Materials for electronic devices

Abstract

The present invention relates to compounds of one of formulae (I) and (II), to processes for producing those compounds, to electronic devices containing one or more of those compounds, and to the use of the compounds in electronic devices.

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. Furthermore, compounds are 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 formulas 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 relates to compounds according to one of the following formulas (I) and (II):

[0009] where the following applies to the groups and indices:

[0010] Z is, if one of the freely drawn bonds is attached to it, equal to C; and if no freely drawn bond is attached to it, chosen at each occurrence, the same or different, from CR 1 and N;

[0011] Z 1 is, when the freely drawn bond is attached to it, equal to C; and when the freely drawn bond is not attached to it, chosen at each occurrence, the same or different, from CR 1 and N; where two adjacent groups Z 1 , to each of which the freely drawn bond is not bound, may in one or more cases in formula (II) be equal to C and part of a unit of the following formula: where the bonds marked with * are bonds to neighboring groups Z1 in the respective six-membered ring, which represents the two neighboring groups Z 1 contains; and

[0012] Y is equal to O, S or NR 1 ; and

[0013] Z 2 is chosen the same or different from N and CR at each occurrence 2 ;

[0014] L is the same or different at each occurrence and is selected from single bond, aromatic ring system with 6 to 40 aromatic ring atoms, which is substituted by radicals R 2 substituted, and heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is substituted with residues R 2 is substituted;

[0015] HetAr is selected at each occurrence, identically or differently, from heteroaryl groups with 5 to 20 aromatic ring atoms, which are substituted by radicals R 2 are substituted;

[0016] Ar L is an aromatic ring system with 6 to 40 aromatic ring atoms, which is linked to residues R 3substituted, or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is substituted with residues R 3 is substituted;

[0017] Ar 1 is in the case of k=1 at each occurrence, the same or different selected 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; and Ar 1 is in the case of k=0 at each occurrence, the same or different selected 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, wherein at least one of the two Ar 1 in the formula is chosen from the following formulas

[0018] Formula (Ar1-7) where:

[0019] L 1 is a single bond, an aromatic ring system with 6 to 40 aromatic ring atoms, which is bonded to residues R 4 substituted, or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is substituted with residues R 4 is substituted;

[0020] L 2 is an aromatic ring system with 6 to 40 aromatic ring atoms, which is linked to residues R 4 substituted, or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is substituted with residues R 4 is substituted;

[0021] V is O, S or NR 4 ;

[0022] R 1 is selected at each occurrence, the same or different, from H, D, F, CI, 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 1 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 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;

[0023] R 2is selected at each occurrence, the same or different, from H, D, F, CI, 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 2 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 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;

[0024] R 3 is selected at each occurrence, the same or different, from H, D, F, CI, 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 3may 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 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, CI, 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 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;

[0025] R 5is 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 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 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;

[0026] R 6 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 6 may 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; k is 0 or 1, where for k=0 the group Ar L is not present, and the [Ar L ] kbonded atoms are directly bonded to one another; i is, on each occurrence, identical or different, 0 or 1, where at least one index i in formula (I) is 1; and where at least once in formula (II) it is stated that two adjacent groups Z 1 , to which the freely drawn bond is not bound, part of a unit of the above formula (Z 1 -kond).

[0027] The following definitions apply to the chemical groups used in this application. They apply unless more specific definitions are given.

[0028] 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.

[0029] 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.

[0030] 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.,

[0031] An aromatic ring system within the meaning of this invention is a system which does not necessarily contain only aryl groups, but which 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 C atoms and no heteroatoms in the ring system. The definition of "aromatic ring system" does not include heteroaryl groups.

[0032] 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.

[0033] 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.

[0034] 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”.

[0035] 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.

[0036] 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.

[0037] 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.,

[0038] For the purposes of the present 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.

[0039] Among formulas (I) and (II), formula (I) is preferred.

[0040] According to a preferred embodiment, formula (I) corresponds to one of the following formulas (I-1), (I-2) and (I-3)

[0041] where the variables appearing are defined as above. According to a preferred embodiment, L in formulas (I-1) to (I-3) is a single bond. Further preferably, in formulas (I-1) to (I-3), Z is CR 1 , if no freely drawn bond is attached thereto, and Z is C if a freely drawn bond is attached thereto. Among the formulas (I-1) to (I-3), formulas (I-1) and (I-3) are preferred, and formula (I-1) is particularly preferred.

[0042] Particularly preferred are the following embodiments of formulas (I-1) to (I-3):

[0043] 30

[0044] where the variables appearing are defined as above. Furthermore, in formulas (I-1-1) to (I-3-4) Z is preferably CR 1, if no freely drawn bond is attached to it, and Z is C if a freely drawn bond is attached to it. Among the formulas (I-1-1) to (I-3-4), the formulas (I-1-1), (I-1-2), (I-1-3), (I-1-4), (I-3-I), (I-3-2), (I-3-3) and (I-3-4) are preferred, particularly preferred are the formulas (I-1-1), (I-1-2), (I-1-3) and (I-1-4).

[0045] A preferred embodiment of formula (I) corresponds to formula (lA)

[0046] where the variables occurring are defined as above.

[0047] The group -L-HetAr preferably corresponds to one of the following

[0048] Formulas (HetAr-1) to (HetAr-13), if L is a single bond as preferred:

[0049] where the bond marked with * represents the bond to the rest of the

[0050] Formula. Preferred embodiments of formula (lA) correspond to the following formulas (lA-1) to (lA-3) According to a preferred embodiment, L in formulas (lA-1) to (lA-3) is a single bond. Furthermore, in formulas (lA-1) to (lA-3), Z is GR 1 , if no freely drawn bond is attached thereto, and Z is C if a freely drawn bond is attached thereto. Among the formulas (lA-1) to (lA-3), the formulas (lA-1) and (lA-3) are preferred, and the formula (lA-1) is particularly preferred.

[0051] Preferred embodiments of formulas (lA-1) to (lA-3) correspond to the following formulas:

[0052] Formula base formula “-L-HetAr” =

[0053] (lA-1 -1) (lA-1) Formula (HetAr-1 )

[0054] (lA-1 -2) (lA-1) Formula (HetAr-2)

[0055] (lA-1 -3) (lA-1) Formula (HetAr-3)

[0056] (lA-1 -4) (lA-1) Formula (HetAr-4)

[0057] (lA-1 -5) (lA-1) Formal (HetAr-5)

[0058] (lA-1 -6) (lA-1) Formal (HetAr-6)

[0059] (lA-1 -7) (lA-1) Formal (HetAr-7)

[0060] (lA-1 -8) (lA-1) Formal (HetAr-8)

[0061] (lA-1 -9) (lA-1) Formal (HetAr-9)

[0062] (lA-1 -10) (lA-1) Formal (HetAr-10)

[0063] (lA-1 -11) (lA-1) Formal (HetAr-11 )

[0064] (lA-1 -12) (lA-1) Formal (HetAr-12)

[0065] (lA-1 -13) (lA-1) Formal (HetAr-13)

[0066] (lA-2-1) (lA-2) Formal (HetAr-1 )

[0067] (lA-2-2) (lA-2) Formal (HetAr-2)

[0068] (lA-2-3) (lA-2) Formal (HetAr-3)

[0069] (lA-2-4) (lA-2) Formal (HetAr-4)

[0070] (lA-2-5) (lA-2) Formal (HetAr-5)

[0071] (lA-2-6) (lA-2) Formal (HetAr-6)

[0072] (lA-2-7) (lA-2) Formal (HetAr-7)

[0073] (lA-2-8) (lA-2) Formal (HetAr-8)

[0074] (lA-2-9) (lA-2) Formal (HetAr-9)

[0075] (lA-2-10) (lA-2) Formal (HetAr-10)

[0076] (lA-2-11) (lA-2) Formal (HetAr-11 )

[0077] (lA-2-12) (lA-2) Formal (HetAr-12) (lA-2-13) (lA-2) Formal (HetAr-13)

[0078] (lA-3-1) (lA-3) Formal (HetAr-1 )

[0079] (lA-3-2) (lA-3) Formal (HetAr-2)

[0080] (lA-3-3) (lA-3) Formal (HetAr-3)

[0081] (lA-3-4) (lA-3) Formal (HetAr-4)

[0082] (lA-3-5) (lA-3) Formal (HetAr-5)

[0083] (lA-3-6) (lA-3) Formal (HetAr-6)

[0084] (lA-3-7) (lA-3) Formal (HetAr-7)

[0085] (lA-3-8) (lA-3) Formal (HetAr-8)

[0086] (lA-3-9) (lA-3) Formal (HetAr-9)

[0087] (lA-3-10) (lA-3) Formal (HetAr-10)

[0088] (lA-3-11) (lA-3) Formal (HetAr-11 )

[0089] (lA-3-12) (lA-3) Formula (HetAr-12)

[0090] (lA-3-13) (lA-3) Formula (HetAr-13)

[0091] Preferred embodiments of formula (II) correspond to the following formulas (II-1) to (II-8)

[0092] where the variables are defined as above, and Z 1 is preferably equal to C if a freely drawn bond is attached to it, and is preferably equal to CR 1 is if no freely drawn binding is attached to it.

[0093] Among the formulas (II-1) to (II-8), the formulas (II-1) to (II-4) are preferred.

[0094] Preferred embodiments of formulas (II-1) to (II-8) correspond to the following formulas:

[0095] Formula Basic Formula Y =

[0096] Formula (II-1-1) Formula (II-1 ) O

[0097] Formula (II-1-2) Formula (II-1 ) S

[0098] Formula (II-1-3) Formula (II-1 ) NO 2

[0099] Formula (II-2-1) Formula (II-2) O

[0100] Formula (II-2-2) Formula (II-2) S

[0101] Formula (II-2-3) Formula (II-2) NO 2

[0102] Formula (II-3-1) Formula (II-3) O

[0103] Formula (II-3-2) Formula (II-3) S

[0104] Formula (II-3-3) Formula (II-3) NO 2 Formula (II-4-1) Formula (II-4) O

[0105] Formula (II-4-2) Formula (II-4) S

[0106] Formula (II-4-3) Formula (II-4) NO 2

[0107] Formula (II-5-1) Formula (II-5) O

[0108] Formula (II-5-2) Formula (II-5) S

[0109] Formula (II-5-3) Formula (II-5) NO 2

[0110] Formula (II-6-1) Formula (II-6) O

[0111] Formula (II-6-2) Formula (II-6) S

[0112] Formula (II-6-3) Formula (II-6) NO 2

[0113] Formula (II-7-1) Formula (II-7) O

[0114] Formula (II-7-2) Formula (II-7) S

[0115] Formula (II-7-3) Formula (II-7) NO 2

[0116] Formula (II-8-1) Formula (II-8) O

[0117] Formula (II-8-2) Formula (II-8) S

[0118] Formula (II-8-3) Formula (II-8) NO 2

[0119] Among these formulas, formulas (II-1-1) to (II-4-3) are preferred.

[0120] It is further preferred that formula (II) corresponds to the following formula (II-A): where the variables appearing are defined as above. Preferred embodiments of formula (II-A) correspond to the following formulas (II-A-1) to (II-A-8) where the variables are defined as above, and where Z 1 preferably CR 1 and where Z 2 preferably CR 2Among the formulas (lA-1) to (lA-8), the formulas (lA-1) to (lA-4) are particularly preferred.

[0121] Preferred embodiments of formulas (II-A-1) to (II-A-8) correspond to the following formulas:

[0122] Formula Basic Formula Y =

[0123] Formula (II-A-1 -1) Formula (II-A-1) O

[0124] Formula (II-A-1 -2) Formula (II-A-1) S

[0125] Formula (II-A-1 -3) Formula (II-A-1) NO 2

[0126] Formula (II-A-2-1) Formula (II-A-2) O

[0127] Formula (II-A-2-2) Formula (II-A-2) S

[0128] Formula (II-A-2-3) Formula (II-A-2) NO 2

[0129] Formula (II-A-3-1) Formula (II-A-3) O

[0130] Formula (II-A-3-2) Formula (II-A-3) S

[0131] Formula (II-A-3-3) Formula (II-A-3) NO 2

[0132] Formula (II-A-4-1) Formula (I lA-4) O

[0133] Formula (II-A-4-2) Formula (I lA-4) S

[0134] Formel (ll-A-4-3) Formel (I l-A-4) NR 2

[0135] Formel (ll-A-5-1) Formel (ll-A-5) O

[0136] Formel (ll-A-5-2) Formel (ll-A-5) S

[0137] Formel (ll-A-5-3) Formel (ll-A-5) NR 2

[0138] Formel (ll-A-6-1) Formel (ll-A-6) O

[0139] Formel (ll-A-6-2) Formel (ll-A-6) S

[0140] Formel (ll-A-6-3) Formel (ll-A-6) NR 2

[0141] Formel (ll-A-7-1) Formel (ll-A-7) O

[0142] Formel (ll-A-7-2) Formel (ll-A-7) S

[0143] Formel (ll-A-7-3) Formel (ll-A-7) NR 2

[0144] Formel (ll-A-8-1) Formel (ll-A-8) O

[0145] Formel (ll-A-8-2) Formel (ll-A-8) S

[0146] Formel (I l-A-8-3) Formel (ll-A-8) NR 2

[0147] Among the formulas (1A-1-1) to (1A-8-3), the formulas (1A-1) to (1A-4-3) are particularly preferred. Preferred generic formulas for compounds according to formulas (I) and (II) of the present application are shown below. Ar1 is defined as Ar 1 in formulas (I) and (II), where for the structures marked with # the definition of Ar 1 for k=1.

[0148]

[0149] 30

[0150]

[0151] Z is preferably equal to C if one of the freely drawn bonds is bonded to it; and is preferably equal to CR 1, if no freely drawn bond is attached to it. Furthermore, it is preferred that at most one of the Z groups in a six-membered ring is N, and the remaining Z groups are C if one of the freely drawn bonds is attached to it; and CR 1 are, if no freely drawn binding is attached to it.

[0152] Z 1 is preferably equal to C if the freely drawn bond is attached to it; and is preferably equal to CR 1 , if no freely drawn bond is attached to it; where two adjacent groups Z 1 , to each of which the freely drawn bond is not bound, in one or more cases, preferably in exactly one case, in formula (II) is part of a unit of the formula (Z 1 -kond) can be.

[0153] It is preferred in formula (II) that in exactly one case two adjacent groups Z 1, to which the freely drawn bond is not bound, part of a unit of the formula (Z 1 -kond).

[0154] Z is preferred 2 in formula (Z 1 -kond) equals CR 2 .

[0155] L is preferably a single bond.

[0156] HetAr is preferably selected, identically or differently at each occurrence, from dibenzofuran; dibenzofuran with a benzene ring fused to one of the two benzene rings; dibenzothiophene; dibenzothiophene with a benzene ring fused to one of the two benzene rings; carbazole bonded to the nitrogen atom or to one of its benzene rings;

[0157] Carbazole with a benzene ring fused to one of the two benzene rings, which is bonded to the nitrogen atom or to one of its benzene rings; indenocarbazole bonded to the nitrogen atom or to one of its benzene rings; and indolocarbazole bonded to one of its nitrogen atoms or to one of its benzene rings; where the said groups are each substituted by radicals R 2 are substituted. Further preferred are the abovementioned groups of the formulas (HetAr-1) to (HetAr-13), particularly preferred are the groups (HetAr-4) and (HetAr-8). Preferably, exactly one index i in formula (I) is 1, and the other indices i are 0. According to an alternative preferred embodiment, exactly two indices i in formula (I) are 1, and the other index i is 0.

[0158] Ar L is preferably an aromatic ring system with 6 to 25 aromatic ring atoms, which is substituted with radicals R 3is 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.

[0159] Ar L is preferably chosen the same or different at each occurrence from

[0160] Groups of the following formulas:

[0161] where the dashed lines represent the bonds to the rest of the formula, and where the formulas Ar L -1 , Ar L -2 and Ar L -3 are particularly preferred.

[0162] According to a preferred embodiment, k=0. According to an alternative preferred embodiment, k=1.

[0163] In case k=1, Ar 1 preferably selected the same or different at each occurrence from the following formulas:

[0164]

[0165] 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 positions shown unsubstituted.

[0166] According to a preferred embodiment, for k=1 at least one Ar 1 at each occurrence, the same or different, selected from the above formulas Ar 1 -1 to Ar 1 -276, and the remaining group Ar 1 is selected from the formulas (Ar1-1) to (Ar1-7). According to an alternative preferred embodiment, for k=1, both groups Ar 1selected from the formulas (Ar1-1) to (Ar1-7).

[0167] For k=0, at least one Ar is preferred 1 at each occurrence, the same or different, selected from the above formulas Ar 1 -1 to Ar 1 -276, and the remaining group Ar 1 is selected from the formulas (Ar1-1) to (Ar1-7). According to an alternative preferred embodiment, for k=0, both groups Ar 1 selected from the formulas (Ar1 -1 ) to (Ar1-7).

[0168] For k=0, at least one Ar is preferred 1 selected from formulas (Ar1-1) and (Ar1-2), particularly preferably (Ar1-1), particularly preferably both Ar 1 selected from formulas (Ar-1-1) and (Ar1-2), particularly preferably (Ar1-1). The embodiments of the above sentence are preferably present for formula (I).

[0169] Among the formulas (Ar1-1) to (Ar1-7), the formulas (Ar1-1), (Ar1-2) and (Ar1-5) are preferred. According to an alternative preferred embodiment, among the formulas (Ar1-1) to (Ar1-7), the formulas (Ar1-6) and (Ar1-7) are preferred. According to a further alternative preferred embodiment, among the formulas (Ar1-1) to (Ar1-1-7), the formulas (Ar1-5) to (Ar1-7), in particular the formula (Ar1-5), are preferred, in particular it is preferred that both Ar 1 are selected from formulas (Ar1-5) to (Ar1-7), in particular formula (Ar1-5). That one of the two Ar 1 , preferably both 1 , are selected from formulas (Ar1-5) to (Ar1-7), in particular formula (Ar1-5), is particularly preferred for formula (II).

[0170] Particularly preferred embodiments of the formulas (Ar1-1) to (Ar1-7) are the formulas Ar defined above 1 -48 to Ar 1 -138, Ar 1 -144, Ar 1 -147 to Ar 1 -149, Ar 1-151 , Ar 1 -153 to Ar 1 -155, Ar 1 -157 to Ar 1 -159, Ar 1 -162, Ar 1 - 176, Ar 1 -178, Ar 1 -179, Ar 1 -182, Ar 1 -184 to Ar 1 -194, Ar 1 -257 to Ar 1 -259, Ar 1 -263, Ar 1 -265 to Ar 1 -269 and Ar 1 -271.

[0171] Preferred is L 1 an aromatic ring system with 6 to 40 aromatic ring atoms, which is linked to residues R 4 substituted, or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is substituted with residues R 4 is substituted. Particularly preferred is L 1 an aromatic ring system with 6 to 40 aromatic ring atoms, which is linked to residues R 4 is substituted. Furthermore, for L 1 the groups of the above formulas Ar L -1 to Ar L-82 are preferred as embodiments, in particular the groups of the above-mentioned formulas Ar L -1 to Ar L -3.

[0172] Preferred is L 2 an aromatic ring system with 6 to 40 aromatic ring atoms, which is linked to residues R 4 is substituted. Furthermore, for L 2 the groups of the above formulas Ar L -1 to Ar L -82 are preferred as embodiments, in particular the groups of the above-mentioned formulas Ar L -1 to Ar L -3.

[0173] Preferred is R 1 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, 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 5are 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. Preference is also given to substituents R 5 by R 1 and substituents R 6 by R 5 by R 1 no heteroaromatic ring systems. R is particularly preferred 1 at each occurrence, identical or different, H or D, most preferably H.

[0174] Preferred Groups R 1 are the following groups:

[0175] 

[0176]

[0177] Particularly preferred among these are the groups R-1, R-2, R-143, R-147, R-148, R-149, R-154, R-175, R-177. According to a preferred embodiment, the compound contains at least one group R 1 which is not H or D, in particular one of the above-mentioned preferred groups R 1 .

[0178] residues R 2 are preferably selected, identically or differently at each occurrence, 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; and wherein in said alkyl groups one or more CH2 groups are substituted by -C C-, -R 5 C=CR5 -, Si(R 5 )2, C=O, C=NR 5 , -NR 5 -, -O-, -S-, -C(=O)O- or -C(=O)NR 5 - can be replaced. Particular preference is given to residues R 2 at each occurrence, identical or different, H or D, most preferably H.

[0179] residues R 3 are preferably selected, identically or differently at each occurrence, 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; 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=NR5 , -NR 5 -, -O-, -S-, -C(=O)O- or -C(=O)NR 5 - can be replaced. Particular preference is given to residues R 3 at each occurrence, identical or different, H or D, most preferably H.

[0180] residues R 4 are preferably selected, identically or differently at each occurrence, 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; 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 - can be replaced. Particular preference is given to residues R 4 at each occurrence, identically or differently, H or D, most preferably H, with the exception of radicals R 4 which bind to the bridgehead atom of a fluorenyl group, which are preferably selected from alkyl groups having 1 to 20 C atoms and aromatic ring systems having 6 to 40 aromatic ring atoms, and with the exception of radicals R 4 which bind to the N of a carbazole group, which are preferably selected from aromatic ring systems with 6 to 40 aromatic ring atoms.

[0181] residues R 5are 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; 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. Particular preference is given to residues R 5at each occurrence, identically or differently selected from H, D, 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 said alkyl groups, said aromatic ring systems and said heteroaromatic ring systems are each substituted by radicals R 6 are substituted. Preferably R 6 at each occurrence, identically or differently selected from H, D, F, CN, alkyl groups having 1 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 said alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by one or more radicals selected from F and CN. R is very particularly preferably 6at each occurrence, identical or different, H or D, most preferably H.

[0182] Preferably, formula (I) corresponds to one of the formulas (lA-1) to (lA-3) as defined above, wherein the following applies to the variables in combination:

[0183] - Z is CR 1 , if no freely drawn bond binds to it, and is C, if a freely drawn bond binds to it

[0184] - L is a single bond

[0185] - HetAr is chosen from formulas (HetAr-1 ) to (HetAr-13)

[0186] - Ar L is selected from phenyl, biphenyl, naphthyl and fluorenyl, each with residues R 3 are substituted

[0187] - Ar 1 is in case k=1 at each occurrence the same or different chosen from formulas Ar 1 -1 to Ar 1 -276; and in case k=0 at least one Ar 1 selected from formulas (Ar1 -1 ) to (Ar1-7), and possibly other Ar1 is chosen from formulas Ar 1 -1 to Ar 1 -276

[0188] - R 1 is the same or different at each occurrence H or D

[0189] - R 2 is the same or different at each occurrence H or D

[0190] - R 3 is the same or different at each occurrence H or D

[0191] - R 4 is chosen at each occurrence, the same or different, from H, D, F,

[0192] 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 5are 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 - can be replaced.

[0193] - R 5 is selected, identically or differently at each occurrence, from H, D, 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.

[0194] - R 6is selected, identically or differently at each occurrence, from H, D, F, CN, alkyl groups having 1 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 said alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by one or more radicals selected from F and CN.

[0195] - k= 0 or 1.

[0196] Preferably, formula (II) corresponds to one of the formulas (II-A-1) to (II-A-8) as defined above, where the variables are:

[0197] - Z 1 is CR 1

[0198] - Z 2 is CR 2

[0199] - Y is O, S or NR 1

[0200] - Ar L is selected from phenyl, biphenyl, naphthyl and fluorenyl, each with residues R 3 are substituted

[0201] - Ar 1is in case k=1 at each occurrence the same or different chosen from formulas Ar 1 -1 to Ar 1 -276; and in case k=0, preferably also in case k=1 , at least one Ar 1 selected from formulas (Ar1-1) to (Ar1-7), preferably formulas (Ar1-5) to (Ar1-7), and optionally the other Ar 1 is chosen from formulas Ar 1 -1 to Ar 1 -276

[0202] - R 1 is the same or different at each occurrence H or D

[0203] - R 2 is the same or different at each occurrence H or D

[0204] - R 3 is the same or different at each occurrence H or D - 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; 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 - can be replaced.

[0205] - R 5is selected, identically or differently at each occurrence, from H, D, 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.

[0206] - R 6 is selected, identically or differently at each occurrence, from H, D, F, CN, alkyl groups having 1 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 said alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by one or more radicals selected from F and CN.

[0207] - k= 0 or 1 .

[0208] The following specific compounds are preferred and are the subject of the present application:

[0209]

[0210] The compounds according to the present application can be prepared using the synthesis methods described below. Those skilled in the art can modify these methods within the scope of their general technical knowledge to prepare further compounds according to the application that cannot be prepared directly by the methods shown below.

[0211] According to the process shown in Scheme 1, starting from a biphenyl derivative substituted with two ortho-positioned reactive groups, a compound can be prepared in a Suzuki coupling with an aryl or heteroaryl boronic acid, which is substituted with the remaining of the two reactive groups ortho to the bond to the introduced aryl or heteroaryl group. The reactive groups are preferably selected from halogen atoms, particularly preferably from I, Br, and Cl.

[0212] Scheme 1

[0213] In a subsequent step, as shown in Scheme 2, a Hartwig-Buchwald coupling can be carried out, introducing an amino group into the molecule at the position of the remaining two reactive groups. This yields a compound according to the present application with index k=0.

[0214] Scheme 2

[0215] Alternatively, in a subsequent step, as shown in Scheme 3, a Suzuki coupling can be performed, introducing an aromatic ring system into the molecule at the position of the remaining two reactive groups. This yields a compound according to the present application in which index k is >0.

[0216] Scheme 3

[0217] Alternatively to Scheme 1, the derivative substituted with a reactive group can also be prepared according to the following Scheme 1b:

[0218] Scheme 1b The intermediate shown in Scheme 1b can be reacted with a secondary amine in a Buchwald reaction, as shown in Schemes 2 and 3, or with an aromatic or heteroaromatic compound bearing a boron-containing group in a Suzuki reaction. Corresponding reactions are shown in Schemes 2b and 3b below.

[0219]

[0220] The definitions of the variable groups in the schemes shown above are as follows:

[0221] R = H or organic residue

[0222] Q 1 , Q 2 = reactive group, preferably halogen, particularly preferably Cl, Br or I;

[0223] X = O, S or NR; n = 0 or integer; preferably 0, 1 or 2

[0224] Ar = optionally substituted aromatic or heteroaromatic.

[0225] The compounds shown above may have substituents on their aromatic rings, preferably D, F, CN, alkyl groups and aromatic or heteroaromatic ring systems.

[0226] The subject matter of the present application is therefore a process for preparing a compound according to the present application, characterized in that a biphenyl derivative substituted with a reactive group, which is substituted with an aryl or heteroaryl group, wherein the reactive group is in the ortho position to the aryl or heteroaryl group or to the phenyl-phenyl bond of the biphenyl, a) is reacted in a coupling reaction with a secondary amine, or b) is reacted in a coupling reaction with an aromatic or heteroaromatic compound which carries a boron-containing group.

[0227] 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.

[0228] Preferably, the biphenyl derivative substituted with a reactive group, which is substituted with an aryl or heteroaryl group, wherein the reactive group is in the ortho position to the aryl or heteroaryl group or to the phenyl-phenyl bond of the biphenyl (hereinafter: the aryl- or heteroaryl-substituted biphenyl derivative), is prepared starting from a biphenyl derivative substituted with two reactive groups, which is reacted by means of a Suzuki coupling reaction with an aryl- or heteroaryl boronic acid to give the aryl- or heteroaryl-substituted biphenyl derivative.

[0229] 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.

[0230] The invention therefore further relates to oligomers, polymers or dendrimers containing one or more compounds according to formula (I) or (II), wherein the bond(s) to the polymer, oligomer or dendrimer are formed at any radicals identified in formula (I) or (II) with R 1 , R 2 , R3 , or R 4substituted positions can be located. Depending on the linkage of the compound according to formula (I) or (II), the compound is part of a side chain of the oligomer or polymer or part of the main chain. An oligomer within the meaning of this invention is understood to be a compound which is composed of at least three monomer units. A polymer within the meaning of the invention is understood to be a compound which is composed of at least ten monomer units. The polymers, oligomers or dendrimers according to the invention can be conjugated, partially conjugated or non-conjugated. The oligomers or polymers according to the invention can be linear, branched or dendritic.In the linearly linked structures, the units according to formula (I) or (II) can be linked directly to one another or they can be linked to one another via a bivalent group, for example via a substituted or unsubstituted alkylene group, via a heteroatom, or via a bivalent aromatic or heteroaromatic group. In branched and dendritic structures, for example, three or more units according to formula (I) or (II) can be linked to form a branched or dendritic oligomer or polymer via a trivalent or higher-valent group, for example via a trivalent or higher-valent aromatic or heteroaromatic group.

[0231] The same preferences apply to the repeating units according to formula (I) or (II) in oligomers, dendrimers and polymers as described above for compounds according to formula (I) or (II).

[0232] To produce the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. Suitable and preferred comonomers are selected from fluorenes, spirobifluorenes, paraphenylenes, carbazoles, thiophenes, dihydrophenanthrenes, cis- and trans-indenofluorenes, ketones, phenanthrenes, or even several of these units. The polymers, oligomers, and dendrimers typically contain further units, for example emitting (fluorescent or phosphorescent) units, such as vinyltriarylamines or phosphorescent metal complexes, and / or charge-transport units, especially those based on triarylamines. The polymers, oligomers, and dendrimers according to the invention have advantageous properties, in particular long lifetimes, high efficiencies, and good color coordinates.

[0233] The polymers and oligomers according to the invention are generally prepared by polymerizing one or more types of monomers, of which at least one monomer in the polymer leads to repeating units of formula (I) or (II). Suitable polymerization reactions are known to the person skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions that lead to CC or CN linkages are the following:

[0234] (A) SUZUKI polymerization;

[0235] (B) YAMAMOTO polymerization;

[0236] (C) STILLE polymerization; and

[0237] (D) HARTWIG-BUCHWALD polymerization.

[0238] How the polymerization can be carried out according to these methods and how the polymers can then be separated from the reaction medium and purified is known to the person skilled in the art and is described in detail in the literature.

[0239] 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, dodecyl benzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetol, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether.

[0240] 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.

[0241] The invention therefore further provides a formulation, in particular a solution, dispersion, or emulsion, comprising at least one compound according to formula (I) or (II) or at least one polymer, oligomer, or dendrimer comprising at least one unit according to formula (I) or (II), and at least one solvent, preferably an organic solvent. The preparation of such solutions is known to those skilled in the art.

[0242] The compound of formula (I) or (II) is suitable for use in an electronic device, in particular an organic electroluminescent device (OLED). Depending on the substitution, the compound of formula (I) or (II) 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.

[0243] The invention therefore further relates to the use of a compound according to formula (I) or (II) 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-quenching devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), and particularly preferably organic electroluminescent devices (OLEDs).

[0244] The invention further relates to an electronic device comprising at least one compound according to formula (I) or (II). The electronic device is preferably selected from the above-mentioned devices.

[0245] 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) or (II). 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) or (II).

[0246] 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.

[0247] In addition to the cathode, anode, and emitting layer, the electronic device may 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 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.

[0248] The sequence of layers of the electronic device is preferably as follows:

[0249] -Anode-

[0250] -Hole injection layer- -Hole transport layer- -Optional additional hole transport layers- -Emitting layer-

[0251] -optional hole blocking layer- -electron transport layer- -electron injection layer- -cathode-,

[0252] It should be noted again that not all of the layers mentioned need to be present and / or that additional layers may be present.

[0253] 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., different 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 that instead of using multiple color-emitting emitter compounds, a single emitter compound emitting in a wide wavelength range may also be suitable for generating white light.

[0254] It is preferred that the compound of formula (I) or (II) 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.

[0255] If the device containing the compound of formula (I) or (II) 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.

[0256] If the compound according to formula (I) or (II) 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.

[0257] According to a preferred embodiment, a hole-transporting layer comprising the compound of formula (I) or (II) 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) or (II) 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%.

[0258] According to a preferred embodiment, a hole-transporting layer comprising the compound of formula (I) or (II) 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.

[0259] 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. Complexes of bismuth in oxidation state (III), in particular bismuth(III) complexes with electron-poor ligands, in particular carboxylate ligands, are also preferred.

[0260] The p-dopants are preferably distributed largely evenly throughout the p-doped layers. This can be achieved, for example, by co-evaporating 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.

[0261] Furthermore, the compounds explicitly depicted on pages 86-87 of published patent application WO2021 / 156323A1 are preferred as p-dopants. 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.

[0262] According to a preferred embodiment of embodiment b), the electron-deficient material is a hexaazatriphenylene derivative as described in US 2007 / 0092755.

[0263] The compound of formula (I) or (II) 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.

[0264] The compound of formula (I) or (II) 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 another compound.

[0265] According to an alternative preferred embodiment, the compound of formula (I) or (II) 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.

[0266] 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.%. 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.%.

[0267] 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.

[0268] It is preferred that the compounds of formula (I) or (II) 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 LUMO (wide-bandgap materials). In a mixed-matrix system, the compound of formula (I) or (II) preferably represents the matrix material with hole-transporting properties.Accordingly, when the compound of formula (I) or (II) 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.

[0269] 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) and (II), are used as a mixture and applied by evaporation.

[0270] 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.

[0271] The following material classes are preferably used in the above-mentioned layers of the device:

[0272] Phosphorescent emitters:

[0273] 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.

[0274] 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, iridium, palladium, platinum, silver, gold, or europium are used as phosphorescent emitters, in particular compounds containing iridium, platinum, or copper.

[0275] For the purposes of the present invention, all luminescent iridium, platinum, or copper complexes are considered phosphorescent compounds. In general, all phosphorescent complexes 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 are suitable for use in the devices according to the invention. Further examples of suitable phosphorescent emitters are shown in the following table:

[0276]

[0277] Fluorescent emitters:

[0278] 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 having 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:.

[0279] 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 in the sense of this invention is to be understood as a compound in which at least three aryl or arylene groups are bonded to one another.

[0280] Matrix materials for phosphorescent emitters:

[0281] Preferred matrix materials for phosphorescent emitters, in addition to the compounds of formula (I) or (II), 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.

[0282] Electron-transporting materials:

[0283] 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.

[0284] 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 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.

[0285] Preferred electron transport and electron injection materials are still the compounds explicitly shown on pages 73-75 of W02020 / 109434A1.

[0286] Hole transporting materials:

[0287] Further compounds which, in addition to the compounds of formula (I) or (II), 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.

[0288] Preferred hole-transporting compounds continue to be the compounds explicitly shown on pages 76-80 of W02020 / 109434A1.

[0289] Particularly suitable for use in layers with hole-transporting function of any OLEDs, not only the OLEDs according to the definitions of the present application, are the following compounds HT-1 to HT-14:

[0290]

[0291] Compounds HT-1 to HT-14 are generally suitable for use in hole-transporting layers. Their use is not limited to specific OLEDs, such as the OLEDs described in the present application.

[0292] Compounds HT-1 to HT-14 can be prepared according to the methods disclosed in the patent applications cited in parentheses in the above table in connection with the compounds. The further teaching regarding the use and preparation of the compounds disclosed in these patent applications is hereby explicitly incorporated and should preferably be combined with the above teaching regarding the use of the above-mentioned compound as a hole-transporting material. The compounds exhibit excellent properties when used in OLEDs, in particular excellent lifetime and efficiency.

[0293] 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 thickness of this layer is preferably between 0.5 and 5 nm.

[0294] Materials with a high work function are preferred as anodes. 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 / NiO) can also be used. x , AI / PtO x) may be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to enable either the irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive, doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of several layers, for example an inner layer made of ITO and an outer layer made of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0295] 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.

[0296] 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 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).

[0297] Further 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) or (II) are required for this purpose. High solubility can be achieved by suitable substitution of the compounds.

[0298] It is further preferred that, to produce an electronic device according to the invention, one or more layers are applied from a solution and one or more layers are applied by a sublimation process. After applying the layers, the device is structured, contacted, and finally sealed, depending on the application, to prevent damaging effects from water and air.

[0299] According to the invention, the electronic devices comprising one or more compounds according to formula (I) or (II) can be used in displays, as light sources in lighting applications and as light sources in medical and / or cosmetic applications.

[0300] Examples

[0301] A) Synthesis examples

[0302] Synthesis of 10-(4-{3-bromo-[1,1'-biphenyl]-4-yl}phenyl)-8-oxatricyclo[7.4.0.0 2 ' 7 ]trideca-1 (9), 2, 4, 6,10,12-hexaene 1 a

[0303] 24 g (83.5 mmol) (4-{8-oxatricyclo[7.4.0.0 2 - 7 [trideca-1(13),2(7),3,5,9,11-hexaen-yl}phenyl)boronic acid, 30 g (83.5 mmol) of 3-bromo-4-iodo-1,T-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: 29 g (73% of theory), purity according to GC-MS >98%. The following compounds are prepared analogously:

[0304] Synthesis of N-(4-{8-oxatricyclo[7.4.0.0 2 ' 7 ]trideca-1(13),2(7),3,5,9,11-hexaen-6-yl}phenyl)-4'-{8-oxatricyclo[7.4.0.0 2 ' 7]trideca-1(13),2,4,6,9,11- hexaen-6-yl}-N-(4-{8-oxatricyclo[7.4.0.0 2 ’ 7 ]trideca-1(13),2,4,6,9,11- hexaen-6-yl}phenyl)-4-phenyl-[1 ,1 '-biphenyl]-2-amin 2a

[0305] 4-{8-oxatricyclo[7.4.0.0 2 ' 7 ]trideca-1(13),2(7),3,5,9,11-hexaen-6-yl}-N-(4-{8- oxatricyclo[7.4.0.0 2 ’ 7 ]trideca- 1 (13), 2, 4, 6, 9, 11 -hexaen-6-yl}phenyl)anilin (37.6 g, 75 mmol), 6-(4-{3-bromo-[1 ,1'-biphenyl]-4-yl}phenyl)-8- oxatricyclo[7.4.0.0 2 ’ 7]trideca-1(13),2,4,6,9,11-hexaene (35.6 g, 75 mmol) and sodium tert-butoxide (14.7 g, 150 mmol) are dissolved in 350 mL of toluene. The solution is degassed and saturated with N2. Tri-tert-butylphosphine (7.5 mL; 7.5 mmol, 1M in xylene) and 3.4 g (3.8 mmol) of Pd2(dba)3 are then added. The reaction mixture is heated to boiling overnight under a protective atmosphere. The mixture is cooled and partitioned between toluene and water. The organic phase is washed three times with water, dried over Na2SO4, and evaporated on a rotary evaporator. After filtration of the crude product through silica gel with toluene, the remaining residue is recrystallized from toluene and finally sublimed under high vacuum. The purity is 99.9%. The yield is 23.9 g (35% of theory). The following compounds are prepared analogously:

[0306] 30

[0307]

[0308] Synthese von N-{[1,T-biphenyl]-4-yl}-2'-{8- oxatricyclo[7.4.0.0 2 ’ 7 ]trideca-1(13),2(7),3,5,9,11-hexaen-6-yl}-N-(4-{8- oxatricyclo[7.4.0.0 2 ’ 7 ]trideca-1(13),2,4,6,9,11-hexaen-6-yl}phenyl)-5'- phenyl-[1,rbiphenyl]-4-amin 3a

[0309] 26.4 g (43 mmol) N-(4-{8-oxatricyclo[7.4.0.0 2 ’ 7 ]trideca-1(13),2,4,6,9,11- hexaen-6-yl}phenyl)-N-[4-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl)phenyl]-[1 ,1'-biphenyl]-4-amine, 17.2 g (43 mmol) 6-{3-bromo-[1 ,T- biphenyl]-4-yl}-8-oxatricyclo[7.4.0.0 2 > 7]trideca-1(13),2,4,6,9,11-hexaene is 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) is added to this suspension, and the reaction mixture is 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 11 g (32% of theory). The following compounds are prepared analogously:

[0310] 30

[0311]

[0312] B) Device examples

[0313] 1 ) General manufacturing process for OLEDs and characterization of OLEDs

[0314] Glass plates coated with 50 nm thick, structured ITO (indium tin oxide) form the substrates onto which the OLEDs are applied. OLEDs generally have the following layer 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), and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of the OLEDs is shown below. The materials required to manufacture the OLEDs are shown in the table below. A fluorene derivative is used as the material "HTM" for the HIL and HTL. NDP-9 from Novaled AG, Dresden, is used as the p-dopant. An anthracene derivative is used as the material "H" for the blue-fluorescent EML.A spirobifluorene diamine is used as the material “SEB” of the blue fluorescent EML.

[0315] All materials are thermally evaporated in a vacuum chamber. The emission layer consists of at least one matrix material (host material) and an emissive dopant (emitter), which is co-evaporated into the matrix material(s) in a specific volume fraction. A specification such as H:SEB (95%:5%) means that the H material is present in the layer at a volume fraction of 95% and SEB at a volume fraction of 5%. Similarly, the electron-transport layer and the hole-injection layer also consist of a mixture of two materials.

[0316] The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, the external quantum efficiency (EQE, measured in %) as a function of luminance, calculated from current-voltage-luminance curves assuming a Lambertian radiation pattern, and the lifetime are determined. The EQE @ 10 mA / cm 2 refers to the external quantum efficiency, which at 10mA / cm 2 is reached. The lifetime LT is defined as the time after which the luminance drops from the initial luminance to a certain level when operating at a constant current density. A value of LT90 means that the specified lifetime corresponds to the time after which the luminance has dropped to 90% of its initial value. The value @80 mA / cm 2 means that the lifetime in question is 80 mA / cm 2 is measured.

[0317] 2) Use in the prime layer (EBL) of blue fluorescent OLEDs

[0318] OLEDs are manufactured with the following structure:

[0319] The following results are obtained:

[0320] The compounds according to the application show very good performance data when used as prime layer material of blue fluorescent OLEDs.

[0321] 3) Use in the prime layer (EBL) of green phosphorescent OLEDs OLEDs with the following structure are manufactured:

[0322] Eg. HIL HTL EBL EML HBL ETL EIL

[0323] Thickness / nm Thickness / nm Thickness / nm Thickness / nm Thickness / nm Thickness / nm

[0324] HTM: p-TMM-1(32%)

[0325] HTM HTM-1 HBM ETM:LiQ(50%) LiQ

[0326] 4 Dopant (3%) TMM-2(60%)

[0327] 50 nm 30 nm 5 nm 30 nm 1 nm

[0328] 10 nm TEG (8%) 35 nm

[0329] HTM: p-TMM-1(32%)

[0330] HTM HTM-2 HBM ETM:LiQ(50%) LiQ

[0331] 5 Dopant (3%) TMM-2(60%)

[0332] 50 nm 30 nm 5 nm 30 nm 1 nm

[0333] 10 nm TEG (8%) 35 nm

[0334] HTM: p-TMM-1(32%)

[0335] HTM HBM ETM:LiQ(50%) LiQ

[0336] 6 Dopant (3%) HTM-3 TMM-2 (60%)

[0337] 50 nm 5 nm 30 nm 1 nm 10 nm TEG (8%) 35 nm

[0338] The following results are obtained:

[0339] OLED data

[0340] Example: EQE (3) 10mA / cm 2 V @ 10mA / cm z LT90 (at 80mA / cm 2 )

[0341] 4 22.74 3.87 125

[0342] 5 22.91 4.10 120 6 23.22 4.33 130

[0343] The compounds according to the application show very good performance data when used as prime layer material of green phosphorescent OLEDs.

Claims

Claims 1. Compound according to one of formulas (I) and (II): where the following applies to the groups and indices: Z is equal to C if one of the freely drawn bonds is attached to it; and if no freely drawn bond is attached to it, it is chosen to be the same or different from CR for each occurrence. 1 and N; Z 1 is equal to C if the freely drawn constraint is bound to it; and if the freely drawn constraint is not bound to it, is chosen the same or different from CR for each occurrence. 1 and N; where two adjacent groups Z 1 , to which the freely drawn bond is not attached, may in one or more cases be equal to C in formula (II) and part of a unit of the following formula: where the bonds marked with * are bonds to neighboring groups Z 1in the relevant six-membered ring, which represents the two adjacent groups Z 1 contains; and Y equals O, S or NR 1 ; and Z 2 is chosen the same or differently from N and CR for each occurrence 2 ; L is chosen to be the same or different in each occurrence, consisting of a single bond, an aromatic ring system with 6 to 40 aromatic ring atoms, and R groups. 2 is substituted, and heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is coupled with R groups 2 is substituted; HetAr is chosen in each occurrence, either the same or differently, from heteroaryl groups with 5 to 20 aromatic ring atoms, which are connected to R substituents. 2 are substituted; Ar L is an aromatic ring system with 6 to 40 aromatic ring atoms, which is connected to R groups 3is substituted, or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is coupled with R groups 3 is substituted; Ar 1 In the case k=1, the number is chosen to be the same or different for each occurrence from aromatic ring systems with 6 to 40 aromatic ring atoms, which are connected to R substituents. 4 are substituted, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms, which are joined with R groups 4 are substituted; and Ar 1 In the case k=0, the number is chosen to be the same or different for each occurrence from aromatic ring systems with 6 to 40 aromatic ring atoms, which are connected to R substituents. 4 are substituted, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms, which are joined with R groups 4 are substituted, with at least one of the two Ar 1 The formula chosen is from the following formulas where: L 1is a single bond, an aromatic ring system with 6 to 40 aromatic ring atoms, which is connected to R groups 4 is substituted, or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is coupled with R groups 4 is substituted; L 2 is an aromatic ring system with 6 to 40 aromatic ring atoms, which is connected to R groups 4 is substituted, or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is coupled with R groups 4 is substituted; V is O, S or NR 4 ; R 1 is chosen the same or different from H, D, F, CI, Br, I, C(=O)R for each occurrence 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 with 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 carbon atoms, alkenyl or alkynyl groups with 2 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein two or more R groups 1 can be linked together and form a ring; wherein the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups and the aforementioned aromatic and heteroaromatic ring systems are each linked with R groups. 5 are substituted; and wherein one or more CH2 groups in the aforementioned alkyl, alkoxy, 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 may be replaced; R 2is chosen the same or different from H, D, F, CI, Br, I, C(=O)R for each occurrence 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 with 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 carbon atoms, alkenyl or alkynyl groups with 2 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein two or more R groups 2 can be linked together and form a ring; wherein the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups and the aforementioned aromatic and heteroaromatic ring systems are each linked with R groups. 5 are substituted; and wherein one or more CH2 groups in the aforementioned alkyl, alkoxy, 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 may be replaced; R 3 is chosen the same or different from H, D, F, CI, Br, I, C(=O)R for each occurrence 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 with 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 carbon atoms, alkenyl or alkynyl groups with 2 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein two or more R groups 3can be linked together and form a ring; wherein the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups and the aforementioned aromatic and heteroaromatic ring systems are each linked with R groups. 5 are substituted; and wherein one or more CH2 groups in the aforementioned alkyl, alkoxy, 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 may be replaced; R 4 is chosen the same or different from H, D, F, CI, Br, I, C(=O)R for each occurrence 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 with 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 carbon atoms, alkenyl or alkynyl groups with 2 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein two or more R groups 4 can be linked together and form a ring; wherein the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups and the aforementioned aromatic and heteroaromatic ring systems are each linked with R groups. 5 are substituted; and wherein one or more CH2 groups in the aforementioned alkyl, alkoxy, 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 may be replaced; R 5 is chosen the same or different from H, D, F, CI, Br, I, C(=O)R for each occurrence6 , 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 with 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 carbon atoms, alkenyl or alkynyl groups with 2 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein two or more R groups 5 can be linked together and form a ring; wherein the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups and the aforementioned aromatic and heteroaromatic ring systems are each linked with R groups. 6 are substituted; and wherein one or more CH2 groups in the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups are replaced 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 may be replaced; R 6 is chosen in each occurrence, either the same or different, from H, D, F, CI, Br, I, CN, alkyl or alkoxy groups with 1 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; wherein two or more R groups 6 can be linked together and form a ring; and wherein the aforementioned alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems can be substituted with one or more residues chosen from F and CN; k is 0 or 1 , where for k=0 the group Ar L is not present, and those at [Ar L]k bonded atoms are directly connected to each other; i is equal to or different from 0 or 1 in each occurrence, where at least one index i in formula (I) is equal to 1; and where at least once in formula (II) it is given that two adjacent groups Z 1 , to which the freely drawn bond is not attached, part of a unit of the above-mentioned formula (Z 1 -kond) are.

2. Compound according to claim 1, characterized in that it has the formula (IA) or (ll-A) corresponds wherein the variables appearing are defined as in claim 1 , and wherein at least one index i in formula (lA) is equal to 1.

3. Compound according to claim 1 or 2, characterized in that it corresponds to one of the formulas (1A-1 ) to (1A-3) and (12-A-1 ) to (12-A-8) wherein the variables occurring are defined as in claim 1 .

4. Compound according to one or more of claims 1 to 3, characterized in that Z is equal to C if one of the freely drawn bonds is attached to it; and equal to CR 1 is, if no freely drawn binding is attached to it; and / or that Z 1 is equal to C if the freely drawn binding is attached to it; and equal to CR 1 is, if no freely drawn constraint is attached to it; where two adjacent groups Z 1 , to which the freely drawn bond is not attached, in one or more cases in formula (II) part of a unit of formula (Z) 1 -kond) can be.

5. Compound according to one or more of claims 1 to 4, characterized in that L is a single bond.

6. Compound according to one or more of claims 1 to 5, characterized in that HetAr is selected as the same or different from groups of formulas (HetAr-1) to (HetAr-13) in each occurrence. where the bond marked with * denotes the bond to the rest of the The formula is...

7. Compound according to one or more of claims 1 to 6, characterized in that exactly one index i is equal to 1, and the other indices i are equal to 0.

8. Compound according to one or more of claims 1 to 7, characterized in that Ar L The chosen compound is phenyl, biphenyl, naphthyl, and fluorenyl, each with R groups. 3 are substituted.

9. Compound according to one or more of claims 1 to 8, characterized in that both groups Ar 1 The formulas chosen are (Ar1-1 ) to (Ar1-7).

10. Compound according to one or more of claims 1 to 9, characterized in that L 1 an aromatic ring system with 6 to 40 aromatic ring atoms, which is connected to R groups 4 is substituted, or is a heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is coupled with R groups 4 is substituted.

11. Compound according to one or more of claims 1 to 10, characterized in that it corresponds to formula (I), and k=0 and at least one Ar 1 , preferably both Ar 1 , formula (Ar1 -1 ) correspond.

12. Compound according to one or more of claims 1 to 11, characterized in that R 1 The choice is the same or different for each occurrence, from H, D, F, CN, Si(R) 5)3, straight-chain alkyl groups with 1 to 20 carbon atoms, branched or cyclic alkyl groups with 3 to 20 carbon atoms, and aromatic ring systems with 6 to 40 aromatic ring atoms, wherein the aforementioned alkyl groups and the aforementioned aromatic ring systems are each equipped with R groups 5 are substituted; and wherein in the aforementioned alkyl groups one or more CH2 groups are replaced 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 - can be replaced; and / or R 2 The choice is the same or different for each occurrence, from H, D, F, CN, Si(R) 5)3, straight-chain alkyl groups with 1 to 20 carbon atoms, branched or cyclic alkyl groups with 3 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein the aforementioned alkyl groups, the aforementioned aromatic ring systems, and the aforementioned heteroaromatic ring systems are each linked to R groups 5 are substituted; and wherein the aforementioned alkyl groups one or more CH2 groups replaced by -C=C-, -R 5 C=CR 5 -, Si(R 5 )2, C=O, C=NR 5 , -NR 5 -, -0-, -S-, -C(=O)O- or -C(=O)NR 5 - can be replaced; and / or R 3 The choice is the same or different for each occurrence, from H, D, F, CN, Si(R) 5)3, straight-chain alkyl groups with 1 to 20 carbon atoms, branched or cyclic alkyl groups with 3 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein the aforementioned alkyl groups, the aforementioned aromatic ring systems, and the aforementioned heteroaromatic ring systems are each linked to R groups 5 are substituted; and wherein in the aforementioned alkyl groups one or more CH2 groups are replaced 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 - can be replaced; and / or R 4 The choice is the same or different for each occurrence, from H, D, F, CN, Si(R) 5)3, straight-chain alkyl groups with 1 to 20 carbon atoms, branched or cyclic alkyl groups with 3 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein the aforementioned alkyl groups, the aforementioned aromatic ring systems, and the aforementioned heteroaromatic ring systems are each linked to R groups 5 are substituted; and wherein in the aforementioned alkyl groups one or more CH2 groups are replaced by -C=C-, -R 5 C=CR 5 -, Si(R 5 )2, C=O, C=NR 5 , -NR 5 -, -0-, -S-, -C(=O)O- or -C(=O)NR 5 - can be replaced; and / or R 5The group is chosen to be the same or different for each occurrence from H, D, F, CN, straight-chain alkyl groups with 1 to 20 carbon atoms, branched or cyclic alkyl groups with 3 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein the aforementioned alkyl groups, the aforementioned aromatic ring systems, and the aforementioned heteroaromatic ring systems are each linked with R groups. 6 are substituted; and wherein in the aforementioned alkyl groups one or more CH2 groups are replaced by -C=C-, -R 6 C=CR 6 -, Si(R 6 )2, C=O, C=NR 6 , -NR 6 -, -0-, -S-, -C(=O)O- or -C(=O)NR 6 - can be replaced.

13. Compound according to one or more of claims 1 to 12, characterized in that it corresponds to one of the formulas (1A-1 ) to (1A-3) as defined in claim 3, wherein the variables are combined as follows: - Z is CR 1 , if no freely drawn constraint binds it, and is C if a freely drawn constraint binds it; - L is a single bond; - HetAr is chosen from formulas (HetAr-1 ) to (HetAr-13) ; - Ar L is chosen from phenyl, biphenyl, naphthyl and fluorenyl, each with R groups 3 are substituted; - Ar 1 In the case k=1, the formula Ar is chosen to be the same or different for each occurrence. 1 -1 to Ar 1 -276; and in the case k=0 there is at least one Ar 1 selected from formulas (Ar1 -1 ) to (Ar1 -7), and the other Ar if applicable 1 is chosen from formulas Ar 1 -1 to Ar 1 -276; - R 1 is the same or different H or D in each occurrence; - R 2 is the same or different H or D in each occurrence; - R 3is the same or different H or D in each occurrence; - R 4 is chosen from H, D, F, the same or different for each occurrence, CN, Si(R 5 )3, straight-chain alkyl groups with 1 to 20 carbon atoms, branched or cyclic alkyl groups with 3 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein the aforementioned alkyl groups, the aforementioned aromatic ring systems, and the aforementioned heteroaromatic ring systems are each linked to R groups 5 are substituted; and wherein in the aforementioned alkyl groups one or more CH2 groups are replaced 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 - can be replaced; - R 5is chosen in each occurrence, either the same or different, from H, D, straight-chain alkyl groups with 1 to 20 carbon atoms, branched or cyclic alkyl groups with 3 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein the aforementioned alkyl groups, the aforementioned aromatic ring systems, and the aforementioned heteroaromatic ring systems are each linked with R groups. 6 are substituted; - R 6 is chosen in each occurrence, either the same or different, from H, D, F, CN, alkyl groups with 1 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; wherein the aforementioned alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted with one or more residues chosen from F and CN; - k= 0 or 1 ; and / or that it corresponds to one of the formulas (ll-A-1 ) to (ll-A-8), as defined in claim 3, wherein the variables are: - Z 1 is CR 1 ; - Z 2 is CR 2 ; - Y is O, S or NR 1 ; - Ar L is chosen from phenyl, biphenyl, naphthyl and fluorenyl, each with R groups 3 are substituted; - Ar 1 In the case k=1, the formula Ar is chosen to be the same or different for each occurrence. 1 -1 to Ar 1 -276; and in the case k=0, preferably also in the case k=1, there is at least one Ar 1 selected from formulas (Ar1 -1 ) to (Ar1 -7), preferably formulas (Ar1 -5) to (Ar1 -7), and the other Ar if applicable 1 is chosen from formulas Ar 1 -1 to Ar 1 -276; - R 1 is the same or different H or D in each occurrence; - R 2is the same or different H or D in each occurrence; - R 3 is the same or different H or D in each occurrence; - R 4 is chosen from H, D, F, the same or different for each occurrence, CN, Si(R 5 )3, straight-chain alkyl groups with 1 to 20 carbon atoms, branched or cyclic alkyl groups with 3 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein the aforementioned alkyl groups, the aforementioned aromatic ring systems, and the aforementioned heteroaromatic ring systems are each linked to R groups 5 are substituted; and wherein in the aforementioned alkyl groups one or more CH2 groups are replaced 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 - can be replaced; - R 5is chosen the same or differently for each occurrence from H, D, straight-chain alkyl groups with 1 to 20 C atoms, branched or cyclic alkyl groups with 3 to 20 carbon atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein the aforementioned alkyl groups, the aforementioned aromatic ring systems, and the aforementioned heteroaromatic ring systems are each equipped with R groups 6 are substituted; - R 6 is chosen in each occurrence, either the same or different, from H, D, F, CN, alkyl groups with 1 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; wherein the aforementioned alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted with one or more residues chosen from F and CN; - k= 0 or 1 .

14. Compound according to one or more of claims 1 to 13, characterized in that it corresponds to formula (II) and comprises at least one Ar 1 , preferably both Ar 1 , selected from formulas (Ar1-5) to (Ar1-7), in particular formula (Ar1-5).

15. A process for the preparation of a compound according to one or more of claims 1 to 14, characterized in that a biphenyl derivative substituted with a reactive group, which is substituted with an aryl or heteroaryl group, wherein the reactive group is in the ortho position to the aryl or heteroaryl group or to the phenyl-phenyl bond of the biphenyl, is a) reacted in a coupling reaction with a secondary amine, or b) reacted in a coupling reaction with an aromatic or heteroaromatic compound bearing a boron-containing group.

16. Oligomer, polymer or dendrimer, comprising one or more compounds according to one or more of claims 1 to 14, wherein the bond(s) to the polymer, oligomer or dendrimer are located at any point in the formulas marked with R 1 , R 2 , R 3 , or R 4 substituted positions may be located.

17. Formulation comprising at least one compound according to one or more of claims 1 to 14 or at least one polymer, oligomer or dendrimer according to claim 16, and at least one solvent.

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

19. Electronic device according to claim 18, characterized in that it is an organic electroluminescent device and includes an anode, cathode and at least one emitting layer, and that the compound is contained in a hole-transporting layer or in an emitting layer of the device.

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

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