Materials for electronic devices

Abstract

The present invention relates to a compound of formula (I), to the use of the compound in an electronic device, to a method for producing said compound, and to an electronic device containing the compound.

Description

[0001] Materials for electronic devices

[0002] The present application relates to aromatic amines containing certain aromatic or heteroaromatic ring systems at the amine nitrogen atom. The compounds are suitable for use in electronic devices.

[0003] Electronic devices within the meaning of this application are understood to be so-called organic electronic devices that contain organic semiconductor materials as functional materials. In particular, this includes 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.

[0004] There is great interest in improving the performance of electronic devices, especially OLEDs. A completely satisfactory solution has not yet been found in these areas.

[0005] 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 are particularly sought that exhibit a high glass transition temperature, high stability, and high hole conductivity. High compound stability is a prerequisite for achieving a long service life of the electronic device. Compounds are also being sought whose use in electronic devices leads to improved device performance, particularly high efficiency, long service life, and low operating voltage.

[0006] 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 room for improvement regarding the above-mentioned properties.

[0007] It has now been found that aromatic amines according to the formula below, which are characterized by having certain aromatic or heteroaromatic ring systems 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, especially 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.

[0008] The present application therefore relates to a compound according to a formula (I)

[0009]

[0010] Formula (I) where the variables occurring are:

[0011] Z 1 is chosen the same or different from N and CR at each occurrence 1 ; where the unit by a unit chosen from units of the following formulas

[0012] may be replaced, where the dashed bonds in the units correspond to the bonds of the unit correspond, and where the

[0013] Variables Z 1 in the unit in these cases are equal to C;

[0014] Ar 0 is equal to phenylene, which with residues R 2 is substituted;

[0015] Ar 1 and Ar 2 are selected, identically or differently at each occurrence, from aromatic ring systems with 6 to 40 aromatic ring atoms, which are substituted by radicals R 4are substituted, and from heteroaromatic ring systems with 5 to 40 aromatic ring atoms, which are substituted with residues R 4 are substituted;

[0016] Ar 3 and Ar 4 are selected, identically or differently at each occurrence, from aromatic ring systems with 6 to 40 aromatic ring atoms, which are substituted by radicals R 5 are substituted, and from heteroaromatic ring systems with 5 to 40 aromatic ring atoms, which are substituted with residues R 5 are substituted; where at least one of Ar 3 and Ar 4 is selected from aryl groups with 10 to 20 aromatic ring atoms, which are substituted by radicals R 5 are substituted;

[0017] Ar L is selected from aromatic ring systems with 6 to 40 aromatic ring atoms, which are linked to residues R 3 are substituted, and from heteroaromatic ring systems with 5 to 40 aromatic ring atoms, which are substituted with residues R 3 are substituted;

[0018] R 1 is selected at each occurrence, the same or different, from H, D, F, CI, 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; where the said alkyl, alkoxy, alkenyl and alkynyl groups are each substituted by 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;

[0019] R 4 is selected at each occurrence, the same or different, from H, D, F, CI, Br, I, C(=O)R6 , CN, Si(R 6 )3, 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 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 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;

[0020] R 2 , R 3 and R 5 are selected at each occurrence, the same or different, from H, D, F, CI, 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 are selected from the radicals R 2 , R 3 and 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;

[0021] R 6 is selected at each occurrence, the same or different, from H, D, F, CI, Br, I, C(=O)R 7 , CN, Si(R 7 )7, P(=O)(R 7 )2, OR 7 , S(=O)R 7 , S(=O)2R 7, 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 6 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 3 are substituted; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted by -R 7 C=CR 7 - , -C≡C-, Si(R 7 )2, C=O, C=NR 7 , -C(=O)O-, -C(=O)NR 7 -, NR 7 , P(=O)(R 7 ), -O-, -S-, SO or SO2;

[0022] R 7is selected, identically or differently at each occurrence, from H, D, F, CI, 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 7 can be linked to one another and form a ring; and wherein the said alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems can be substituted by one or more radicals selected from F and CN; m is 0, 1, 2 or 3; n is 0, 1, 2 or 3; k is 0 or 1.

[0023] If n or m is 0, the groups bonded to the respective group Ar° are directly bonded to each other and the respective group Ar° is omitted.

[0024] If k is 0, the elements attached to the group Ar Lbonded groups are directly connected to each other, and the group Ar L is omitted. The following definitions apply to the chemical groups used in this application. They apply unless more specific definitions are given.

[0025] An aryl group, within the meaning of this invention, is understood to be either a single aromatic ring, 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 rings condensed together. Condensation between rings means that the rings 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 the aromatic ring atom, but only carbon atoms.

[0026] A heteroaryl group within the meaning of this invention is understood to be either a single heteroaromatic cycle, for example pyridine, pyrimidine, or thiophene, or a fused heteroaromatic polycycle, for example quinoline or carbazole. A fused heteroaromatic polycycle within the meaning of the present application consists of two or more fused individual aromatic or heteroaromatic cycles, where at least one of the aromatic and heteroaromatic cycles is a heteroaromatic cycle. Condensation between cycles means that the cycles share at least one edge. A heteroaryl group within the meaning of this invention contains 5 to 40 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms of the heteroaryl group are preferably selected from N, O, and S.

[0027] An aryl or heteroaryl group, which may be substituted by the above-mentioned radicals, is understood to mean, in particular, groups 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, Benzpyrimidine, quinoxaline, pyrazine, phenazine,Naphthyridin, Azacarbazol, Benzocarbolin, Phenan- throlin, 1 ,2,3-Triazol, 1 ,2,4-Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1 ,2,4-Oxadiazol, 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, 1 ,2,3-Triazin, Tetrazol, 1 ,2,4,5-Tetrazin, 1 ,2,3,4-Tetrazin, 1 ,2,3,5-Tetrazin, Purin, Pteridin, Indolizin und Benzothiadiazol.,

[0028] 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 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 carbon atoms and no heteroatoms in the ring system. The definition of "aromatic ring system" does not include heteroaryl groups.

[0029] 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 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, with the heteroatoms preferably being 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, with at least one of the ring atoms being a heteroatom. The heteroatoms of the heteroaromatic ring system are preferably selected from N, O, and S.

[0030] The terms "heteroaromatic ring system" and "aromatic ring system" as defined in the present application differ from each other 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.

[0031] 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”.

[0032] 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 from combinations of these groups.

[0033] 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.

[0034] Unter einer Alkoxy- oder Thioalkylgruppe mit 1 bis 20 C-Atomen, 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,Pentynylthio, hexynylthio, heptynylthio or octynylthio.,

[0035] For the purposes of this application, 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. Furthermore, the above 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.

[0036] The compound of formula (I) is preferably a monoamine. This means that the compound has only a single triarylamino group, and preferably only one amino group. A triarylamino group is understood to mean a unit that has three groups selected from aromatic and heteroaromatic groups bonded to the amino nitrogen atom.

[0037] Z 1 is preferably equal to CR 1 , where the unit may be replaced by a unit selected from units of formulas (Z-1) to (Z-6), where the dashed bonds in the units represent the

[0038] Bonds of Unity and where the variables Z 1 in the unit in these cases are equal to C.

[0039] According to a preferred embodiment, all groups Z 1 even

[0040] CR 1 , and units cannot be replaced by units of formulas (Z-1 ) to (Z-6). Ar 0 preferably corresponds to one of the following formulas where the dashed lines represent the bonds to the rest of the formula; particularly preferably the formula (Ar 0-1). According to a preferred embodiment, m is 0 or 1. According to a preferred embodiment, n is 0 or 1. According to a particularly preferred embodiment, n is 1. According to an alternative particularly preferred embodiment, n is 0. According to a preferred embodiment, at least one index is selected from indices m and n greater than 0, particularly preferably at least one index is selected from indices m and n equal to 1, and the other index selected from indices m and n is equal to 0 or 1, preferably equal to 0. Ar L is preferably an aromatic ring system with 6 to 25 aromatic ring atoms, which is substituted with radicals R 3 is substituted, and particularly preferably selected from phenyl, biphenyl, naphthyl and fluorenyl, each substituted with radicals R 3 are substituted; and most preferably selected from phenyl which is substituted with radicals R 3 is substituted. Ar Lis preferably chosen the same or different at each occurrence from

[0041] Groups of the following formulas: 5

[0042] 30 5 O

[0043] M Q

[0044] Q '"

[0045] ■OQ 0^ where the dashed lines represent the bonds to the rest of the formula, and where the groups at the unsubstituted positions each have a radical R 3 can wear.

[0046] Among the formulas listed above, the formulas Ar L -1 , Ar L -2, Ar L -3 and Ar L -4 is particularly preferred.

[0047] According to a preferred embodiment, k is equal to 0. According to an alternative preferred embodiment, k is equal to 1.

[0048] Preferred Groups Ar 1 and Ar 2are, 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 1 and Ar 2at 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 is substituted.

[0049] Particularly preferred groups Ar 1 and Ar 2are at each occurrence, identically or differently selected from 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 are each substituted with radicals R 4 are substituted.

[0050] Ar 1 and Ar 2 are preferably selected the same or different at each occurrence from the following formulas: 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. Preferably Ar 3 and Ar 4 at each occurrence, identically or differently selected from aromatic ring systems having 6 to 40 aromatic ring atoms, which are substituted by radicals R 5 are substituted.

[0051] Particularly preferred groups Ar 3 and Ar 4are at each occurrence, identically or differently selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, fluoranthenyl, 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, phenyl substituted with a group selected from naphthyl, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidyl and triazinyl, where the groups are each substituted with radicals R 5 are substituted. Particularly preferred are Ar 3 and Ar 4 at each occurrence, identically or differently selected from phenyl, biphenyl, naphthyl, phenanthrenyl, fluoranthenyl, triphenylenyl and fluorenyl, in particular 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, where the groups are each substituted with radicals R5 are substituted.

[0052] Ar 3 and Ar 4 are preferably selected at each occurrence, identically or differently, from the formulas shown above (Ar 1 -1 ) to (Ar 1 -276), where the dashed line represents the bond to the nitrogen atom and where the groups at the unsubstituted positions are substituted with residues R 5 may be substituted, and preferably have only H in the positions shown unsubstituted.

[0053] The at least one group selected from groups Ar 3 and Ar 4 , which must be selected from aryl groups with 10 to 20 aromatic ring atoms, which are linked to radicals R 5 are substituted, is preferably selected from naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylenyl, each substituted with radicals R 5 are substituted, particularly preferably selected from naphthyl, phenanthrenyl, and fluoranthenyl, which are substituted with radicals R 5are substituted, most preferably naphthyl, which is substituted with residues R 5 is substituted. R residues 5 are in these cases preferably selected from H, D, alkyl groups with 1 to 20 C atoms, and aromatic ring systems with 6 to 20 aromatic ring atoms, which are substituted by radicals R 6 are substituted, where R 6 in this case H or D is preferred.

[0054] Particularly preferably, the at least one group is selected from groups Ar 3 and Ar 4 , which must be selected from aryl groups with 10 to 20 aromatic ring atoms, which are linked to radicals R 5 are substituted, selected from the groups of the following formulas: where the variables occurring are as defined above and preferably correspond to their preferred embodiments, and where the dashed line represents the bond of the group Ar 3 or Ar 4 to the rest of the connection.

[0055] If Ar 3and Ar 4 are each naphthyl, which is substituted with residues R 5 is substituted, preferably at least one index is selected from indices m and n greater than 0.

[0056] In the case n=0, it is preferred that Ar 4 is not selected from naphthyl, which is substituted with residues R 5 is substituted, and phenanthrenyl, which is substituted with residues R 5 is substituted. In the case k=0, it is preferred that Ar 4 is not selected from naphthyl, which is substituted with residues R 5 is substituted, and phenanthrenyl, which is substituted with residues R 5 is substituted. Furthermore, it is particularly preferred that Ar 4 is not selected from naphthyl, which is substituted with residues R 5 is substituted, and phenanthrenyl, which is substituted with residues R 5 is substituted.

[0057] In the case n=0, it is preferred that Ar 4 is selected from phenyl, anthracenyl, fluoranthenyl, and triphenylenyl, each of which is substituted with radicals R 5are substituted, in particular that Ar 4 is phenyl, which is substituted with residues R 5 is substituted. In the case k=0, it is preferred that Ar 4 is selected from phenyl, anthracenyl, fluoranthenyl, and triphenylenyl, each of which is substituted with radicals R 5 are substituted, in particular that Ar 4 is phenyl, which is substituted with residues R 5 is substituted. Furthermore, it is particularly preferred that Ar 4 is selected from phenyl, anthracenyl, fluoranthenyl, and triphenylenyl, each of which is substituted with radicals R 5 are substituted, in particular that Ar 4 is phenyl, which is substituted with residues R 5 is substituted.

[0058] R 1 is preferably selected at each occurrence, identically or differently, from H, D, F, CN, Si(R 6 )s, N(R 6)2, straight-chain alkyl groups having 1 to 20 C atoms, and branched or cyclic alkyl groups having 3 to 20 C atoms; wherein the said alkyl groups are each substituted by radicals R 6 are 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 - can be replaced. R 1 is particularly preferably 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; where the alkyl groups mentioned are each substituted by radicals R 6 are substituted. R is particularly preferably 1 chosen at each occurrence, the same or different from H and D.

[0059] R 2 , R 3 and R 5are preferably selected, identically or differently at each occurrence, from H, D, F, CN, Si(R 6 )s, 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, and aromatic ring systems having 6 to 40 aromatic ring atoms; wherein the said alkyl groups and the said aromatic ring systems are each substituted by radicals R 6 are 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 - can be replaced. R 2 , R 3 and R 5are particularly preferably 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, and aromatic ring systems having 6 to 40 aromatic ring atoms; where the said alkyl groups and the said aromatic ring systems are each substituted by radicals R 6 are substituted.

[0060] R 4 is preferably selected at each occurrence, identically or differently, from H, D, F, CN, Si(R 6 )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 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 - can be replaced. R 4 is particularly preferably 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; where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by radicals R 6 are substituted.

[0061] Preferred is R 6 at each occurrence, the same or different, selected from H, D, F, CN, Si(R 7 )3, N(R 7)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 7 are substituted; and wherein in said alkyl groups one or more CH2 groups are substituted by -C=C-, -R 7 C=CR 7 -, Si(R 7 )2, C=O, C=NR 7 , -NR 7 -, -O-, -S-, -C(=O)O- or -C(=O)NR 7 - can be replaced. R 6is particularly preferably 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; where the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 7 are substituted. Most preferably R 6 chosen at each occurrence, the same or different from H and D.

[0062] Preference is given to groups R 1 , R 2 , R 3 , R 4 and R 5 , especially groups R 1 , R 2 and R 5 , chosen the same or different at each occurrence from the following groups

[0063] The compound of formula (I) preferably corresponds to one of the following

[0064] Formulas (lA) to (AD) where the variables appearing are defined as for formula (I) and preferably correspond to their preferred embodiments. The numerical indices, for example 2 and 4 for the groups R 1 in formula (lB), mean that in this case 2 or 4 groups R 1 bound to the ring in question, corresponding to the number of unsubstituted positions on this ring.

[0065] Numerical indices appearing in the further embodiments of this application have the same meaning.

[0066] Preferred embodiments of formulas (lA) to (lD) are the following formulas: where the variables occurring are defined as for formula (I) and preferably correspond to their preferred embodiments.

[0067] Preferred embodiments of formula (lA) further correspond to the following formulas:

[0068] where Ar k is selected from aryl groups with 10 to 20 aromatic ring atoms, which are substituted by radicals R 5 are substituted; and where Ar 3 and Ar 4 are selected at each occurrence, identically or differently, from aromatic ring systems having 6 to 40 aromatic ring atoms, which are substituted by radicals R 5 are substituted, and from heteroaromatic ring systems with 5 to 40 aromatic ring atoms, which are substituted with residues R 5 are substituted; where the other variables occurring are defined as for formula (I) and preferably correspond to their preferred embodiments. Ar kis preferably selected from naphthyl, phenanthrenyl, anthracenyl, chrysenyl, pyrenyl and fluoranthenyl, each of which is substituted with radicals R 5 are substituted.

[0069] Particularly preferred is Ar k chosen from the groups of formulas (Ar k - 1 ) to (Ar k -6), as defined above, wherein the variables occurring are as defined above and preferably correspond to their preferred embodiments, and wherein the dashed line represents the bond of the group Ar k to the rest of the connection.

[0070] Among the above-mentioned formulas (lAa) to (lAd), the formulas (lA- a) (lAb) and (lAd) are particularly preferred, and the formula (lAa) is very particularly preferred.

[0071] The following formulas are particularly preferred: 5

[0072] 30 5

[0073] 30 where Ar kis selected from aryl groups with 10 to 20 aromatic ring atoms, which are substituted by radicals R 5 are substituted, preferably selected from the formulas (Ar k -1 ) to (Ar k -6), as defined above, and wherein the other variables occurring are defined as for formula (I) and preferably correspond to their preferred embodiments. According to a preferred embodiment, k in one of the above-mentioned formulas is 0. According to an alternative preferred embodiment, k = 1 and Ar L is a phenyl group which can be substituted with residues R 3 is substituted.

[0074] Preferred among the above-mentioned formulas are the formulas (lAa-1 ), (lAa-2), (lAa-4), (lAb-1 ) to (lAb-4), (lAc-1 ), (lAc-2), (lAd-1 ) and (lAd-2).

[0075] Preferred among the above-mentioned formulas are also the formulas (lAa-1), (lAa-2), (lAa-4), (lAb-1), (lAb-2), (lAb-4), (lAd-1), and (lAd-2). Further preferred embodiments of compounds of formula (I) correspond to the following formulas:

[0076] where the groups “An” in the above formulas are each Ar 1 and Ar 2 as defined above, and where “R1” R 5 as defined above. According to a preferred embodiment, the following embodiments of the variables in combination apply to the compounds of formula (I):

[0077] - Z 1 is equal to CR 1 , and units cannot be replaced by units the formulas (Z-1 ) to (Z-6) must be replaced;

[0078] - Ar 1 and Ar 2are, at each occurrence, identically or differently selected from benzene, biphenyl, terphenyl, quaterphenyl, naphthyl, 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, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidyl and triazinyl, where the groups are each substituted with radicals R 4 are substituted;

[0079] - Ar 3 and Ar 4are at each occurrence, identically or differently selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, fluoranthenyl, 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, phenyl substituted with a group selected from naphthyl, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidyl and triazinyl, where the groups are each substituted with radicals R 5 are substituted; wherein at least one group is selected from the groups Ar 3 and Ar 4 must be selected from naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, and triphenylenyl, each with radicals R 5 are substituted; Ar Lis selected from phenyl, biphenyl, naphthyl and fluorenyl, each with residues R 3 are substituted;

[0080] - R 1 is selected, identically or differently, 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; where the alkyl groups mentioned are each substituted by radicals R 6 are substituted;

[0081] - R 2 , R 3 , R 5 are identical or different 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; where the said alkyl groups and the said aromatic ring systems are each substituted by radicals R 6 are substituted;

[0082] - R 4is 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; where the said alkyl groups, the said aromatic ring systems and the said heteroaromatic ring systems are each substituted by radicals R 6 are substituted;

[0083] - R 6 is chosen at each occurrence, the same or different, from H and D;

[0084] - m is equal to 0 or 1 ;

[0085] - n is equal to 0 or 1 .

[0086] In general, it is preferred that preferred embodiments disclosed in the present application be combined with one another, even if this is not explicitly stated in the above-mentioned combination of preferred embodiments. Preferred embodiments of compounds according to formula (I) are listed below: 5

[0087] 30

[0088] The compounds according to the present application can be prepared using the synthesis methods described below. Those skilled in the art can modify and adapt the synthesis methods shown within the scope of their general technical knowledge to obtain further compounds according to the application.

[0089] According to the procedure shown in Scheme 1, starting from an aryl-phenyl derivative substituted with two reactive groups in a Suzuki coupling, a chain-like tris-aryl derivative can be prepared which is substituted with a reactive group in a position ortho to the newly formed phenyl-aryl bond.

[0090]

[0091] In a subsequent step, as shown in Scheme 2, a Hartwig-Buchwald coupling can be performed, introducing an amino group into the molecule at the position of the reactive group. This yields a compound according to the present application with index k=0.

[0092] Alternatively, in a subsequent step, as shown in Scheme 3, a Suzuki coupling can be performed at the position of the reactive group, introducing an aromatic ring system containing an amino group into the molecule. This yields a compound according to the present application in which index k is >0.

[0093]

[0094] The definitions of the variable groups in the schemes shown above are as follows:

[0095] Z = N or CR

[0096] R = H or organic residue

[0097] Q 1 , Q 2 = reactive group

[0098] Ar, Ar a and Ar b = optionally substituted aromatic or heteroaromatic

[0099] The compounds shown in the above process steps may have further substituents.

[0100] As an alternative to the compounds formed in step of Scheme 1, commercially available compounds having the corresponding chemical structures of the reactants of Schemes 2 and 3 can also be used in step of Schemes 2 and 3.

[0101] The present application therefore relates to a process for preparing a compound according to the present application, characterized in that a chain-like tris-aryl derivative substituted with a reactive group is either a) reacted in a coupling reaction with a secondary amine, or b) reacted in a coupling reaction with an aromatic or heteroaromatic compound which has a boron-containing group and has an amino group.

[0102] The reactive group is preferably selected from Cl, Br, and I, particularly preferably from Br and I. The coupling reaction in reaction a) is preferably a Hartwig-Buchwald coupling reaction. The coupling reaction in b) is preferably a Suzuki coupling reaction.

[0103] Preferably, the chain-like tris-aryl derivative substituted with one reactive group is prepared starting from an aryl-phenyl derivative substituted with two reactive groups by means of a Suzuki coupling reaction with an aryl-boronic acid compound.

[0104] The above-described compounds of the invention, particularly 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.

[0105] The invention therefore further relates to oligomers, polymers or dendrimers containing one or more compounds according to formula (I), wherein the bond(s) to the polymer, oligomer or dendrimer are formed at any desired number denoted by R in formula (I). 1 , R 2 , R 3 , R4 or R 5 substituted positions can be located. 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.

[0106] 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.

[0107] 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, alpha-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, Decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate,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 or mixtures of these solvents.

[0108] The invention therefore further provides a formulation, in particular a solution, 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), as well as at least one solvent, preferably an organic solvent. The preparation of such solutions is known to those skilled in the art.

[0109] 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 of formula (I) in an electronic device.The electronic device is preferably selected from the group consisting of organic integrated circuits (OLCs), 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).

[0110] The invention further relates to an electronic device comprising at least one compound according to formula (I). The electronic device is preferably selected from the above-mentioned devices.

[0111] Particularly preferred is an organic electroluminescent device comprising an anode, a cathode, and at least one emitting layer, characterized in that at least one organic layer is present in the device, which contains at least one compound according to formula (I). Preferred is an organic electroluminescent device comprising 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).

[0112] A hole-transporting layer is understood to mean all layers arranged between the anode and the emitting layer, preferably a hole-injection layer, a hole-transport layer, and an electron-blocking layer. A hole-injection layer is understood to be a layer that is directly adjacent to the anode. A hole-transport layer is understood to be a layer that is present between the anode and the emitting layer, but is not directly adjacent to the anode, and preferably also not directly adjacent to the emitting layer. An electron-blocking layer is understood to be a layer that is present between the anode and the emitting layer and is directly adjacent to the emitting layer. An electron-blocking layer preferably has a high-energy LUMO and thus prevents electrons from escaping from the emitting layer.

[0113] In addition to the cathode, anode, and emitting layer, the electronic device may contain further layers. These may be 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 are necessarily present, and the choice of layers always depends on the compounds used and, in particular, on whether the electroluminescent device is fluorescent or phosphorescent.

[0114] The sequence of layers of the electronic device is preferably as follows:

[0115] -Anode-

[0116] -Hole injection layer- -Hole transport layer- -Optional additional hole transport layers- -Emitting layer-

[0117] -optional hole blocking layer- -electron transport layer- -electron injection layer- -cathode-

[0118] It should be pointed out again that not all of the layers mentioned have to be present and / or that additional layers can be present. The organic electroluminescent device according to the invention can contain a plurality of emitting layers. These emitting layers particularly preferably have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, i.e. different emitting compounds which can fluoresce or phosphoresce and which 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 in each case one of the three layers exhibits blue emission, in each case one of the three layers exhibits green emission and in each case 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 that, instead of using multiple color-emitting emitter compounds, a single emitter compound that emits over a broad wavelength range may also be suitable for generating white light.

[0119] 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 a phosphorescent emitting layer. Preferably, the emitting layer is a blue fluorescent layer or a green phosphorescent layer.

[0120] If the device containing the compound of formula (I) contains a phosphorescent emitting layer, it is preferred that this layer contains two or more, preferably exactly two, different matrix materials (mixed-matrix system). Preferred embodiments of mixed-matrix systems are described in more detail below.

[0121] 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, ie in a proportion of 100% in the hole transport layer, or it can be used in combination with one or more other compounds.

[0122] 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-transport materials specified below. In the described preferred embodiment, 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%.

[0123] 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 preferably used are those organic electron acceptor compounds that can oxidize one or more of the other compounds in the mixture.

[0124] Particularly preferred p-dopants are quinodimethane compounds, azaindenofluorenediones, azaphenalenes, azatriphenylenes, 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 as dopants are transition metal oxides, preferably oxides of rhenium, molybdenum, and tungsten, particularly preferably Re2O3, MoO3, WO3, and ReO3. Complexes of bismuth in oxidation state (III), in particular bismuth(III) complexes with electron-poor ligands, in particular carboxylate ligands, are further preferred. The p-dopants are preferably present 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.

[0125] Furthermore, preferred p-dopants are the compounds explicitly shown on pages 86 - 87 of the published patent application WO2021 / 156323A1.

[0126] According to a preferred embodiment, the device contains a hole-injection layer that 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.

[0127] According to a preferred embodiment of embodiment b), the electron-deficient material is a hexaazatriphenylene derivative as described in US 2007 / 0092755.

[0128] The compound of formula (I) can be present in a hole-injection layer, a hole-transport layer, and / or an electron-blocking layer of the device. If the compound is present in a hole-injection layer or 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.

[0129] The compound of formula (I) is preferably contained 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 the admixture of any other compound.

[0130] 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.

[0131] In this case, the proportion of the matrix material in the emitting layer 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.%.

[0132] 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.%.

[0133] An emitting layer of an organic electroluminescent device can also contain systems comprising multiple matrix materials (mixed-matrix systems) and / or multiple emitting compounds. In this case, too, the emitting compounds are generally those compounds whose proportion is the smaller in the system, and the matrix materials are those compounds whose proportion is the larger in the system. In individual cases, however, the proportion of a single matrix material in the system may be smaller than the proportion of a single emitting compound.

[0134] It is preferred that the compounds of 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. Preferably, one of the two materials is 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 LIIMO (wide-bandgap materials). In a mixed-matrix system, the compound of formula (I) preferably represents the matrix material with hole-transporting properties.Accordingly, when 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 having electron-transporting properties is present in the emitting layer. The two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1, and most preferably 1:4 to 1:1.

[0135] 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.

[0136] 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 other mixed-matrix component(s) fulfilling other functions.

[0137] The following material classes are preferably used in the above-mentioned layers of the device:

[0138] Phosphorescent emitters:

[0139] The term phosphorescent emitters typically includes 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.

[0140] Particularly suitable phosphorescent emitters are compounds which, upon suitable excitation, emit light, preferably in the visible range, and which also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, indium, palladium, platinum, silver, gold, or europium are used as phosphorescent emitters, in particular compounds containing indium, platinum, or copper.

[0141] For the purposes of the present invention, all luminescent iridium, platinum or copper complexes are considered to be phosphorescent compounds.

[0142] In general, all phosphorescent complexes used in the prior art for phosphorescent OLEDs and known to those skilled in the art in the field of organic electroluminescent devices are suitable for use in the devices according to the invention. Further examples of suitable phosphorescent emitters are shown in the following table: 5

[0143] 30 5

[0144] 30

[0145] Fluorescent emitters:

[0146] 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 in the 1,6-position. 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.

[0147] Matrix materials for fluorescent emitters:

[0148] 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, as used herein, 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:

[0149] Preferred matrix materials for phosphorescent emitters, in addition to the compounds of formula (I), 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.

[0150] Electron-transporting materials:

[0151] Suitable electron-transporting materials are, for example, the compounds disclosed 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.

[0152] All materials that are used as electron-transport materials in the electron-transport layer according to the state of the art can be used as materials for the electron-transport layer. Particularly suitable are aluminum complexes, for example, Alqs; 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.

[0153] Preferred electron transport and electron injection materials continue to be the compounds explicitly shown on pages 73-75 of W02020 / 109434A1. Hole-transporting materials:

[0154] 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.

[0155] Preferred hole-transporting compounds continue to be the compounds explicitly shown on pages 76-80 of W02020 / 109434A1.

[0156] 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.Particularly preferred materials are indium tin oxide (ITO) or indium zinc oxide (IZO). 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.

[0157] 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' 7 mbar.

[0158] 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' 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 (e.g., BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0159] Also preferred is an electronic device characterized in that one or more layers are produced from solution, such as by spin coating, or by any printing process, such as screen printing, flexographic printing, nozzle printing, or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or inkjet printing. Soluble compounds according to formula (I) are required for this purpose. High solubility can be achieved by suitable substitution of the compounds.

[0160] 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.

[0161] After the layers have been applied, the device is structured, contacted and finally sealed, depending on the application, to prevent damaging effects from water and air.

[0162] According to the invention, the electronic devices comprising one or more compounds according to formula (I) can be used in displays, as light sources in lighting applications and as light sources in medical and / or cosmetic applications.

[0163] Examples

[0164] A) Synthesis examples

[0165] Synthesis 3-bromo-4-[4-(naphthalen-1-yl)phenyl]-1,T-biphenyl 1a 16.5 g (66.5 mmol) of [4-(naphthalen-1-yl)phenyl]boronic acid, 23.8 g (66.5 mmol) of 3-bromo4-iodo-1,1'-biphenyl, 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: 25 g (85% of theory), purity according to GC-MS >94%.

[0166] Analogously, the following connections are made:

[0167] 92

[0168] 9

[0169]

[0170] Synthesis of N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-N-{4-[4-(naphthalen-1-yl)phenyl]-[1,T-biphenyl]-3-yl}-9H-fluoren-2-amine 2a

[0171] N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluoren-2-amine (32.3 g, 75 mmol), 3-bromo-4-[4-(naphthalen-1-yl)phenyl]-1,1'-biphenyl (29 g, 75 mmol), and sodium tert-butylate (14.7 g, 150 mmol) were dissolved in 350 mL of toluene. The solution was degassed and saturated with N2. Tri-tert-butylphosphine (7.5 mL; 7.5 mmol, 1 M in xylene) and 3.4 g (3.8 mmol) of Pd2(dba)3 were then 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 was 23.9 g (42% of theory).

[0172] Analogously, the following connections are made:

[0173] co cn

[0174]

[0175]

[0176] Synthese von N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-N-(4-{4-[4- (naphthalen-1-yl)phenyl]-[1,T-biphenyl]-3-yl}phenyl)-9H-fluoren-2-amin 3a

[0177] 25.9 g (43 mmol) of N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-9H-fluoren-2-amine and 18.7 g (43 mmol) of 3-bromo-4-[4-(naphthalen-1-yl)phenyl]-1,1'-biphenyl were suspended in 400 mL of dioxane and 13.7 g of cesium fluoride (90 mmol). 4.0 g (5.4 mmol) of palladium dichloride bis(tricyclohexylphosphine) were added to this suspension, and the reaction mixture was heated under reflux for 18 h. After cooling, the organic phase is separated, filtered through silica gel, washed three times with 80 mL of water, and then evaporated to dryness. After filtration of the crude product through silica gel with toluene, the remaining residue is recrystallized from toluene and finally sublimed under high vacuum. Purity is 99.9%. The yield is 12.5 g (35% of theory).

[0178] Analogously, the following compounds are prepared: 5

[0179] 30 5

[0180] 30

[0181]

[0182] B) Device examples

[0183] The compounds according to the application can be used in OLEDs with the following structure: Substrate I 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.

[0184] The exact 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.

[0185] 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 and HTM-2:

[0186] The following data are obtained for the OLEDs, which demonstrate the advantageous use of the compounds:

[0187] The following examples demonstrate that the compounds according to the application can be used advantageously in the EBL of blue fluorescent OLEDs.

[0188] The following data are obtained for the OLEDs, which demonstrate the advantageous use of the compounds: 5

[0189] 30

[0190] The following compounds HTM-3 to HTM-8 can also be used advantageously in the above setups, instead of HTM-1 and HTM-2, and provide comparable device measurement results:

[0191] The compounds HTM-3 to HTM-8 are particularly suitable for use in the construction of Examples 1 and 2 shown above, instead of the compound HTM-1 or HTM-2, and provide comparable results as shown above for the compounds HTM-1 and HTM-2.

Claims

Claims 1 . Compound according to a formula (I) Formula (I) where the variables occurring are: Z 1 is chosen the same or different from N and CR at each occurrence 1 ; where the unit by a unit chosen from units of the following formulas may be replaced, where the dashed bonds in the units correspond to the bonds of the unit correspond, and where the 1 Variables Z 1 in the unit in these cases are equal to C; Ar 0 is equal to phenylene, which with residues R 2 is substituted; Ar 1 and Ar 2 are selected, identically or differently at each occurrence, from aromatic ring systems with 6 to 40 aromatic ring atoms, which are substituted by radicals R 4 are substituted, and from heteroaromatic ring systems with 5 to 40 aromatic ring atoms, which are substituted by residues R 4 are substituted; Ar 3 and Ar 4 are selected, identically or differently at each occurrence, from aromatic ring systems with 6 to 40 aromatic ring atoms, which are substituted by radicals R 5 are substituted, and from heteroaromatic ring systems with 5 to 40 aromatic ring atoms, which are substituted with residues R 5 are substituted; where at least one of Ar 3 and Ar 4 is selected from aryl groups with 10 to 20 aromatic ring atoms, which are substituted by radicals R 5 are substituted; Ar L is selected from aromatic ring systems with 6 to 40 aromatic ring atoms, which are linked to residues R 3 are substituted, and from heteroaromatic ring systems with 5 to 40 aromatic ring atoms, which are substituted with residues R 3 are substituted; R 1is selected at each occurrence, the same or different, from H, D, F, CI, 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; where the said alkyl, alkoxy, alkenyl and alkynyl groups are each substituted by 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 4 is selected at each occurrence, the same or different, from H, D, F, CI, Br, I, C(=O)R 6 , CN, Si(R 6)3, P(=O)(R 6 )2, OR 6 , S(=O)R 6 , S(=O)2R 6 , straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 C atoms, alkenyl or alkynyl groups with 2 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 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 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 2 , R 3 and R 5 are selected at each occurrence, identically or differently, from H, D, F, CI, 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 are selected from the radicals R 2 , R 3 and R 5 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 R6 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 at each occurrence, the same or different, from H, D, F, CI, Br, I, C(=O)R 7 , CN, Si(R 7 )7, P(=O)(R 7 )2, OR 7 , S(=O)R 7 , S(=O)2R 7 , straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 C atoms, alkenyl or alkynyl groups with 2 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; where two or more radicals R 6may 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 3 are substituted; and wherein one or more CH2 groups in said alkyl, alkoxy, alkenyl and alkynyl groups are substituted by -R 7 C=CR 7 - , -C≡C-, Si(R 7 )2, C=O, C=NR 7 , -C(=O)O-, -C(=O)NR 7 -, NR 7 , P(=O)(R 7 ), -O-, -S-, SO or SO2; R 7 is selected, identically or differently at each occurrence, from H, D, F, CI, 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 7can be linked to one another and form a ring; and wherein the said alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems can be substituted by one or more radicals selected from F and CN; m is 0, 1, 2 or 3; n is 0, 1, 2 or 3; k is 0 or 1.

2. Compound according to claim 1, characterized in that all Groups Z 1 equal to CR 1 are, and that units cannot be replaced by units of the formulas (Z-1 ) to (Z-6).

3. A compound according to claim 1 or 2, characterized in that index m is 0 or 1.

4. Compound according to one or more of claims 1 to 3, characterized in that index n is 0 or 1.

5. Compound according to one or more of claims 1 to 4, characterized in that at least one index selected from indices m and n is greater than 0.

6. Compound according to one or more of claims 1 to 5, characterized in that index k=0, or that index k=1 and Ar L is phenyl, which is substituted with residues R 3 is substituted.

7. Compound according to one or more of claims 1 to 6, characterized in that Ar 3 and Ar 4 are selected at each occurrence, identically or differently, from phenyl, biphenyl, naphthyl, phenanthrenyl, fluoranthenyl, triphenylenyl and fluorenyl, in particular 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, where the groups are each substituted by radicals R 5 are substituted.

8. Compound according to one or more of claims 1 to 7, characterized in that the at least one group is selected from groups Ar 3 and Ar 4, which must be selected from aryl groups with 10 to 20 aromatic ring atoms, which are linked to radicals R 5 are substituted, is selected from groups of the following formulas: wherein the variables occurring are as defined in one or more of claims 1 to 7, and wherein the dashed line represents the bond of the group Ar 3 or Ar 4 to the rest of the connection.

9. Compound according to one or more of claims 1 to 8, characterized in that - R 1 is selected at each occurrence, the same or different, from H, D, F, CN, Si(R 6 )3, N(R 6 )2, straight-chain alkyl groups having 1 to 20 C atoms, and branched or cyclic alkyl groups having 3 to 20 C atoms; where the said alkyl groups are each substituted by radicals R 6 are substituted; and wherein in said alkyl groups one or more CH2 groups are substituted by - C≡C-, -R6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , -NR 6 -, -O-, -S-, -C(=O)O- or - C(=O)NR 6 - can be replaced; and - R 2 , R 3 and R 5 are selected at each occurrence, identically or differently, 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, and aromatic ring systems having 6 to 40 aromatic ring atoms; wherein the said alkyl groups and the said aromatic ring systems are each substituted by radicals R 6 are substituted.

10. A compound according to one or more of claims 1 to 9, characterized in that the compound corresponds to one of the following formulas wherein the occurring variables are defined as in one or more of claims 1 to 8.

11. Compound according to one or more of claims 1 to 10, characterized in that Ar 4 is phenyl, which is substituted with residues R 5 is substituted.

12. A compound according to one or more of claims 1 to 10, characterized in that it corresponds to one of the following formulas 5 30 where Ar k is selected from aryl groups with 10 to 20 aromatic ring atoms, which are substituted by radicals R 5 are substituted, and wherein the other variables occurring are defined as in one or more of claims 1 to 10.

13. A process for preparing a compound according to one or more of claims 1 to 12, characterized in that a chain-like tris-aryl derivative substituted with a reactive group is either a) reacted in a coupling reaction with a secondary amine, or b) reacted in a coupling reaction with an aromatic or heteroaromatic compound which has a boron-containing group and has an amino group.

14. Oligomer, polymer or dendrimer containing one or more compounds according to one or more of claims 1 to 12, wherein the bond(s) to the polymer, oligomer or dendrimer are at any positions indicated in the formulas with R 1 , R 2 , R 3 , R 4 or R 5 substituted positions can be located.

15. Formulation comprising at least one compound according to one or more of claims 1 to 12 or at least one polymer, oligomer or dendrimer according to claim 14, and at least one solvent.

16. An electronic device comprising at least one compound according to one or more of claims 1 to 12, or at least one polymer, oligomer or dendrimer according to claim 14.

17. Electronic device according to claim 16, 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.

18. Use of a compound according to one or more of claims 1 to 12 in an electronic device.

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