]

[0083] Formula (3) Formula (4) where the symbols used have the meanings given above, where q in formula (3) is preferably = 1, and furthermore:

[0084] X a stands for CR, the same or different at each occurrence a or N, preferably for CR a , provided that no more than two of the groups X a in a cycle for N; or two adjacent X a together represent a group of the following formula (X a -1 ) or (X a -2),

[0085] (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 stands;

[0086] X b stands for CR, the same or different at each occurrence b or N, preferably for CR b , provided that no more than two of the groups X b in a cycle for N; or two adjacent Xb together represent a group of the following formula (X b -1 ) or (X b -2),

[0087] (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 stands.

[0088] Preferred embodiments for the group Z in formulas (3) and (4) are the formulas (Z-1) to (Z-5) shown above, and particularly preferred structures are the formulas (Z-1-1) to (Z-1-3), (Z-2-1), (Z-2-2), (Z-3-1) to (Z-3-8), (Z-4-1), (Z-5-1) shown above, and very particularly preferred structures are the formulas (Z-1-1), (Z-1-2), (Z-1-3), (Z-2a) to (Z-2d), (Z-3a) to (Z-3zz) and (Z-4a) to (Z-4i) shown above. The structures (Z-1-1) and (Z-2a) to (Z-2d) are particularly preferred.

[0089] In a preferred embodiment of the invention, formula (3) or (4) contains not more than two groups Xa and X b for N. Particular preference is given to all groups X a and X b for CR a or CR b or for the condensed (X a -1 ), (X a -2), (X b -1 ) or (X b -2).

[0090] In a particularly preferred embodiment of the invention, the compounds according to the invention are selected from the compounds of formula (5) or (5a) to (5f), or (6) or (6a) to (6f),

[0091] Formula (5)

[0092] Formula (6)

[0093]

[0094] Formula (6e) Formula (6f) where the compounds may also be partially or fully deuterated, Z stands for a group of the formula (Z-1), (Z-2), (Z-3), (Z-4) or (Z-5), the further 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.

[0095] The following embodiments are therefore suitable:

[0096] 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.

[0097] Y is also preferred 1 in formulas (1 ), (2), (3), (4), (5), (5a) to (5f), (6) and (6a) to (6f) for S.

[0098] In a further preferred embodiment of the invention, Y 3 in formulas (1) and (2) and the preferred embodiments for a bond, C(R)2, O, S or NR d , and at the same time group Y 2 for C(R e )2, and at the same time the group Y 1is S or Se, preferably S. In a particularly preferred embodiment of the invention, Y 3 for a bond or C(R 3 )2, in particular for a bond, and Y 2 stands for C(R d )2, and Y 1 stands for S. In the compounds of formulas (5a) to (5f) and (6a) to (6f) the group Y is preferably 2 for C(R e )2, and the group Y 1 stands for S.

[0099] If Y 2 for C(R e )2, R e preferably identically or differently on each occurrence represents a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 12 C atoms, where the alkyl group may in each case be partially or completely deuterated and with one or more radicals R 1may be substituted, or for an aryl or heteroaryl group having 5 to 12 aromatic ring atoms, preferably a phenyl group, which may be partially or completely deuterated and by one or more radicals R 1 may be substituted, where the two radicals R e of group Y 2 together can form a ring. If two radicals R e together form a ring, a spiro system is formed, where the ring formed by the two residues R e The ring formed is preferably a 5-membered ring or a 6-membered ring. If Y 2 for C(R e )2, R e particularly preferably represents F, methyl, ethyl, neo-pentyl or phenyl, where these groups may also be partially or completely deuterated and where the two groups R e can also form a ring with each other, or the two groups R etogether with the C atom to which they bind, form a cyclopentyl, cyclohexyl or adamantanyl group, which may also be partially or fully deuterated. Particularly preferably, R e for methyl, which can also be partially or completely deuterated.

[0100] In a further preferred embodiment of the invention, the radical R c for H, D, a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 12 C atoms, wherein the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, or an aryl or heteroaryl group having 5 to 12 aromatic ring atoms, preferably a phenyl group, which may be substituted by one or more radicals R 1 may be substituted, where the radical R c can form a ring with the radical R. In a particularly preferred embodiment of the invention, the radical R crepresents H, D, optionally deuterated methyl or optionally deuterated phenyl, most preferably H or D.

[0101] In a further preferred embodiment of the invention, the radical R d 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 is in each case substituted with one or more radicals R 1 may be substituted, or an aryl or heteroaryl group having 5 to 12 aromatic ring atoms, preferably a phenyl group, which may be substituted by one or more radicals R 1 can be substituted.

[0102] 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),

[0103]

[0104]

[0105] 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). Compounds of the formulas (7-2), (7-5) and (7-6) are preferred, and compounds of the formula (7-6) are particularly preferred.

[0106] 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.

[0107] When two residues, 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 each other, this can be mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic. The radicals forming a ring system can be adjacent, meaning that these radicals are bonded to the same carbon atom or to carbon atoms that are directly bonded to each other, or they can be further apart.

[0108] 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.

[0109] Furthermore, preferred compounds according to the invention are characterized in that they are sublimable.

[0110] Preferred substituents R, R a , R b , Rc , R d and R e described.

[0111] In a preferred embodiment of the invention, R, R a , R b , R c , R d and R e identically or differently at each occurrence selected from the group consisting of H, D, F, CN, Si(R 1 )s, B(OR 1 )2, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, wherein the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system having 6 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 may be substituted; two or more radicals may form a ring system with each other. In a particularly preferred embodiment of the invention, R, R a , R b , R c , R d and Re identically or differently on each occurrence selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms, preferably having 1 to 4 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, preferably having 3 to 6 C atoms, where the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, particularly preferably having 6 to 18 aromatic ring atoms, most preferably having 6 to 13 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted; two or more residues can form a ring system with each other.

[0112] It may be preferred if at least one of the substituents R, R a , R b , R c , R d , R eidentically or differently on each occurrence represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, particularly preferably having 6 to 18 aromatic ring atoms, very particularly preferably having 6 to 13 aromatic ring atoms, which in each case is substituted by one or more radicals R 1 can be substituted.

[0113] Preferred aromatic or heteroaromatic ring systems R, R a , R b , R c , R d and / or R eare selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which may be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which may be linked via the 1-, 2-, 3- or 4-position, naphthalene, in particular 1- or 2-linked naphthalene, indole, benzofuran, benzothiophene, carbazole, which may be linked via the 1-, 2-, 3-, 4- or 9-position, dibenzofuran, which may be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, which may be linked via the 1-, 2-, 3- or 4-position may be indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which is substituted with one or more radicals R, R 1 or R 2 can be substituted.

[0114] 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 at each occurrence, from the groups of the following formulas R-1 to R-184,

[0115]

[0116] R-23 R-24

[0117] R-22

[0118]

[0119]

[0120]

[0121]

[0122] R-152

[0123]

[0124] where R 1 has the meanings given above, the dashed bond represents the bond and furthermore:

[0125] Ar 3is at each occurrence, identically or differently, a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, each of which is substituted by one or more radicals R 1 can be substituted;

[0126] A 1 is the same or different each time it occurs BR 1 , C(R 1 )2, C=O, NR 1 , 0 or S, where A 1 in the formulas R-150, R-151 and R-152 for BR 1 , C=O, NR 1 , 0 or S;

[0127] A 2 is the same or different at each occurrence C(R 1 )2, NR 1 , 0 or S; p is 0 or 1 , where p = 0 means that the group Ar 3is not present and that the corresponding aromatic or heteroaromatic group is directly bonded to the associated atom, for example a carbon atom or to a heteroatom such as a nitrogen, where, in the case of bonding to a heteroatom, for the formulas R-44, R-49, R-53, R-57, R-58, R-62, R-66, R-70, R-71, R-112, R-152 to R-160, R-167, R-172, R-177, R-182 p is 1; r is 0 or 1, where r = 0 means that no group A is present at this position. 1 and the corresponding carbon atoms are instead bound to residues R 1 are bound.

[0128] In a preferred embodiment, Ar comprises 3 bivalent aromatic or heteroaromatic ring systems based on the groups R-1 to R-184, where p is 0 and the dashed bond and an R 1 represents the bond to the aromatic or heteroaromatic group according to R-1 to R-184.

[0129] If the above groups R-1 to R-184 contain several groups A 1 all combinations from the definition of A 1 Preferred embodiments are then those in which a group A 1 for C(R 1 )2, NR 1 , 0 or S and the other group A 1 for C(R 1 )2, NR 1 , 0 or S.

[0130] If A 1 for NR 1 the substituent R 1 which is bonded to the nitrogen atom, preferably represents an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 2 In a particularly preferred embodiment, this substituent R 1identical or different on each occurrence represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, and which in each case can also be substituted by one or more radicals R 2 Particularly preferred are phenyl, biphenyl, terphenyl and quaterphenyl with linkage patterns as listed above for R-1 to R-35, where these structures are substituted by one or more radicals R 1 may be substituted, but are preferably unsubstituted.

[0131] If A 1 for C(R 1 )2, the substituents R 1which are bonded to this carbon atom, preferably identically or differently on each occurrence, represent a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 2 R is particularly preferably 1 represents a methyl group or a phenyl group. The radicals R 1 also form a ring system with each other, which leads to a spiro system.

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

[0133] Ar 4 and Ar 2 with each other and / or Ar 2 and Ar 3 with each other also by a group selected from C(R 1 )2, NR 1 , O or S. Preferably, the linking of Ar 4 and Ar 2 with each other or from Ar 2 and Ar 3 are ortho to the position of the linkage to the nitrogen atom. In a further embodiment of the invention, none of the groups Ar 2 , Ar 3 or Ar 4 connected to each other. Ar is preferred 4an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted. Particularly preferred is Ar 4 selected from the group consisting of ortho-, meta- or para-phenylene or ortho-, meta- or para-biphenyl, each of which is substituted by one or more radicals R 1 may be substituted, but are preferably unsubstituted. Ar is particularly preferred 4 an unsubstituted phenylene group.

[0134] Preference is given to Ar 2 and Ar 3 identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 1 Particularly preferred groups Ar 2 or Ar 3are, identically or differently at each occurrence, selected from the group consisting of benzene, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spiro-bifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene, 1-, 2-

[0135] 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-,

[0136] 4- or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene or triphenylene, each of which is substituted with one or more radicals R 1 may be substituted. Particularly preferred are Ar 2 and Ar 3identically or differently on each occurrence selected from the group consisting of benzene, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, in particular 1-, 2-, 3- or 4-fluorene, or spirobifluorene, in particular 1-, 2-, 3- or 4-spirobifluorene.

[0137] In a further preferred embodiment of the invention, R 1 identically or differently on each occurrence selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl group is in each case substituted with one or more radicals R 2 may be substituted, or an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, each substituted by one or more radicals R2 may be substituted; two or more radicals R 1 form a ring system with each other. In a particularly preferred embodiment of the invention, R 1 identically or differently on each occurrence selected from the group consisting of H, a straight-chain alkyl group having 1 to 6 C atoms, in particular having 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group having 3 to 6 C atoms, where the alkyl group is in each case substituted with one or more radicals R 2 may be substituted, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, each substituted by one or more radicals R 2 may be substituted, but is preferably unsubstituted; two or more radicals R 1 form a ring system with each other.

[0138] In a further preferred embodiment of the invention, R 2identical or different on each occurrence H, D, an alkyl group having 1 to 4 C atoms or an aryl group having 6 to 10 C atoms, which may be substituted by an alkyl group having 1 to 4 C atoms, but is preferably unsubstituted.

[0139] In compounds according to the invention that are processed by vacuum evaporation, the alkyl groups preferably have no more than five carbon atoms, particularly preferably no more than 4 carbon atoms, and most preferably no more than 1 carbon atom. Also suitable for compounds that are processed from solution are compounds that are substituted by alkyl groups, particularly branched alkyl groups, with up to 10 carbon atoms, or that are substituted by oligoarylene groups, for example ortho-, meta-, para-, or branched terphenyl or quaterphenyl groups.

[0140] 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 preferences occur simultaneously. Examples of preferred compounds according to the above-mentioned embodiments are the compounds listed in the following table:

[0141]

[0142] The compounds of the invention can, in principle, be prepared by various methods. However, the methods described below have proven particularly suitable.

[0143] Therefore, a further subject 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.

[0144] 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 Z group, followed by the introduction of the Z group, for example by formylation or acylation of the position at which the Z group 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 having an aromatic amino group (1) can be reacted with a 5-membered ring heterocycle (2) (thienothiophene, selenolothiophene, selenoloselenophene) in an Ullmann coupling. The compound (3) thus obtained can be reacted with a carbonyl compound (4) in a hydroxyalkylation reaction 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 into a carbonyl compound (8) by formylation or acylation in step 4. In step 5, the carbonyl compound (8) can be reacted in a Knoevenagel condensation with a CH-acidic compound H2CZ' (9), such as malononitrile, 1,3-inandione, barbituric acids, thiobarbituric acids, 2-(4,5,5-trimethyl-2(5-phenyl)-furanylidene)-propanedinitriles and 2-(4,5,5-trimethyl-2(5-phenyl)-thiophenylidene)-propanedinitriles and their derivatives (9) to form 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.

[0145] Scheme 1 :

[0146] Step 1 : Ullmann coupling

[0147] CR2, SiR2, NR, O, S, Se, etc.

[0148] Step 2: Hydroxyalkylation Step 3: Cyclization

[0149] Step 5: Knoevenagel condensation

[0150] The synthesis of the compounds according to the invention can furthermore be carried out according to the following Scheme 2, by which in particular compounds with further groups Y 2 can be obtained, such as 0, 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 containing an aromatic amino group (11) can be reacted with a 2,3-bishalofunctionalized 5-membered ring heterocycle (12) by double Ullmann coupling. The resulting compound (13) can be prepared by formylation or

[0151] Acylation can be derivatized 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:

[0152] Step 1 : Ullmann coupling

[0153] Step 2: Formylation or acylation

[0154] Step 3: Knoevenagel condensation

[0155] The synthesis of the compounds according to the invention can also be carried out according to the following Scheme 3, by 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:

[0156] Step 1 : Ullmann coupling

[0157] 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 by R. Furthermore, for reasons of clarity, the use of symbols to represent possible nitrogen atoms in the heteroaromatic rings has often been omitted, as these are represented, for example, in formulas (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 presented above and below, in particular in the examples, to compounds in which one or more of the symbols Symbols Xa and X b represent nitrogen or which contain other aromatic groups, such as naphthalene, instead of the benzene groups in the basic structure.

[0158] 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).

[0159] The compounds of the invention can also be mixed with a polymer. It is also possible to incorporate these compounds covalently into a polymer.

[0160] Of particular interest are compounds according to the invention that are characterized by a high glass transition temperature. In this context, particular preference is given to compounds according to the invention of formula (1) or (2) or the preferred embodiments that have a glass transition temperature of at least 70 °C, more preferably of at least 110 °C, most preferably of at least 125 °C, and especially preferably of at least 150 °C, determined according to DIN 51005 (version 2005-08).

[0161] For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, Cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP,p-Cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butylmethyl ether, triethylene glycol butylmethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyloctanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents.

[0162] The present invention therefore further provides a formulation or a composition comprising at least one compound according to the invention and at least one further compound. The further compound can, for example, be a solvent, in particular one of the abovementioned solvents or a mixture of these solvents. 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, wherein 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.

[0163] The present invention therefore further provides a composition comprising a compound according to the invention and at least one further organic functional material. Functional materials are generally the organic or inorganic materials introduced between the anode and cathode. The organic functional material is preferably selected from the group consisting of photosensitizers, electron-transport materials, electron-injection materials, hole-conducting materials, hole-injection materials, electron-blocking materials, and hole-blocking materials, preferably photosensitizers, electron-transport materials, electron-injection materials, and hole-blocking materials.

[0164] A further object of the present invention is the use of a compound according to the invention in an electronic device, preferably an organic, photoelectric device, in particular in an organic optical detector, preferably as a photosensitizer, particularly preferably as a green, red, infrared or blue photosensitizer, especially preferably as a green photosensitizer.

[0165] The present invention further relates to an electronic device comprising at least one compound according to the invention. An electronic device within the meaning of the present invention is a device that contains at least one layer containing at least one organic compound. The component may also contain inorganic materials or layers composed entirely of inorganic materials.

[0166] The electronic device is preferably selected from the group consisting of organic photoelectric devices, organic electroluminescent devices (OLEDs, sOLEDs, PLEDs, LECs, etc.), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), organic plasmon emitting devices (DM Koller et al., Nature Photonics 2008, 1-4), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic 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.

[0167] The organic optical detector contains a cathode, an anode, and at least one light-absorbing layer. In addition to these layers, it may contain further layers, for example, one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers, and / or charge-generation layers. Interlayers, which, for example, have an exciton-blocking function, may also be inserted between two light-absorbing layers. It should be noted, however, that not all of these layers are necessarily present. The organic optical detector may contain one light-absorbing layer, or it may contain multiple light-absorbing layers.

[0168] 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, where the color indicates the color of the light absorbed by the photosensitizer.

[0169] When the compound of the invention is used as a photosensitizer in a light-absorbing layer, a suitable co-material known per se is preferably used. The co-material is used either as a mixture with the photosensitizer or in a layer adjacent to the layer containing the photosensitizer.

[0170] Suitable co-materials which can be used in combination, i.e. as a mixture with the compounds according to the invention or in a layer adjacent to the layer containing the compounds according to the invention, are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g. according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triarylamines, carbazole derivatives, e.g. B. CBP (N,N-biscarbazolylbiphenyl) or those in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176, indolocarbazole derivatives, e.g. according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, e.g. according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776, azacarbazole derivatives, e.g. B. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar comaterials, e.g. B. according to WO 2007 / 137725, silanes, e.g. B. according to WO 2005 / 111172, azaboroles or boron esters, e.g. b.according to WO 2006 / 117052, triazine derivatives, e.g. according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, diazasilole or tetraazasilole derivatives, e.g. according to WO 2010 / 054729, diazaphosphole derivatives, e.g. according to WO 2010 / 054730, bridged carbazole derivatives, e.g. B. according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080, triphenylene derivatives, e.g. according to WO 2012 / 048781, dibenzofuran derivatives, e.g. according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565 or biscarbazoles, e.g. according to JP 3139321 B2.

[0171] 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, or hole-blocking materials. Particular preference is given to using, among others, subphthalocyanines, subphthalocyanine derivatives, fullerenes, or fullerene derivatives. Such compounds are known to those skilled in the art for use in organic optical detectors.

[0172] 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.

[0173] Preferred subphthalocyanines, subphthalocyanine derivatives, fullerenes, or fullerene derivatives are described, inter alia, in European patent application EP 3848374 A1, which is incorporated herein by reference for disclosure purposes. These materials are set forth in particular on pages 84 to 86 (see paragraphs

[0322] to

[0332] ).

[0174] In the further layers of the organic optical detector according to the invention, all materials commonly used in the prior art can be used. Therefore, without inventive effort, the skilled person can 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.

[0175] Also preferred is an organic optical detector characterized in that one or more layers are coated using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10' 5 mbar, preferably less than 10' 6 mbar. However, it is also possible that the initial pressure is even lower, for example less than 10' 7 mbar.

[0176] Also preferred is an organic optical detector, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are sublimated at a pressure between 10' 5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured.

[0177] Also preferred is an organic optical detector characterized in that one or more layers are produced from solution, such as by spin coating, or by any printing process, such as screen printing, flexographic printing, offset printing, LITI (Light Induced Thermal Imaging, thermal transfer printing), inkjet printing, or nozzle printing. Soluble compounds are required for this purpose, 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.

[0178] 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.

[0179] Further details of preferred electronic devices, in particular organic optical detectors, as well as their manufacture, are known from the prior art. These are described, inter alia, in European patent application EP 3848374 A1, which is incorporated herein by reference for disclosure purposes. Reference is made in particular to Figures 1 to 10 described in EP 3848374 A1, which are set forth, inter alia, on pages 83 to 90 of document EP 3848374 A1.

[0180] 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:

[0181] 1 . In particular, compounds according to formula (1) and (2) and the preferred embodiments which contain thienothiophene structures, in which X 1stands for S, have the advantage that they are less toxic than compounds in which one or more X 1 stand for Se.

[0182] 2. The compounds according to formulas (1) and (2) and the preferred embodiments described above exhibit a very high extinction coefficient. This is a significant advantage for the use of the materials in organic optical detectors.

[0183] 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 lifetime.

[0184] 4. Electronic devices, in particular organic optical detectors, containing compounds according to formula (1) or (2) or the preferred embodiments described above as photosensitizers exhibit excellent efficiency. The compounds according to the invention according to formula (1) or (2) or the preferred embodiments described above result in a low operating voltage when used in electronic devices.

[0185] 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.

[0186] 6. Compounds according to formula (1) or (2) or the preferred embodiments described above can be used to prevent the formation of optical loss channels in electronic devices, particularly organic optical detectors. As a result, these devices are characterized by high photocurrent efficiency of photosensitizers and excellent energy transfer.

[0187] 7. Compounds according to formula (1) or (2) or the preferred embodiments described have excellent glass film formation.

[0188] These advantages mentioned above are not accompanied by a deterioration of the other electronic properties.

[0189] The invention is further illustrated by the following examples, without intending to limit it. From these descriptions, one skilled in the art can practice the invention within the entire disclosed scope and, without inventive step, prepare further compounds according to the invention and use them in electronic devices or apply the method according to the invention.

[0190] Description of the characters

[0191] Figure 1 shows the absorption spectra of two compounds according to the invention (compounds B1 and B500) in a concentration of approximately 10 -5 M in degassed dichloromethane. Figure 2 shows the absorption spectra of eight further compounds according to the invention (compounds B301, B400, B700, B800, B801, B900, B907 and B1002) in a concentration of approximately 10 -5 M in degassed dichloromethane.

[0192] Examples:

[0193] Unless otherwise stated, the following syntheses were carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be obtained, for example, from Sigma-ALDRICH or ABCR. The respective information in square brackets or the numbers given for individual compounds refer to the CAS numbers of the compounds known from the literature. For compounds that can exhibit multiple enantiomeric, diastereomeric, or tautomeric forms, one form is shown as a representative.

[0194] Procedure analogous to K. Mazzio et al, Appl. Mat. & Interfaces, 2011 , 3, 2, 271 . A solution of 3.46 g (10 mmol) of (6) (step 3 with X = single bond & Y = S) and 1.59 g (10 mmol) of 4-methyl-3-cyclohexene-1-carbonyl chloride [16695-95-7] ​​in 150 ml of DCM, cooled to 0 °C, is treated dropwise over 10 min with a solution of 1.73 g (13 mmol) of anhydrous aluminum chloride, and stirred for 1 h. The mixture is quenched by careful addition of 50 g of ice, the organic phase is separated, washed twice with 50 ml of water each time, once with 50 ml of saturated sodium chloride solution and dried over magnesium sulfate:sodium carbonate (1:1). The desiccant is filtered off, the filtrate is concentrated in vacuo, 30 g of 85% polyphosphoric acid is added to the orange oil, the mixture is homogenized at 50 °C, and the temperature is then increased to 100 °C. After 30 minutes, the mixture is allowed to cool to 50 °C, and then 200 ml of water is added 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 bicarbonate solution, twice with 50 ml of water each, and once with 50 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The drying agent is removed with suction, and the filtrate is concentrated to dryness in vacuo. The crude product is further purified by chromatography (Torrent column chromatography from A. Semrau). Yield: 937 mg (2.0 mmol) 20%; Purity: approximately 97% pure. 1 H-NMR.

[0195]

[0196] Synthesis of the compounds according to the invention:

[0197] 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-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 reacted 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-inandedione, 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) are reacted to give the compounds (10) according to the invention.

[0198] Scheme 1 :

[0199] Step 1 : Ullmann coupling

[0200] X: single bond,

[0201] CR2, NR, O, S, Se, Te

[0202] Step 2: Hydroxyalkylation

[0203] Step 4: Formylation or acylation

[0204] Step 5: Knoevenagel condensation

[0205]

[0206] Alternative procedure to step 2: Suzuki clutch

[0207] A well-stirred mixture of 100 mmol of (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, and the organic phase is washed three times with 300 mL of water and once with 200 mL of saturated sodium chloride solution, and dried over magnesium sulfate. The drying agent is removed by filtration through a silica gel bed pre-slurried with EA, and the solvent is removed in vacuo. The residue is reacted further without further purification.

[0208] Alternative procedure to step 3: Cyclization

[0209] A well-stirred mixture of 100 mmol of (11 ) and 400 g of polyphosphoric acid is heated to 90 °C for 1 h. The reaction mixture is allowed to cool to 60 °C, poured into 5 l of ice water with vigorous stirring, stirred for 30 min, and the precipitated solid is filtered off with suction or extracted with EA or dichloromethane (DCM). The crude product is recrystallized from DCM / acetonitrile or chromatographed.

[0210] Alternative procedure to step 5: Knoevenagel condensation,

[0211] A well-stirred mixture of 100 mmol of (8), 110 mmol of (9) or the other acceptors, especially the 1,3-diones, 105 mmol of piperidine, and 500 ml of acetonitrile is heated under reflux for 20 h. After cooling, the precipitated product is filtered off with suction, washed three times with a little acetonitrile, and dried in vacuo. Products that do not precipitate can be isolated by extraction in a water / dichloromethane system. The crude product is purified by chromatography (Torrent column chromatography machine from A. Semrau) and / or repeated hot extraction crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) as well as fractional sublimation or annealing under high vacuum.

[0212] Alternative method for introducing BR, SiRz, GeRz, NR, S bridges:

[0213] Example B1:

[0214] 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 in high vacuum (p approx. 10' 5 mbar).

[0215] Yield: 29.8 g (71 mmol) 71%; Purity: approximately 99.9% by HPLC.

[0216] 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(5H)-thiophenylidene)-propanedinitrile and their derivatives can be used.

[0217] Analogously, the following compounds can be prepared via the 5 steps, in yields of typically 10-40%:

[0218]

[0219] Determination of the LUMO of the acceptor groups

[0220] The LUMO value of the acceptor groups Z is determined by quantum chemical calculations as described below. The LUMO of the electron acceptor group in the context of the present compound is defined as the LUMO of the group Z that has a hydrogen atom instead of the thienothiophene substituent.

[0221] The Gaussian16 program package (Rev. B.01) is used for all quantum chemical calculations. The neutral singlet ground state is optimized at the B3LYP / 6-31 G(d) level. LUMO calc. values ​​are determined at the B3LYP / 6-31 G(d) level for the ground state energy optimized with B3LYP / 6-31 G(d). The default settings for SCF and gradient convergence are used.

[0222] The LUMO calc. value in eV derived from the quantum chemical calculation is additionally scaled with the following factors: LUMO = 0.99687 * LUMO calc. - 0.72445.

[0223] Absorption spectra

[0224] The absorption spectra of the compounds B1 and B500 according to the invention in degassed dichloromethane at a concentration of approximately 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 approximately 10 -5 M are shown in Figure 2.

[0225] Examples of photodiodes:

[0226] 1) Manufacturing of mono-layer photodiodes (MLPD)

[0227] Cleaned quartz substrates (15 min. ultrasound in an acetone / isopropanol / water bath (1:1:1 v:v:v), followed by UV-ozone) are sputtered with a 150 nm thick indium tin oxide (ITO) anode. A 30 nm thick layer of HTM2 (see Table 3) is then deposited on top of this under high vacuum, followed by an 80 nm thick layer of the inventive compounds B and Ceo in a volume ratio of 1:1 by co-evaporation. A 1.5 nm thick ytterbium layer is then 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).

[0228] Table 1 :

[0229] 2) Manufacturing of bi-layer photodiodes (BLPD)

[0230] Cleaned quartz substrates (15 min. ultrasound in an acetone / isopropanol / water bath (1:1:1 v:v:v), followed by UV ozone) are sputtered with a 150 nm thick indium tin oxide (ITO) anode. All other materials are thermally deposited in a vacuum chamber. The materials used to fabricate the BLPDs are shown in Table 3. The electron transport layer 2 (ETL2) can be fabricated by co-evaporation of two materials. A designation such as ETM1:EIL (50:50) means that the co-evaporated layer contains 50% by volume of each of the individual materials.

[0231] Structure of the BLPD:

[0232] ITO substrate BLPD hole injection layer (HIL) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 10 nm

[0233] Hole transport layer 1 (HTL1), see Table 2

[0234] 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

[0235] 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).

[0236] 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 following applies to the symbols and indices used: Ar a is an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is linked to one or more radicals R a can be substituted; Ar b is an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is linked to one or more radicals R b can be substituted; Z is an electron acceptor group; Z can be substituted with R c also form a ring system; Y 1 is the same or different at each occurrence: 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 dor an aromatic or heteroaromatic ring system with 5 to 10 aromatic ring atoms, which is substituted by one or more radicals R d can be substituted; 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 is linked by one or more radicals R e can be substituted; R a , R b , R c , R d , R e is the same or different at each occurrence: H, D, OH, F, CI, Br, I, CN, NO2, N(R 1 )2, C(=O)N(R 1 )2, C(R 1 )3, Si(R 1 )3, B(R 1 )2, C(=O)R 1 , P(=O)(R 1 )2, P(R 1 )2, S(=O)R 1 , S(=O)2R 1 , OSO2R 1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 1 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R 1 C=CR 1 , C^C, Si(R 1 )2, C=O, C=S, C=Se, C=NR 1 , C(=O)O, C(=O)NR 1 , NR 1 , P(=O)(R 1 ), Se, Te, BR 1 , Ge(R 1 )2, O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R1 may be substituted, or an arylthio or heteroarylthio group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 may be substituted, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 may be substituted, or an aralkyl or heteroarylalkyl group having 5 to 60 aromatic ring atoms and 1 to 10 C atoms in the alkyl radical, which may be substituted by one or more radicals R 1 can be substituted; two radicals R, R a , R b , R c , R d , R e also form a ring system with each other or with another group; R 1 is the same or different at each occurrence H, D, F, CI, Br, I, CN, NO2, N(R 2 )2, C(=O)R 2 , P(=O)(R 2 )2, P(R 2 )2, B(R 2 )2, C(R 2 )3, Si(R2 )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 is substituted by one or more radicals R 2 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R 2 C=CR 2 , C=C, Si(R 2 )2, C=O, C=S, C=Se, C=NR 2 , C(=O)O, C(=O)NR 2 , NR 2 , P(=O)(R 2 ), O, S, SO or SO2 and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2may be substituted, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms which may be substituted with one or more radicals R 2 may be substituted, or a combination of these systems; two or more radicals R 1 form a ring system; one or more radicals R 1 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 may be replaced by D, F, CI, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, where two or more substituents R 2form a ring system; q is 1 or 2.

2. 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 Y 1 , Y 2 and Y 3 applies: Y 1 is S or Se; Y 2 is a bond, C(R d )2, 0, 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 ein claim 1 and wherein one or more non-adjacent CH2 groups may be replaced by O, S, Se or Si(R)2, with the proviso that the alkenyl group has at least two CN groups or at least one CN group and one substituted carbonyl group; the alkenyl group may be substituted with R c form a ring system; (B) a terminal alkenyl group having 2 to 10 C atoms, which may be substituted by one or more substituents R, where R has the same meanings as R a to R e in claim 1 and wherein the terminal C atom is substituted with a group -C(=O)-LC(=O)-; wherein the group L is a divalent organic group; (C) an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R, with the proviso that the group has at least two CN groups; where R is analogous to R a to Re defined 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) where R and R 1 have the meanings given in claims 1 and 4, the dashed bond represents the attachment point and furthermore: R' stands for CN or for C(=O)R", where R" stands for OH, OD, an alkyl group with 1 to 6 C atoms or an alkoxy group with 1 to 6 C atoms X is 0, S or Se; p is 0, 1 or 2; or that the group Z represents a group of formula (Z-3), where the dashed bond represents the linkage of this group, R has the meanings given in claim 4 and furthermore: L is a bivalent aryl or heteroaryl group having 5 to 14 aromatic ring atoms, each of which may be substituted by one or more radicals R, or a group according to one of the formulas -NR-C(=O)-NR-, -NR-C(=S)-NR, -NR-C(=C(CN)2)-NR, -CR2-CR2-, -CR2-CR2-CR2-, -CR2-C(=O)-CR2- or -NR-NR-; or that group Z represents a group according to formula (Z-4), where the dashed bond represents the linkage of this group, R has the meanings given in claim 4 and furthermore: X 1 is the same or different on each occurrence CR or N, with the proviso that a maximum of three X 1 represent N and that a maximum of two N atoms are directly bonded to each other, and further with the proviso that at least two groups X 1 represent C-CN; or that the group Z represents a group of formula (Z-5), where the dashed bond represents the linkage of this group, R has the meanings given in claim 4 and furthermore: R"' is an optionally deuterated alkyl group having 1 to 6 C atoms; or the two groups R"' together form a ring and stand for -CR2-CR2- or -CR2-CR2-CR2-, where R in each case preferably stands for H, D or an optionally deuterated alkyl group having 1 to 6 C atoms and several radicals R can also form a ring with one another.

6. A 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 may also be partially or completely deuterated, where the dashed bond represents the attachment site, R represents H, D, optionally deuterated methyl or CN and R 1identically or differently on each occurrence represents H, D or optionally deuterated methyl; or that group Z is selected from the structures of the formulas (Z-3-1) to (Z-3-9), wherein the dashed bond represents the linkage of this group and R has the meanings given in claim 4; or that the group Z represents a structure of the formula (Z-4-1 ), wherein the dashed bond represents the linkage of this group, R has the meanings given in claim 4 and at least two groups R represent CN; or that the group represents a structure of the formula (Z-5-1), wherein the dashed bond represents the attachment of this group and R"' has the meanings given in claim 5 and the group may 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 may also be partially or completely deuterated, - - - - wherein the dashed bond represents the attachment point and R has the meanings given in claim 4.

8. Compound according to one or more of claims 1 to 7, characterized in that Ar a and Ar b identically or differently on each occurrence each represent an aryl or heteroaryl group having 6 to 13 aromatic ring atoms which, with one or more radicals R a or R b can be substituted.

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 for CR, the same or different at each occurrence a or N, provided that no more than two of the groups X a represent N; or two adjacent X a together represent 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 stands; X b stands for CR, the same or different at each occurrence b or N, provided that no more than two of the groups X b represent N; or two adjacent X btogether 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 stands.

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 may also be partially or fully deuterated, Z represents a group according to claim 5, the further 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 invention is R, R a , R b , R c , R d , R e selected the same or different at 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, wherein the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system with 6 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted.

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.

Images