Materials for electronic devices

Abstract

The present invention relates to compounds of a formula (I), to their use in electronic devices, to electronic devices containing at least one compound of formula (I), and to methods for producing compounds of formula (I).

Description

[0001] Materials for electronic devices This application relates to aromatic amines that contain certain carbazolyl, dibenzofuranyl, or dibenzothiophenyl groups on the amine nitrogen atom. The compounds are suitable for use in electronic devices. Electronic devices within the meaning of this application are understood to mean so-called organic electronic devices (organic electronic devices) that contain organic semiconductor materials as functional materials. In particular, this refers to OLEDs (organic electroluminescent devices). The term OLEDs refers to electronic devices that have one or more layers containing organic compounds and emit light when an electrical voltage is applied. The structure and general operating principle of OLEDs are known to those skilled in the art.There is great interest in improving the performance of electronic devices, particularly OLEDs. A completely satisfactory solution has not yet been found in these areas. Furthermore, alternative compounds for use in electronic devices, particularly OLEDs, are needed. Emission layers and layers with hole-transporting functions have a significant influence on the performance of electronic devices. New compounds are still being sought for use in these layers, particularly hole-transporting compounds and compounds that can serve as hole-transporting matrix materials, particularly for phosphorescent emitters, in an emitting layer. For this purpose, compounds with a high glass transition temperature, high stability, and high hole conductivity are particularly sought.High compound stability is a prerequisite for achieving a long service life of the electronic device. Furthermore, compounds are sought whose use in electronic devices leads to improved device performance, in particular high efficiency, long service life, and low operating voltage. In the prior art, triarylamine compounds such as spirobifluorenamines and fluorenamines are known as hole-transporting materials and hole-transporting matrix materials for electronic devices. However, there is still a need for alternative compounds for this application, as well as a fundamental need for improvements with regard to the aforementioned properties.It has now been found that aromatic amines according to the formula below, which are characterized by having certain carbazolyl, dibenzofuranyl, or dibenzothiophenyl groups on the amine nitrogen atom, are outstandingly suitable for use in electronic devices. They are particularly suitable for use in OLEDs, particularly therein for use as hole-transport materials and for use as hole-transporting matrix materials, in particular for phosphorescent emitters. The compounds lead to long lifetimes, high efficiency, and low operating voltage of the devices. Furthermore, the compounds found preferably have a high glass transition temperature, high stability, a low sublimation temperature, good solubility, good synthetic accessibility, and high hole conductivity. The present application thus provides a compound according to a formula (I) Form I). where the variables appearing are: X is equal to O, S or NR 2 ; Z is the same or different at each occurrence CR 3 or N; Z 1 is chosen the same or different for each occurrence from CR 1 and CA; Z 2 is chosen the same or different for each occurrence from CR 1 and CA; where at least one group is selected from the groups Z 1 and Z 2 in formula (I) is CA; A is a group of the following formula Formula (A), where the dashed bond is the bond to the C atom of the unit CA; Ar 1 is selected at each occurrence, identically or differently, from aromatic ring systems with 6 to 40 aromatic ring atoms, which are substituted by radicals R 4 are substituted, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms, which are substituted with residues R 4 are substituted, where the two groups Ar 1in formula (A) may be linked to one another via a bond or a group E; E is the same or different at each occurrence and is selected from C(R 4 )2, -C(R 4 )2-C(R 4 )2-, -C(R 4 )=C(R 4 )-, C=O, Si(R 4 )2, NR 4 , O, S, S=O, and SO2; R 1 is selected at each occurrence, the same or different, from H, D, F, Cl, Br, I, C(=O)R 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5 , straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 1may be linked to one another and form an aromatic ring; wherein the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems are each linked to radicals R 5 are substituted; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted by -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), -O-, -S-, SO or SO2; R 2is selected from straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein the said alkyl, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems are each substituted by radicals R 5 are substituted; and wherein one or more CH2 groups in said alkyl, alkenyl and alkynyl groups are substituted by -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), -O-, -S-, SO or SO2; R 3 is selected at each occurrence, the same or different, from H, D, F, Cl, Br, I, C(=O)R 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR5 , S(=O)R 5 , S(=O)2R 5 , straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 1 may be linked to one another and form an aromatic ring; wherein the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems are each linked to radicals R 5 are substituted; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted by -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5), -O-, -S-, SO or SO2; R 4 is selected at each occurrence, the same or different, from H, D, F, Cl, Br, I, C(=O)R 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5 , straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 4 may be linked to one another and form a ring; wherein the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems are each linked to radicals R 5are substituted; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted by -R 5 C=CR 5 - , -C≡C-, Si(R 5 )2, C=O, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), -O-, -S-, SO or SO2; R 5 is selected at each occurrence, the same or different, from H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 5may be linked to one another and form a ring; wherein the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems are each linked to radicals R 6 are substituted; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted by -R 6 C=CR 6 - , -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 ), -O-, -S-, SO or SO2; R 6 is selected, identically or differently at each occurrence, from H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 6may be linked together to form a ring; and wherein said alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by one or more radicals selected from F and CN; wherein in the case of X = NR 2 at least one group Z 2in formula (I) must be equal to CA. The following definitions apply to the chemical groups used in the present application. They apply unless more specific definitions are given. An aryl group within the meaning of this invention is understood to be either a single aromatic cycle, i.e., benzene, or a condensed aromatic polycycle, for example, naphthalene, phenanthrene, or anthracene. A condensed aromatic polycycle within the meaning of the present application consists of two or more individual aromatic cycles condensed together. Condensation between cycles is understood to mean that the cycles share at least one edge. An aryl group within the meaning of this invention contains 6 to 40 aromatic ring atoms. Furthermore, an aryl group does not contain a heteroatom as an aromatic ring atom.but only carbon atoms. A heteroaryl group in the sense of this invention is understood to be either a single heteroaromatic cycle, for example pyridine, pyrimidine or thiophene, or a condensed heteroaromatic polycycle, for example quinoline or carbazole. A condensed heteroaromatic polycycle in the sense of the present application consists of two or more individual aromatic or heteroaromatic cycles condensed together, where at least one of the aromatic and heteroaromatic cycles is a heteroaromatic cycle. Condensation between cycles is understood to mean that the cycles share at least one edge. A heteroaryl group in the sense of this invention contains 5 to 40 aromatic ring atoms, of which at least one is a heteroatom. The heteroatoms of the heteroaryl group are preferably selected from N, O and S. An aryl or heteroaryl group,which may be substituted with the above-mentioned radicals are understood in particular to mean groups which are derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, triphenylene, fluoranthene, benzanthracene, benzphenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, benzimidazolo[1,2- a]benzimidazole, naphthimidazole, Phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, Phenazine, 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. An aromatic ring system within the meaning of this invention is a system that does not necessarily contain only aryl groups, but may additionally contain one or more non-aromatic rings fused with at least one aryl group. These non-aromatic rings contain exclusively carbon atoms as ring atoms. Examples of groups encompassed by this definition are tetrahydronaphthalene, fluorene, and spirobifluorene. Furthermore, the term aromatic ring system encompasses systems consisting of two or more aromatic ring systems.which are linked to one another via single bonds, for example biphenyl, terphenyl, 7-phenyl-2-fluorenyl, quaterphenyl, and 3,5-diphenyl-1-phenyl. An aromatic ring system within the meaning of this invention contains 6 to 40 C atoms and no heteroatoms in the ring system. The definition of "aromatic ring system" does not include heteroaryl groups. A heteroaromatic ring system corresponds to the above definition of an aromatic ring system, with the difference that it must contain at least one heteroatom as a ring atom. As is the case with the aromatic ring system, the heteroaromatic ring system does not have to contain exclusively aryl groups and heteroaryl groups, but can additionally contain one or more non-aromatic rings that are fused with at least one aryl or heteroaryl group. The non-aromatic rings can contain exclusively C atoms as ring atoms, or they can additionally contain one or more heteroatoms.wherein the heteroatoms are preferably selected from N, O, and S. An example of such a heteroaromatic ring system is benzopyranyl. Furthermore, the term "heteroaromatic ring system" refers to systems consisting of two or more aromatic or heteroaromatic ring systems linked to one another via single bonds, such as, for example, 4,6-diphenyl-2-triazinyl. A heteroaromatic ring system within the meaning of this invention contains 5 to 40 ring atoms selected from carbon and heteroatoms, wherein at least one of the ring atoms is a heteroatom. The heteroatoms of the heteroaromatic ring system are preferably selected from N, O, and S. The terms "heteroaromatic ring system" and "aromatic ring system" as defined in the present application thus differ from one another in that an aromatic ring system cannot have a heteroatom as a ring atom.whereas a heteroaromatic ring system must have at least one heteroatom as a ring atom. This heteroatom can be present as a ring atom of a non-aromatic heterocyclic ring or as a ring atom of an aromatic heterocyclic ring. According to the above definitions, any aryl group is encompassed by the term "aromatic ring system," and any heteroaryl group is encompassed by the term "heteroaromatic ring system." An aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms is understood to mean, in particular, groups derived from the groups mentioned above under aryl groups and heteroaryl groups, as well as from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, indenocarbazole,or combinations of these groups. In the context of the present invention, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, in which individual H atoms or CH2 groups can also be substituted by the groups mentioned above in the definition of the radicals, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neo-pentyl, n-hexyl, cyclohexyl, neo-hexyl, 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 or octynyl. Under an alkoxy or thioalkyl group with 1 to 20 carbon atoms,in der auch einzelne H-Atome oder CH2-Gruppen durch die oben bei der Definition der Reste genannten Gruppen substituiert sein können, werden bevorzugt Methoxy, Trifluormethoxy, Ethoxy, n-Propoxy, i-Propoxy, n- Butoxy, i-Butoxy, s-Butoxy, t-Butoxy, n-Pentoxy, s-Pentoxy, 2-Methyl- butoxy, n-Hexoxy, Cyclohexyloxy, n-Heptoxy, Cycloheptyloxy, n-Octyloxy, Cyclooctyloxy, 2-Ethylhexyloxy, Pentafluorethoxy, 2,2,2-Trifluorethoxy, Methylthio, Ethylthio, n-Propylthio, i-Propylthio, n-Butylthio, i-Butylthio, s- Butylthio, t-Butylthio, n-Pentylthio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclooctylthio, 2-Ethylhexylthio, Trifluormethylthio, Pentafluorethylthio, 2,2,2-Trifluorethylthio, Ethenylthio, Propenylthio, Butenylthio, Pentenylthio, Cyclopentenylthio, Hexenylthio, Cyclohexenylthio, Heptenylthio, Cycloheptenylthio, Octenylthio, Cyclooctenylthio, Ethinylthio, Propinylthio, Butinylthio, Pentinylthio, Hexinylthio,Heptynylthio or octynylthio. The phrase "two or more residues can form a ring with each other" is understood in the context of the present application to mean, inter alia, that the two residues are linked to each other by a chemical bond. Furthermore, the above-mentioned phrase also means 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. According to a preferred embodiment, the compound of formula (I) is a monoamine, i.e., it contains exactly one and no further amino group. X is preferably O or NR, 2 , particularly preferably O. According to an alternative, likewise preferred embodiment, X is O or S, particularly preferably O. Z is preferably CR 3. According to a further preferred embodiment, at most 3 groups Z in formula (I) are N, particularly preferably at most 2 groups Z in formula (I) are N, and very particularly preferably at most 1 group Z in formula (I) is N. Furthermore, it is preferred that groups Z which are N are not directly bonded to one another. According to a preferred embodiment, exactly one group is selected from the groups Z 1 and Z 2 in formula (I) is CA. According to a particularly preferred embodiment, at least one group is selected from the groups Z 2 in formula (I) is CA. According to an alternative preferred embodiment, at least one group is selected from the groups Z 1 in formula (I) is equal to CA. Ar 1 is preferably selected, identically or differently at each occurrence, from aromatic ring systems having 6 to 40 aromatic ring atoms, which are substituted by radicals R 4 are substituted. Preferred groups Ar1 are, at each occurrence, identically or differently selected from monovalent groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, phenanthrene, fluorene, in particular 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine, and triazine, where each of the monovalent groups is substituted with radicals R 4 is substituted. Preferred groups are Ar 1at each occurrence, identically or differently selected from combinations of 2 to 4 groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, phenanthrene, fluorene, in particular 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine, and triazine, where each of the monovalent groups is substituted with radicals R 4 Particularly preferred groups Ar 1are selected, identically or differently at each occurrence, from the groups benzene, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, fluorenyl, in particular 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, and phenyl substituted with a group selected from naphthyl, phenanthrenyl, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidyl and triazinyl, where the groups mentioned are each substituted with radicals R 4 are substituted. Ar 1 is preferably selected at each occurrence, identically or differently, from groups of the following formulas:

[0002] where the dashed line represents the bond to the nitrogen atom and where the groups at the unsubstituted positions are bonded to residues R 4 may be substituted, and preferably have only H in the unsubstituted positions shown. According to a preferred embodiment, the two groups Ar 1 in formula (A) are not connected via a bond or via a group E. According to an alternative preferred embodiment, the two groups Ar 1 in formula (A) are either not bonded to each other or are bonded to each other. According to a preferred embodiment, R 1 at each occurrence, the same or different, selected from H, D, F, CN, Si(R 5 )3, N(R 5)2, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5 are substituted; and wherein in said alkyl groups one or more CH2 groups are substituted by -C≡C-, -R 5 C=CR 5 -, Si(R 5 )2, C=O, C=NR 5 , -NR 5 -, -O-, -S-, -C(=O)O- or -C(=O)NR 5 - may be replaced. R is particularly preferred 1at each occurrence, identically or differently selected from H, D, straight-chain alkyl groups having 1 to 10 C atoms, branched or cyclic alkyl groups having 3 to 10 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where said alkyl groups, said aromatic ring systems and said heteroaromatic ring systems are each substituted by radicals R 5 are substituted. R is particularly preferably 1 at each occurrence, identically or differently selected from H, D, straight-chain alkyl groups having 1 to 10 C atoms, branched or cyclic alkyl groups having 3 to 10 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, where the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5are substituted. Most preferably R 1 is selected at each occurrence, identically or differently, from H and D, with H being preferred. According to a preferred embodiment, R 2 selected from straight-chain alkyl groups having 1 to 10 C atoms, branched or cyclic alkyl groups having 3 to 10 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein said alkyl groups, said aromatic ring systems and said heteroaromatic ring systems are each substituted by radicals R 5 are substituted. R is particularly preferably 2 selected from aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein said aromatic ring systems and said heteroaromatic ring systems are each substituted by radicals R 5are substituted. R is particularly preferably 2 selected from aromatic ring systems with 6 to 40 aromatic ring atoms, which are linked to residues R 5 are substituted. According to a preferred embodiment, R 3 at each occurrence, the same or different, selected from H, D, F, CN, Si(R 5 )3, N(R 5 )2, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5 are substituted; and wherein in said alkyl groups one or more CH2 groups are substituted by -C≡C-, -R 5 C=CR 5 -, Si(R 5 )2, C=O, C=NR 5 , -NR 5 -, -O-, -S-, -C(=O)O- or -C(=O)NR5 - may be replaced. R is particularly preferred 3 at each occurrence, identically or differently selected from H, D, straight-chain alkyl groups having 1 to 10 C atoms, branched or cyclic alkyl groups having 3 to 10 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where said alkyl groups, said aromatic ring systems and said heteroaromatic ring systems are each substituted by radicals R 5 are substituted. R is particularly preferably 3at each occurrence, identically or differently selected from H, D, straight-chain alkyl groups having 1 to 10 C atoms, branched or cyclic alkyl groups having 3 to 10 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, where the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5 are substituted. Most preferably R 3 at each occurrence, identically or differently, is selected from H and D, with H being preferred. R is preferably 4 at each occurrence, the same or different, selected from H, D, F, CN, Si(R 5 )3, N(R 5)2, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5 are substituted; and wherein in said alkyl groups one or more CH2 groups are substituted by -C≡C-, -R 5 C=CR 5 -, Si(R 5 )2, C=O, C=NR 5 , -NR 5 -, -O-, -S-, -C(=O)O- or -C(=O)NR 5 - may be replaced. R is particularly preferred 4 at each occurrence, the same or different, selected from H, D, F, CN, Si(R 5)3, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5 are substituted. Preferably R 5 at each occurrence, the same or different, selected from H, D, F, CN, Si(R 6 )3, N(R 6 )2, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 6are substituted; and wherein in said alkyl groups one or more CH2 groups are substituted by -C≡C-, -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , -NR 6 -, -O-, -S-, -C(=O)O- or -C(=O)NR 6 - may be replaced. R is particularly preferred 5 at each occurrence, identically or differently selected from H, D, F, CN, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms. Formula (I) preferably corresponds to one of the following formulas (IA) to (IC): wherein the variables occurring are defined as above and preferably correspond to one of their preferred embodiments, and wherein for formula (IA) and (IB) at least one group is selected from the groups Z 1 and Z 2is CA, and where for formula (IC) at least one group Z 2 is equal to CA. In formulas (IA) to (IC) R 1 at each occurrence, identical or different, is H, D or phenyl, particularly preferably H. Particularly preferred embodiments of the formula (I) correspond to the following formulas (IA-1) to (IA-6), (IB-1) to (IB-6) and (IC-1) and (IC-2):

[0003] wherein the variables occurring are defined as above and preferably correspond to one of their preferred embodiments. Among the above-mentioned formulas, the formulas (IA-1), (IA-4), (IB-1), (IB-4), (IC-1), and (IC-2) are particularly preferred. Very particular preference is given to the formulas (IA-1), (IA-4), (IB-1), and (IB-4). Most preferred among these are the formulas (IA-1) and (IA-4). According to a preferred embodiment, formula (I) corresponds to one of the formulas (IA-1) to (IA-3), (IB-1) to (IB-3) and (IC-1), with formulas (IA-1), (IB-1), and (IC-1) being particularly preferred among them. Particularly preferred embodiments of the formula (I) further correspond to the following formulas:

[0004] wherein the variables occurring are as defined above and preferably correspond to their preferred embodiments mentioned above. According to a preferred embodiment, the compound of formula (I) corresponds to one of the formulas (IA-1) to (IA-6), (IB-1) to (IB-6), (IC-1), or (IC-2), wherein the following applies to the variables occurring: - Ar 1is selected, identically or differently, from the groups benzene, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, fluorenyl, in particular 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, and phenyl substituted with a group selected from naphthyl, phenanthrenyl, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidyl and triazinyl, wherein the groups mentioned are each substituted with radicals R 4 are substituted; - R 1is selected, identically or differently at each occurrence, from H, D, straight-chain alkyl groups having 1 to 10 C atoms, branched or cyclic alkyl groups having 3 to 10 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5 are substituted; and - R 2 is selected from aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5 are substituted; and - R 3is selected, identically or differently at each occurrence, from H, D, straight-chain alkyl groups having 1 to 10 C atoms, branched or cyclic alkyl groups having 3 to 10 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5 are substituted; and - R 4 is selected at each occurrence, the same or different, from H, D, F, CN, Si(R 5)3, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5 are substituted; and - R 5 is selected, identically or differently at each occurrence, from H, D, F, CN, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms. Examples of preferred compounds of formula (I) are shown in the following table:

[0005] The compounds of formula (I) can be prepared by known reactions of organic synthetic chemistry. The synthesis process shown in Scheme 1 below is preferably used. The skilled person can modify and adapt the process described therein within the scope of their general technical knowledge to obtain compounds similar to those shown therein.

[0006] Scheme 1 The following applies to the variables that appear in the scheme: R is, identically or differently at each occurrence, H or an organic residue; X is O, S or NR; Y is a reactive group, preferably halide; W is a reactive group, preferably halide; Ar is, identically or differently at each occurrence, selected from aromatic and heteroaromatic groups. The starting materials of the process shown in Scheme 1 are commercially available or can be obtained using methods known from the literature. In a first step, these starting materials are converted by Suzuki coupling at one of their reactive groups, the group W, which is preferably the more reactive of the two groups W and Y in the Suzuki coupling reaction, to the corresponding intermediates in which a phenyl group is introduced in place of the group W. The Suzuki coupling is preferably carried out with a phenyl boronic acid compound. Furthermore, the group W is preferably Br.In a second step, the compound formed in the first step is reacted in a Buchwald coupling with a secondary amine containing two Ar groups, as defined above. This forms the compound of formula (I). The reacting reactive group Y is preferably Cl. The present application therefore relates to a process for preparing a compound according to formula (I), characterized in that a compound containing a carbazole group, a dibenzofuran group or a dibenzothiophene group, as well as a reactive group Y and a reactive group W, is first reacted in a Suzuki coupling with a phenylboronic acid derivative, and then the resulting compound is reacted in a Buchwald coupling with a secondary amine. In this case, the reactive group W is reacted in the Suzuki coupling, and the reactive group Y is reacted in the Buchwald coupling.Preferably, the reactive group W is more reactive in the Suzuki coupling than the reactive group Y. More preferably, the reactive group W is Br, and the reactive group Y is Cl. The above-described compounds according to the invention, in particular compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boronic acid, or boronic esters, can be used as monomers to produce corresponding oligomers, dendrimers, or polymers. Suitable reactive leaving groups include, for example, bromine, iodine, chlorine, boronic acids, boronic esters, amines, alkenyl or alkynyl groups with a terminal CC double bond or CC triple bond, oxiranes, oxetanes, and groups that undergo cycloaddition, for example, a 1,3-dipolar cycloaddition, such as dienes or azides, carboxylic acid derivatives, alcohols, and silanes.The invention therefore further relates to oligomers, polymers or dendrimers comprising one or more compounds according to formula (I), wherein the bond(s) to the polymer, oligomer or dendrimer are connected to any desired group denoted by R in formula (I). 1 , R 2 , R 3 , or R 4substituted positions. Depending on the linkage of the compound according to formula (I), the compound is part of a side chain of the oligomer or polymer or part of the main chain. Further disclosure concerning oligomers, polymers, or dendrimers can be found on page 49, line 26 - page 51, line 17 of WO 2020 / 109434 A1. The disclosure of these passages is hereby incorporated in its entirety by citation into the present application. For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes, formulations of the compounds according to the invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferable to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-, or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF,Methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetol, 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 or mixtures of these solvents. The invention therefore further relates to a formulation, in particular a solution,A dispersion or emulsion comprising at least one compound of formula (I) or at least one polymer, oligomer, or dendrimer comprising at least one unit of formula (I), and at least one solvent, preferably an organic solvent. How such solutions can be prepared is known to the person skilled in the art. The compound of formula (I) is suitable for use in an electronic device, in particular an organic electroluminescent device (OLED). Depending on the substitution, the compound of formula (I) can be used in different functions and layers. Preference is given to use as a hole-transporting material in a hole-transporting layer and / or as a matrix material in an emitting layer.particularly preferably in combination with a phosphorescent emitter. The invention therefore further relates to the use of a compound according to formula (I) in an electronic device. The electronic device is preferably selected from the group consisting of organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), and particularly preferably organic electroluminescent devices (OLEDs). The invention further relates to an electronic device,containing at least one compound according to formula (I). The electronic device is preferably selected from the above-mentioned devices. Particular preference is given to an organic electroluminescent device containing an anode, a cathode, and at least one emitting layer, characterized in that at least one organic layer is contained in the device which contains at least one compound according to formula (I). Preferred is an organic electroluminescent device containing an anode, a cathode, and at least one emitting layer, characterized in that at least one organic layer in the device, selected from hole-transporting and emitting layers, contains at least one compound according to formula (I). A hole-transporting layer is understood to mean all layers that are arranged between the anode and the emitting layer, preferably a hole injection layer, a hole transport layer,and electron blocking layer. A hole injection layer is understood to be a layer that directly borders the anode. A hole transport layer is understood to be a layer that is present between the anode and the emitting layer, but not directly borders the anode, and preferably not directly borders the emitting layer either. An electron blocking layer is understood to be a layer that is present between the anode and the emitting layer and directly borders the emitting layer. An electron blocking layer preferably has a high-energy LUMO and thus prevents electrons from escaping from the emitting layer. In addition to the cathode, anode, and emitting layer, the electronic device can contain further layers. These are selected, for example, from one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers,Electron injection layers, electron blocking layers, exciton blocking layers, interlayers, charge generation layers, and / or organic or inorganic p / n junctions. It should be noted, however, that not all of these layers necessarily need to be present, and the choice of layers always depends on the compounds used and, in particular, on whether the device is fluorescent or phosphorescent. The sequence of layers of the electronic device is preferably as follows: -anode- -hole injection layer- -hole transport layer- -optional further hole transport layers- -emitting layer- -optional hole blocking layer- -electron transport layer- -electron injection layer- -cathode-. It should be noted again that not all of the aforementioned layers need to be present.and / or that additional layers may be present. The organic electroluminescent device according to the invention can contain a plurality of emitting layers. Particularly preferably, these emitting layers have a total of several emission maxima between 380 nm and 750 nm, resulting in overall white emission, i.e., various emitting compounds that can fluoresce or phosphoresce and that emit blue, green, yellow, orange, or red light are used in the emitting layers. Particular preference is given to three-layer systems, i.e., systems with three emitting layers, wherein one of the three layers exhibits blue emission, one of the three layers exhibits green emission, and one of the three layers exhibits orange or red emission. The compounds according to the invention are preferably present in a hole-transporting layer or in the emitting layer. It should be noted thatthat for the generation of white light, instead of several color-emitting emitter compounds, a single emitter compound which emits in a broad wavelength range can also be suitable. It is preferred that the compound of formula (I) is used as the hole-transport material. The emitting layer can be a fluorescent emitting layer or it can be a phosphorescent emitting layer. The emitting layer is preferably a blue fluorescent layer or a green phosphorescent layer. If the device comprising the compound of formula (I) contains a phosphorescent emitting layer, it is preferred that this layer has two or more, preferably exactly two,contains various matrix materials (mixed matrix system). Preferred embodiments of mixed matrix systems are described in more detail below. If the compound according to formula (I) is used as a hole-transport material in a hole-transport layer, a hole-injection layer, or an electron-blocking layer, the compound can be used as a pure material, i.e., in a proportion of 100%, in the hole-transport layer, or it can be used in combination with one or more further compounds. According to a preferred embodiment, a hole-transporting layer comprising the compound of formula (I) additionally contains one or more further hole-transporting compounds. These further hole-transporting compounds are preferably selected from triarylamine compounds,particularly preferably from mono-triarylamine compounds. They are most preferably selected from the preferred embodiments of hole-transporting materials specified below. In the preferred embodiment described, the compound of formula (I) and the one or more further hole-transporting compounds are preferably each present in a proportion of at least 10%, particularly preferably each present in a proportion of at least 20%. According to a preferred embodiment, a hole-transporting layer comprising the compound of formula (I) additionally contains one or more p-dopants. According to the present invention, p-dopants are preferably those organic electron acceptor compounds which can oxidize one or more of the other compounds of the mixture. Particularly preferred p-dopants are quinodimethane compounds, azaindenofluorenediones, azaphenalenes, azatriphenylenes, I2, metal halides,Preferably, transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or a metal of main group 3, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd, and Pt with ligands containing at least one oxygen atom as a bonding site. Also preferred are transition metal oxides as dopants, preferably oxides of rhenium, molybdenum, and tungsten, particularly preferably Re2O7, MoO3, WO3, and ReO3. Even more preferred are complexes of bismuth in the oxidation state (III), in particular bismuth(III) complexes with electron-deficient ligands.in particular carboxylate ligands. The p-dopants are preferably largely uniformly distributed in the p-doped layers. This can be achieved, for example, by co-evaporation of the p-dopant and the hole-transport material matrix. The p-dopant is preferably present in a proportion of 1 to 10% in the p-doped layer. Furthermore, preferred p-dopants are the compounds explicitly depicted on pages 86-87 of published patent application WO2021 / 156323A1. According to a preferred embodiment, a hole-injection layer is present in the device, which corresponds to one of the following embodiments: a) it contains a triarylamine and a p-dopant; or b) it contains a single electron-deficient material (electron acceptor). According to a preferred embodiment of embodiment a), the triarylamine is a mono-triarylamine,in particular one of the preferred triarylamine derivatives mentioned below. According to a preferred embodiment of embodiment b), the electron-poor material is a hexaazatriphenylene derivative, as described in US 2007 / 0092755. The compound of formula (I) can be present in a hole-injection layer, in a hole-transport layer, and / or in an electron-blocking layer of the device. If the compound is present in a hole-injection layer or in a hole-transport layer, it is preferably p-doped, i.e., it is present in the layer mixed with a p-dopant, as described above. The compound of formula (I) is preferably present in an electron-blocking layer. In this case, it is preferably not p-doped. Furthermore, in this case, it is preferably present as a single compound in the layer.without admixture of another compound. According to an alternative preferred embodiment, the compound of formula (I) is used in an emitting layer as a matrix material in combination with one or more emitting compounds, preferably phosphorescent emitting compounds. The phosphorescent emitting compounds are preferably selected from red phosphorescent and green phosphorescent compounds. The proportion of matrix material in the emitting layer in this case is between 50.0 and 99.9 vol.%, preferably between 80.0 and 99.5 vol.%, and particularly preferably between 85.0 and 97.0 vol.%. Accordingly, the proportion of the emitting compound is between 0.1 and 50.0 vol.%.preferably between 0.5 and 20.0 vol.% and particularly preferably between 3.0 and 15.0 vol.%. An emitting layer of an organic electroluminescent device can also contain systems comprising several matrix materials (mixed-matrix systems) and / or several emitting compounds. In this case, too, the emitting compounds are generally those compounds whose proportion in the system is the smaller, and the matrix materials are those compounds whose proportion in the system is the larger. In individual cases, however, the proportion of an individual matrix material in the system can be smaller than the proportion of an individual emitting compound. It is preferred that the compounds according to formula (I) are used as a component of mixed-matrix systems, preferably for phosphorescent emitters. The mixed-matrix systems preferably comprise two or three different matrix materials,Particularly preferably, two different matrix materials are used. One of the two materials is preferably a material with hole-transporting properties and the other material is a material with electron-transporting properties. It is further preferred if one of the materials is selected from compounds with a large energy difference between HOMO and LUMO (wide-bandgap materials). The compound of formula (I) in a mixed-matrix system preferably represents the matrix material with hole-transporting properties. Accordingly, if the compound of formula (I) is used as a matrix material for a phosphorescent emitter in the emitting layer of an OLED, a second matrix compound is present in the emitting layer which has electron-transporting properties. The two different matrix materials can be used in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1.particularly preferably 1:10 to 1:1, and very particularly preferably 1:4 to 1:1. According to a preferred embodiment, in the case of mixed-matrix systems, the two or more matrix materials contained in the mixed-matrix system, at least one of which preferably corresponds to one of the formulas (I), are used as a mixture and applied by evaporation. However, the desired electron-transporting and hole-transporting properties of the mixed-matrix components can also be combined mainly or completely in a single mixed-matrix component, with the further mixed-matrix component(s) fulfilling other functions. The following material classes are preferably used in the above-mentioned layers of the device: Phosphorescent emitters: The term phosphorescent emitters typically encompasses compounds in which light emission occurs through a spin-forbidden transition.for example, a transition from an excited triplet state or a state with a higher spin quantum number, for example, a quintet state. Particularly suitable phosphorescent emitters are compounds that, upon suitable excitation, emit light, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are used as phosphorescent emitters, in particular compounds containing iridium, platinum, or copper. For the purposes of the present invention, all luminescent iridium, platinum, or copper complexes are considered phosphorescent compounds. In general, all phosphorescent complexes are suitable.as used in the prior art for phosphorescent OLEDs and as known to those skilled in the art in the field of organic electroluminescent devices, for use in the devices according to the invention. Further examples of suitable phosphorescent emitters are shown in the following table:

[0007] Fluorescent emitters: Preferred fluorescent emitting compounds are selected from the class of arylamines. An arylamine or an aromatic amine within the meaning of this invention is understood to be a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, particularly preferably with at least 14 aromatic ring atoms. Preferred examples are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to be a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position.An aromatic anthracenediamine is understood to be a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, with the diarylamino groups on the pyrene preferably being bonded in the 1-position or 1,6-position, respectively. Further preferred emitting compounds are indenofluorenamines and diamines, benzoindenofluorenamines and diamines, and dibenzoindenofluorenamines and diamines, as well as indenofluorene derivatives with fused aryl groups. Pyrene-arylamines are also preferred. Also preferred are benzoindenofluoreneamines, benzofluoreneamines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives bonded to furan units or thiophene units.Matrix materials for fluorescent emitters: Preferred matrix materials for fluorescent emitters are selected from the classes of oligoarylenes (e.g., 2,2',7,7'-tetraphenylspirobifluorene), in particular oligoarylenes containing condensed aromatic groups, oligoarylenevinylenes, polypodal metal complexes, hole-conducting compounds, electron-conducting compounds, in particular ketones, phosphine oxides, and sulfoxides; atropisomers, boronic acid derivatives, or benzanthracenes. Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene, and / or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides, and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzphenanthrene and / or pyrene or atropisomers of these compounds.An oligoarylene, within the meaning of this invention, is understood to mean a compound in which at least three aryl or arylene groups are bonded to one another. Matrix materials for phosphorescent emitters: In addition to the compounds of formula (I), preferred matrix materials for phosphorescent emitters are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, e.g., CBP (N,N-biscarbazolylbiphenyl) or carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, silanes, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasilole or tetraazasilole derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or lactams. Electron-transporting materials: Suitable electron-transporting materials include those described in Y. Shirota et al., Chem. Rev.2007, 107(4), 953-1010, or other materials as used in these layers according to the prior art. All materials that are used in the prior art as electron-transport materials in the electron-transport layer can be used as materials for the electron-transport layer. Particularly suitable are aluminum complexes, for example Alq3; zirconium complexes, for example Zrq4; lithium complexes, for example Liq; benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives. Preferred electron-transport and electron-injection materials are also the compounds explicitly shown on pages 73-75 of WO2020 / 109434A1.Hole-transporting materials: Further compounds which, in addition to the compounds of formula (I), are preferably used in hole-transporting layers of the OLEDs according to the invention are indenofluorenamine derivatives, amine derivatives, hexaazatriphenylene derivatives, amine derivatives with condensed aromatics, monobenzoindenofluorenamines, dibenzoindenofluorenamines, spirobifluorene amines, fluorene amines, spiro-dibenzopyran amines, dihydroacridine derivatives, spirodibenzofurans and spirodibenzothiophenes, phenanthrene diarylamines, spiro-tribenzotropolones, spirobifluorenes with meta-phenyldiamine groups, spiro-bisacridines, xanthene diarylamines, and 9,10-dihydroanthracene spiro compounds with diarylamino groups. Preferred hole-transporting compounds are still the compounds explicitly shown on pages 76-80 of WO2020 / 109434A1.Metals with a low work function, metal alloys, or multilayer structures made of different metals are preferred as the cathode of the electronic device, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys of an alkali or alkaline earth metal and silver, for example, an alloy of magnesium and silver, are also suitable. In multilayer structures, in addition to the metals mentioned, other metals with a relatively high work function can be used, such as Ag or Al, in which case combinations of the metals, such as Ca / Ag, Mg / Ag, or Ba / Ag, are generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor.Suitable materials for this purpose include alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Lithium quinolinate (LiQ) can also be used. The layer thickness of this layer is preferably between 0.5 and 5 nm. Materials with a high work function are preferred as the anode. The anode preferably has a work function greater than 4.5 eV vs. vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Metal / metal oxide electrodes (e.g., Al / Ni / NiOx, Al / PtOx) may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to enable either the irradiation of the organic material (organic solar cell) or the extraction of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides.Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Also preferred are conductive, doped organic materials, especially conductive doped polymers. Furthermore, the anode can also consist of multiple layers, for example, an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide, or vanadium oxide. In a preferred embodiment, the electronic device is 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 -7mbar. Also preferred is an electronic device characterized in that one or more layers are coated using the OVPD (Organic Vapour Phase Deposition) process or by means of carrier gas sublimation. The materials are deposited at a pressure between 10 -5mbar and 1 bar. A special case of this process is the OVJP (Organic Vapour Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (e.g. BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301). Also preferred is an electronic device characterized in that one or more layers are produced from solution, for example by spin coating, or using any printing process, such as screen printing, flexographic printing, nozzle printing or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble compounds according to formula (I) are required. High solubility can be achieved by suitable substitution of the compounds.It is further preferred that, to produce an electronic device according to the invention, one or more layers are applied from solution and one or more layers are applied by a sublimation process. After application of the layers, the device is structured, contacted, and finally sealed, depending on the application, in order to exclude the damaging effects of water and air. According to the invention, the electronic devices comprising one or more compounds of the formula (I) can be used in displays, as light sources in lighting applications, and as light sources in medical and / or cosmetic applications. Examples A) Synthesis Examples Synthesis 3-chloro-5-phenyl-8-oxatricyclo[7.4.0.0. 2,7 ]trideca‐1(9),2,4,6,10,12‐hexaene 1a 8.1 g (66.5 mmol) phenyl-boronic acid, 18.7 g (66.5 mmol) 5-bromo-3-chloro-8-oxatricyclo[7.4.0.0 2,7]trideca‐1(9),2,4,6,10,12‐hexaene: 1.2 g (2 mmol) of bis(triphenylphosphine)Pd(II) chloride and 23 g (167 mmol) of potassium carbonate are suspended in 520 mL of acetonitrile and 220 mL of methanol. The reaction mixture is heated to boiling overnight under a protective atmosphere. The mixture is then filtered off with suction and washed with MeOH, water, and again with MeOH. The residue is purified by crystallization with MeOH. Yield: 14.8 g (80% of theory), purity according to GC-MS >99%. The following compounds are prepared analogously: 1h Br Cl Cl

[0008] Synthesis N,N-bis({[1,1'-biphenyl]-4-yl})-5-phenyl-8-oxatricyclo[7.4.0.0 2,7 ]trideca‐1(13),2,4,6,9,11‐hexaen‐3‐amine 2a N‐{[1,1'‐biphenyl]‐4‐yl}‐[1,1'‐biphenyl]‐4‐amine (24 g, 75 mmol), 3‐chloro‐5‐phenyl‐8‐oxatricyclo[7.4.0.0 2,7[Trideca‐1(9),2,4,6,10,12‐hexaene (20.9 g, 75 mmol) and sodium tert‐butoxide (14.7 g, 150 mmol) were dissolved in 350 mL of toluene. The solution was degassed and saturated with N2. Then, tri‐tert‐butylphosphine (7.5 mL; 7.5 mmol, 1M in xylene) and 3.4 g (3.8 mmol) of Pd2(dba)3 were added. The reaction mixture was heated to boiling overnight under a protective atmosphere. The mixture was cooled and partitioned between toluene and water. The organic phase was washed three times with water, dried over Na2SO4, and concentrated by rotary evaporation. After filtration of the crude product through silica gel with toluene, the remaining residue was recrystallized from toluene and finally sublimed under high vacuum. The purity was 99.9%. The yield is 21.1 g (50% of theory). The following compounds are prepared analogously:

[0009] B) Device examples The compounds according to the application can be used in OLEDs with the following structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emission layer (EML) / hole blocking layer (HBL) / electron transport layer (ETL) / electron injection layer (EIL) / cathode. The cathode is formed by a 100 nm thick aluminum layer. Glass plates coated with 50 nm thick structured ITO (indium tin oxide) form the substrates onto which the OLEDs are applied. The precise structure of the OLEDs is shown below. A fluorene derivative is used as the "HTM" material for the HIL and HTL. NDP-9 from Novaled AG, Dresden, is used as the p-dopant. The compounds according to the application can be advantageously used in the EBL of green phosphorescent OLEDs, as shown below for the compounds HTM-1 to HTM-3: Very good results are obtained for the parameters lifetime and external quantum efficiency, as shown below:

Claims

Claims 1. Compound according to a formula (I) where the variables appearing are: X is equal to O, S or NR 2 ; Z is the same or different at each occurrence CR 3 or N; Z 1 is chosen the same or different for each occurrence from CR 1 and CA; Z 2 is chosen the same or different for each occurrence from CR 1 and CA; where at least one group is selected from the groups Z 1 and Z 2 in formula (I) is CA; A is a group of the following formula Formula (A), where the dashed bond is the bond to the C atom of the unit CA; Ar 1 is selected at each occurrence, the same or different, from aromatic ring systems with 6 to 40 aromatic Ring atoms that are linked to residues R 4 are substituted, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms, which are substituted with residues R 4are substituted, where the two groups Ar 1 in formula (A) may be linked to one another via a bond or a group E; E is the same or different at each occurrence and is selected from C(R 4 )2, -C(R 4 )2-C(R 4 )2-, -C(R 4 )=C(R 4 )-, C=O, Si(R 4 )2, NR 4 , O, S, S=O, and SO2; R 1 is selected at each occurrence, the same or different, from H, D, F, Cl, Br, I, C(=O)R 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5 , straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 1may be linked to one another and form an aromatic ring; wherein the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems are each linked to radicals R 5 are substituted; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted by -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), -O-, -S-, SO or SO2; R 2is selected from straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein the said alkyl, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems are each substituted by radicals R 5 substituted and wherein one or more CH2 groups in said alkyl, alkenyl and alkynyl groups are replaced by -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), -O-, -S-, SO or SO2; R 3 is selected at each occurrence, the same or different, from H, D, F, Cl, Br, I, C(=O)R 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5 , straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 1 may be linked to one another and form an aromatic ring; wherein the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems are each linked to radicals R 5 are substituted; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted by -R 5 C=CR 5 -, -C≡C-, Si(R 5 )2, C=O, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5), -O-, -S-, SO or SO2; R 4 is selected at each occurrence, the same or different, from H, D, F, Cl, Br, I, C(=O)R 5 , CN, Si(R 5 )3, N(R 5 )2, P(=O)(R 5 )2, OR 5 , S(=O)R 5 , S(=O)2R 5 , straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 4 may be linked to one another and form a ring; wherein the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems are each linked to radicals R 5 are substituted; and wherein one or more CH2 groups in said Alkyl, alkoxy, alkenyl and alkynyl groups replaced by -R 5 C=CR 5 - , -C≡C-, Si(R 5 )2, C=O, C=NR 5 , -C(=O)O-, -C(=O)NR 5 -, NR 5 , P(=O)(R 5 ), -O-, -S-, SO or SO2; R 5 is selected at each occurrence, the same or different, from H, D, F, Cl, Br, I, C(=O)R 6 , CN, Si(R 6 )3, N(R 6 )2, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 5may be linked to one another and form a ring; wherein the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic ring systems and heteroaromatic ring systems are each linked to radicals R 6 are substituted; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted by -R 6 C=CR 6 - , -C≡C-, Si(R 6 )2, C=O, C=NR 6 , -C(=O)O-, -C(=O)NR 6 -, NR 6 , P(=O)(R 6 ), -O-, -S-, SO or SO2; R 6 is selected, identically or differently at each occurrence, from H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R 6may be linked together to form a ring; and wherein said alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by one or more radicals selected from F and CN; wherein in the case of X = NR 2 at least one group Z 2 in formula (I) must be equal to CA.

2. A compound according to claim 1, characterized in that the compound is a monoamine.

3. A compound according to claim 1 or 2, characterized in that Z is CR 3 4. A compound according to one or more of claims 1 to 3, characterized in that Ar 1is selected at each occurrence, identically or differently, from the groups benzene, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, fluorenyl, in particular 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, benzofuranyl, benzothiophenyl, benzo-fused dibenzofuranyl, benzo-fused dibenzothiophenyl, and phenyl substituted with a group selected from naphthyl, phenanthrenyl, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidyl and triazinyl, where the groups mentioned are each substituted with radicals R 4 are substituted.

5. A compound according to one or more of claims 1 to 4, characterized in that the following applies in combination: - R 1is selected, identically or differently at each occurrence, from H, D, straight-chain alkyl groups having 1 to 10 C atoms, branched or cyclic alkyl groups having 3 to 10 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, where the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5 are substituted; - R 2 is selected from aromatic ring systems with 6 to 40 aromatic ring atoms, which are linked to residues R 5 are substituted; - R 3 is selected at each occurrence, identically or differently, from H, D, straight-chain alkyl groups having 1 to 10 C atoms, branched or cyclic alkyl groups having 3 to 10 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, wherein the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5 are substituted; - R 4 is selected at each occurrence, the same or different, from H, D, F, CN, Si(R 5 )3, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 5 are substituted; - R 5is selected, identically or differently at each occurrence, from H, D, F, CN, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms.

6. A compound according to one or more of claims 1 to 5, characterized in that the compound according to formula (I) corresponds to one of the formulas (IA-1) to (IA-6), (IB-1) to (IB-6) and (IC-1) and (IC-2): where the variables occurring are defined according to one or more of claims 1 to 5.

7. A compound according to claim 6, characterized in that the compound corresponds to one of the formulas (IA-1), (IA-4), (IB-1), (IB-4), (IC-1) and (IC-2).

8. A compound according to claim 6, characterized in that the compound corresponds to one of the formulas (IA-1) to (IA-3), (IB-1) to (IB-3) and (IC-1). 9.A process for preparing a compound according to one or more of claims 1 to 8, characterized in that a compound containing a carbazole group, a dibenzofuran group or a dibenzothiophene group, and also a reactive group Y and a reactive group W, is first reacted with a phenylboronic acid derivative in a Suzuki coupling, and then the resulting compound is reacted with a secondary amine in a Buchwald coupling, the reactive group W being reacted in the Suzuki coupling and the reactive group Y being reacted in the Buchwald coupling.

10. Oligomer, polymer or dendrimer containing one or more compounds according to one or more of claims 1 to 8, wherein the. Bond(s) to the polymer, oligomer or dendrimer at any of the groups denoted by R in the formulas 1 , R 2 , R 3 , or R 4substituted positions can be located.

11. A formulation comprising at least one compound according to one or more of claims 1 to 8 or at least one polymer, oligomer or dendrimer according to claim 10, and at least one solvent.

12. An electronic device comprising at least one compound according to one or more of claims 1 to 8, or at least one polymer, oligomer or dendrimer according to claim 10.

13. An electronic device according to claim 12, characterized in that it is an organic electroluminescent device and contains an anode, a cathode and at least one emitting layer, and in that the compound is contained in a hole-transporting layer or in an emitting layer of the device.

14. Use of a compound according to one or more of claims 1 to 8 in an electronic device.

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