CONNECTIONS AND ORGANIC ELECTRONIC DEVICES

Description

[0001] The present invention relates to novel organic compounds and an electronic device containing at least one of the compounds. Furthermore, the present invention relates to a method for preparing the compounds, as well as compositions and formulations containing at least one of the compounds.

[0002] The development of functional compounds for use in electronic devices is currently the subject of intensive research. The aim is, in particular, to develop compounds that can improve the properties of electroluminescent devices in one or more relevant aspects, such as power efficiency, lifetime, or the color coordinates of the emitted light.

[0003] According to the present invention, the term electronic device includes, among others, organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs).

[0004] Of particular interest is the provision of connections for use in the aforementioned electronic devices, known as OLEDs. The general structure and operating principle of OLEDs are well known to those skilled in the art and are described, among other places, in US 4539507, US 5151629, EP 0676461 and WO 1998 / 27136.

[0005] Further improvements are needed regarding the performance characteristics of OLEDs, particularly with a view to widespread commercial use, for example in display devices or as light sources. Of particular importance in this context are the lifetime, efficiency, and operating voltage of the OLEDs, as well as the achieved color values. Furthermore, it is desirable that the compounds used as functional materials in electronic devices exhibit high thermal stability and a high glass transition temperature, and that they can be sublimated without decomposition.

[0006] In this context, there is a particular need for alternative perforation materials. With state-of-the-art perforation materials, the voltage generally increases with increasing thickness of the perforation layer. In practice, a greater thickness of the perforation layer would often be desirable, but this frequently results in higher operating voltages and poorer performance. Therefore, there is a need for new perforation materials that exhibit high charge carrier mobility, enabling the use of thicker perforation layers with only a slight increase in operating voltage.

[0007] The prior art describes the use of various fluorenes as charge transport materials in electronic and electroluminescent devices.

[0008] In WO 2011 / 055493, secondary amines are disclosed which are multiplely substituted with fluorenes at position 3.

[0009] JP 2008-34701 and WO 2007 / 072952 disclose fluorenes which are substituted at position 4 with an amine group, the amine group itself containing several fluorenes.

[0010] WO 2010 / 110553 discloses fluorenes substituted with amine groups in position 2, 3 or 4, wherein the amine groups contain carbazole groups.

[0011] JP 05303221 discloses fluorenes that can be substituted with an amine group at position 2 or 4. The compounds with the amine group at position 4 of the fluorene contain phenyl groups. These compounds are used as photoreceptors.

[0012] Despite the known compounds, there remains a need for new hole transport and hole injection materials for use in OLEDs. In particular, there is a need for materials that can achieve the highly desirable improvements in the performance and properties of OLEDs mentioned above.

[0013] There is also a need for new matrix materials for use in OLEDs and other electronic devices. In particular, there is a need for matrix materials for phosphorescent dopants and for mixed-matrix systems, which preferably result in good efficiency, long lifetime, and low operating voltage of the electronic devices.

[0014] The present invention is therefore based on the objective of providing electroluminescent devices and compounds suitable for use in electroluminescent devices such as fluorescent or phosphorescent OLEDs, and which can be used in particular as hole transport materials and / or as hole injection materials in a hole transport or exciton blocking layer or as matrix material in an emitting layer.

[0015] Within the scope of the present invention, it was surprisingly found that compounds of formula (1) given below are excellently suited for the above-mentioned uses in electronic and, in particular, electroluminescent devices.

[0016] The subject of the invention is therefore a combination of the general formula (1) the following applies to the symbols and indices used: R1< is the same or different in each occurrence, preferably the same, H, D, F, Cl, Br, I, C(=O)R4<, CN, Si(R4<)3, NO2, P(=O)(R4<)2, S(=O)R4<, S(=O)2R4<, a straight-chain alkyl, alkoxy, or thioalkyl group with 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkyl group with 3 to 20 carbon atoms, or an alkenyl or alkynyl group with 2 to 20 carbon atoms, wherein the above-mentioned groups may each be substituted with one or more R4< substituents, and wherein one or more CH2 groups in the above-mentioned groups are replaced by -R4<C=CR4<-. -C≡C-, Si(R 4< ) 2 , C=O, C=S, C=NR 4< , -C(=O)O-, -C(=O)NR 4< -, P(=O)(R 4< ), -O-, -S-, SO or SO 2 may be replaced and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO 2, or an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms,which may each be substituted by one or more R 4< residues, or an aryloxy group with 5 to 60 aromatic ring atoms which may be substituted by one or more R 4< residues, or an aralkyl group with 5 to 60 aromatic ring atoms which may each be substituted by one or more R 4< residues, wherein the two R 1< residues may be linked together and may form a ring, so that a spiro compound is formed at position 9 of the fluorene, excluding spirobifluorenes; R 2< , R 3< are the same or different in each occurrence, preferably the same, H, D, F, Cl, Br, I, C(=O)R 4< , CN, Si(R 4< ) 3 , NO 2 , P(=O)(R 4< ) 2 , S(=O)R 4< , S(=O) 2 R 4< , N(R 4< ) 2 , a straight-chain alkyl, alkoxy or thioalkyl group with 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 20 C atoms or an alkenyl or alkynyl group with 2 to 20 C atoms,wherein the above-mentioned groups may each be substituted with one or more R 4< residues and wherein one or more CH 2 groups in the above-mentioned groups may be replaced by -R 4< C=CR 4< -, -C=C-, Si(R 4< ) 2 , C=O, C=S, C=NR 4< , -C(=O)O-, -C(=O)NR 4< -, P(=O)(R 4< ), -O-, -S-, SO or SO 2 and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO 2, or an aromatic ring system with 6 to 30 aromatic ring atoms, each of which may be substituted by one or more R 4< residues; R 4< is the same or different in each occurrence: H, D, F, Cl, Br, I, C(=O)R 5< , CN, Si(R 5< ) 3 , NO 2 , P(=O)(R 5< ) 2 , S(=O)R 5< , S(=O) 2 R 5< , , N(R 5< ) 2 , a straight-chain alkyl, alkoxy or thioalkyl group with 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 20 C atoms or an alkenyl or alkynyl group with 2 to 20 C atoms,wherein the above-mentioned groups may each be substituted with one or more R 5< residues and wherein one or more CH 2 groups in the above-mentioned groups may be replaced by -R 5< C=CR 5< -, -C≡C-, Si(R 5< ) 2 , C=O, C=S, C=NR 5< , -C(=O)O-, -C(=O)NR 5< -, P(=O)(R 5< ), -O-, -S-, SO or SO 2 and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO 2, or an aromatic ring system with 5 to 30 aromatic ring atoms, each of which may be substituted by one or more R 5< residues; R 5< is selected from the group consisting of H, D, F, an aliphatic hydrocarbon residue with 1 to 20 C atoms in which one or more H atoms may be replaced by D or F, wherein two or more adjacent substituents R 5< may together form a mono- or polycyclic, aliphatic, ring system; rist 1; p, q are 0; Z a< 0 ,Zb < 0 are equal or different at every occurrence; R3 < Zc < 1 is equal. B' is a single bond, an aryl group with 6 to 30 ring atoms, or a mono- or bicyclic heteroaryl group with 5 to 30 ring atoms, each of which may be substituted with one or more R4< groups, preferably a single bond or a phenylene, biphenylene, terphenylene, naphthylene, pyridinylene, pyrimidinylene, pyrazinylene, pyridazinylene, triazinylene, dibenzofuranylene, or dibenzothiophenylene group, which may be substituted with one or more R4< groups, most preferably a single bond or a phenylene, biphenylene, terphenylene, naphthylene, dibenzofuranylene, or dibenzothiophenylene group, which may be substituted with one or more R4< groups, most preferably B' is a single bond or a phenylene group substituted with one or more R4< groups R 4< can be substituted, in particular preferably B' is a single bond, wherein, if B' is a single bond, the nitrogen atom is directly bonded to the fluorene.Ar 1< , Ar 2< are selected, in each occurrence, either the same or different from the following groups of formulas (37) to (66), (69) to (72) and (76) to (96), which may be substituted with one or more residues R 6< . where the dashed line indicates the linkage position to the nitrogen atom; R 6< is the same or different in each occurrence H, D, F, Cl, Br, I, C(=O)R 5< , CN, Si(R 5< ) 3 , NO 2 , P(=O)(R 5< ) 2 , S(=O)R 5< , S(=O) 2 R 5< , a straight-chain alkyl, alkoxy or thioalkyl group with 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 20 C atoms or an alkenyl or alkynyl group with 2 to 20 C atoms, wherein the above-mentioned groups may each be substituted with one or more R 5< residues and wherein one or more CH 2 groups in the above-mentioned groups are replaced by -R 5< C=CR 5< -, -C=C-, Si(R 5< ) 2 , C=O, C=S, C=NR 5< , -C(=O)O-, -C(=O)NR 5< -, P(=O)(R 5< ), -O-, -S-, SO or SO 2 may be replaced and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO 2.

[0017] Furthermore, it is preferred in the sense of the present invention if the compound according to formula (1) does not contain any further fluorenes or carbazoles.

[0018] The counting method on the fluorene is defined as follows.

[0019] An aryl group according to this invention contains 6 to 60 aromatic ring atoms; a heteroaryl group according to this invention contains 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms are preferably selected from N, O, and S. This constitutes the basic definition. If other preferences are specified in the description of the present invention, for example, regarding the number of aromatic ring atoms or the heteroatoms included, these preferences shall apply.

[0020] In this context, an aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e., benzene, or a simple heteroaromatic cycle, for example, pyridine, pyrimidine, or thiophene, or a condensed (annelated) aromatic or heteroaromatic polycycle, for example, naphthalene, phenanthrene, quinoline, or carbazole. For the purposes of this application, a condensed (annelated) aromatic or heteroaromatic polycycle consists of two or more fused simple aromatic or heteroaromatic cycles.

[0021] An aryl or heteroaryl group, which may be substituted with any of the aforementioned residues and which may be linked via any position on the aromatic or heteroaromatic compound, is understood to include, in particular, groups derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, 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, and 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, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, Pteridine, indolizine and benzothiadiazole.

[0022] An aryloxy group, as defined in the present invention, is understood to be an aryl group, as defined above, which is bonded via an oxygen atom. An analogous definition applies to heteroaryloxy groups.

[0023] An aromatic ring system according to this invention contains 6 to 60 carbon atoms in the ring system. A heteroaromatic ring system according to this invention contains 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms are preferably selected from nitrogen, oxygen, and / or sulfur. An aromatic or heteroaromatic ring system according to this invention is understood to be a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups may also be linked by a non-aromatic unit (preferably less than 10% of the atoms other than hydrogen), such as an sp³-hybridized carbon, silicon, nitrogen, or oxygen atom, an sp²-hybridized carbon or nitrogen atom, or an sp-hybridized carbon atom. This includes systems such as 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ether, stilbene, etc.Aromatic ring systems within the meaning of this invention are understood to include systems in which two or more aryl groups are linked, for example, by a linear or cyclic alkyl, alkenyl, or alkynyl group, or by a silyl group. Furthermore, systems in which two or more aryl or heteroaryl groups are linked to one another via single bonds are also understood to be aromatic or heteroaromatic ring systems within the meaning of this invention, such as systems like biphenyl, terphenyl, or diphenyltriazine.

[0024] An aromatic or heteroaromatic ring system with 5–60 aromatic ring atoms, which may be further substituted with substituents as defined above and which may be linked via any positions on the aromatic or heteroaromatic compound, is understood to include, in particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzphenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, and indole. Isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine,Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1,2-Thiazol, 1,3-Thiazol, Benzothiazol, Pyridazin, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1,5-Diazaanthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1,6-Diazapyren, 1,8-Diazapyren, 4,5-Diazapyren, 4,5,9,10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 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 oder Kombinationen dieser Gruppen.,

[0025] Within the scope of the present invention, the following are preferably defined as a straight-chain alkyl group with 1 to 40 carbon atoms, a branched or cyclic alkyl group with 3 to 40 carbon atoms, or an alkenyl or alkynyl group with 2 to 40 carbon atoms, in which individual hydrogen atoms or CH₂ groups may also be substituted by the groups mentioned above in the definition of the residues: methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, 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.Unter einer Alkoxy- oder Thioalkylgruppe mit 1 bis 40 C-Atomen werden bevorzugt Methoxy, Trifluormethoxy, Ethoxy, n-Propoxy, i-Propoxy, n-Butoxy, i-Butoxy, s-Butoxy, t-Butoxy, n-Pentoxy, s-Pentoxy, 2-Methylbutoxy, n-Hexoxy, Cyclohexyloxy, n-Heptoxy, Cycloheptyloxy, n-Octyloxy, Cyclooctyloxy, 2-Ethylhexyloxy, Pentafluorethoxy, 2,2,2-Trifluorethoxy, Methylthio, Ethylthio, n-Propylthio, i-Propylthio, n-Butylthio, i-Butylthio, s-Butylthio, t-Butylthio, n-Pentylthio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclooctylthio, 2-Ethylhexylthio, Trifluormethylthio, Pentafluorethylthio, 2,2,2-Trifluorethylthio, Ethenylthio, Propenylthio, Butenylthio, Pentenylthio, Cyclopentenylthio, Hexenylthio, Cyclohexenylthio, Heptenylthio, Cycloheptenylthio, Octenylthio, Cyclooctenylthio, Ethinylthio, Propinylthio, Butinylthio, Pentinylthio, Hexinylthio, Heptinylthio oder Octinylthio verstanden.

[0026] It is preferred if B' in the compound according to formula (1) is a single bond.

[0027] It is further preferred if B' in the compound according to formula (1) is an o-phenylene, m-phenylene or p-phenylene group, a 1,4-naphthylene, 2,4-naphthylene, 1,5-naphthylene or 2,5-naphthylene group, a 3,7-dibenzofuranylene group or a 3,7-dibenzothiophenylene group, wherein it is most preferred if B' is an o-phenylene, m-phenylene or p-phenylene group and it is particularly preferred if B' is a p-phenylene group, wherein the groups may be substituted with one or more R 4< substituents, which may be the same or different at each occurrence, wherein it is preferred if the groups are unsubstituted.

[0028] A compound of general formula (1) is further preferred, characterized in that R1< is, in each occurrence, the same or different, preferably the same, a straight-chain alkyl or alkoxy group with 1 to 20 carbon atoms, or a branched or cyclic alkyl or alkoxy group with 3 to 20 carbon atoms, wherein the above-mentioned groups may each be substituted with one or more R4< groups, or an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, each of which may be substituted by one or more R4< groups, or an aryloxy group with 5 to 60 aromatic ring atoms, which may be substituted with one or more R4< groups, or an aralkyl group with 5 to 60 aromatic ring atoms, each of which may be substituted with one or more R4< groups, wherein the two R1< groups may be linked together and form a ring can formso that a spiro compound is formed at position 9 of the fluorene, excluding spirobifluorenes.

[0029] Furthermore, a compound of general formula (1) is most preferably characterized in that R 1< is, in each occurrence, the same or different, preferably the same, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the above-mentioned groups may each be substituted with one or more R 4< residues, or an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, each of which may be substituted by one or more R 4< residues, wherein the two R 1< residues may be linked together and may form a ring, such that a spiro compound is formed at position 9 of the fluorene, excluding spirobifluorenes.

[0030] Furthermore, a compound of general formula (1) is particularly preferred, characterized in that R 1< is, in each instance, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the above-mentioned groups may each be substituted with one or more R 4< groups, wherein it is particularly preferred if R 1< is a methyl, ethyl, n- / i-propyl or n- / i- / t-butyl group.

[0031] Finally, a compound of general formula (1) is particularly preferred, characterized in that R 1< is, in each instance, an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, which may each be substituted by one or more substituents R 4<, wherein the ring system is particularly preferably selected from the group consisting of a phenyl, biphenyl, terphenyl or pyridyl group.

[0032] A further preferred compound is of the general formula (1), characterized in that R 2< is selected, in each instance, from H, D, F, Cl, Br, I, N(R 5< ) 2 , a straight-chain alkyl, alkoxyl group with 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy group with 3 to 20 C atoms or an alkenyl or alkynyl group with 2 to 20 C atoms, wherein the above-mentioned groups may each be substituted with one or more R 4< groups and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic ring system with 6 to 30 aromatic ring atoms, each of which may be substituted by one or more R 4< groups.

[0033] Furthermore, a compound of general formula (1) is most preferably characterized in that R 2< is selected, in each occurrence, as the same or different, preferably as the same, from H, D, F, Cl, Br, I, N(R 5< ) 2 , a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the above-mentioned groups may each be substituted with one or more R 4< groups and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic ring system with 6 to 30 aromatic ring atoms, which may each be substituted by one or more R 4< groups.

[0034] In a particularly preferred embodiment, the present invention relates to a compound of the general formula (1) characterized in that R 2< is equal to H.

[0035] In a further particularly preferred embodiment, the present invention relates to a compound of the general formula (1) characterized in that R 2< is a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms.

[0036] In yet another particularly preferred embodiment, the present invention relates to a compound of general formula (1) characterized in that R 2< represents an aromatic ring system with 6 to 30 aromatic ring atoms.

[0037] A further preferred compound is of the general formula (1), characterized in that R 3< is selected in each instance as the same or different from H, D, F, Cl, Br, I, N(R 5< ) 2 , a straight-chain alkyl or alkoxy group with 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group with 3 to 20 C atoms, wherein the above-mentioned groups may each be substituted with one or more R 4< groups and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic ring system with 6 to 30 aromatic ring atoms, which may each be substituted by one or more R 4< groups.

[0038] In a preferred embodiment, the present invention relates to a compound of the general formula (5) the above definitions apply to the symbols and indices used.

[0039] In a further preferred embodiment, the present invention relates to a compound of the general formula (8) the above definitions apply to the symbols and indices used.

[0040] In a further particularly preferred embodiment, the present invention relates to a compound of the general formula (11) the above definitions apply to the symbols and indices used.

[0041] In a further particularly preferred embodiment, the present invention relates to a compound of the general formula (14) the above definitions apply to the symbols and indices used.

[0042] A further preferred combination is of the above-mentioned formulas in which B' is selected from the groups of formulas (15) to (36), wherein these groups may be further substituted by one or more independent residues R 4< and wherein R 4< is defined as above. where the dashed lines indicate the linking positions.

[0043] A combination of the above-mentioned formulas (1) to (14) in which B' is selected from the groups of formulas (15) to (36), wherein these groups are unsubstituted, is most preferred.

[0044] A combination of the above-mentioned formulas (1) to (14) in which B' corresponds to formula (15) is particularly preferred, where this group is unsubstituted.

[0045] Particularly preferred is a compound of formulas (1) to (14), characterized in that B' is a single bond, wherein the nitrogen atom is directly bonded to the fluorene via a single bond.

[0046] In a further preferred embodiment, the present invention relates to a compound of the general formula (8), wherein the symbols used are such that R 1< is the same or different in each occurrence, preferably the same, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the above-mentioned groups may each be substituted with one or more R 4< residues or an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, each of which may be substituted by one or more R 4< residues, wherein the two R 1< residues may be linked together and may form a ring, such that a spiro compound is formed at position 9 of the fluorene, excluding spirobifluorenes;R 2< equals H, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the groups may be substituted by one or more R 4< residues, an aromatic ring system with 6 to 30 aromatic ring atoms, which may be substituted by one or more R 4< residues; R 3< is equivalent to H, D, F, Cl, Br, I, a straight-chain alkyl or alkoxy group with 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group with 3 to 20 C atoms, wherein the above-mentioned groups may each be substituted with one or more R 4< residues and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO 2, or an aromatic ring system with 6 to 30 aromatic ring atoms, each of which may be substituted by one or more R 4< residues;B' is selected from H or the groups of formulas (15) to (36), wherein these groups may be further substituted by one or more independent residues R 4< and wherein R 4< is defined as above; Ar 1< , Ar 2< being the same or different in each occurrence, are a phenyl naphthyl, biphenyl, terphenyl or quarterphenyl group which may be substituted by one or more residues R 6< which may be the same or different from each other, wherein the rings in Ar 1< and in Ar 2< are unbridged rings.

[0047] In a particularly preferred embodiment, the present invention relates to a compound of the general formula (8), wherein the symbols used are such that R 1< in each occurrence the same or different, preferably the same, is a straight-chain alkyl group with 1 to 20 C atoms, wherein said group may be substituted with one or more R 4< residues or an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, each of which may be substituted by one or more R 4< residues, wherein the two R 1< residues may be linked together and may form a ring, such that a spiro compound is formed at position 9 of the fluorene, excluding spirobifluorenes; R 2< equals H, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the groups may be substituted by one or more R 4< residues, an aromatic ring system with 6 to 30 aromatic ring atoms, which may be substituted by one or more R 4< residues;R3< is equal to H or an aromatic ring system with 6 to 30 aromatic ring atoms, each of which may be substituted by one or more R4< groups, wherein R3< is equal to H is particularly preferred; B' is a single bond; Ar1<, Ar2<, whether identical or different in each occurrence, are a biphenyl, terphenyl, or quarterphenyl group, which may be substituted by one or more R6< groups, which may be identical or different from each other, wherein the rings in Ar1< and Ar2< are unbridged, Ar1< and Ar2< are particularly preferred, and Ar1< and Ar2< are a biphenyl group, which may be substituted by one or more R6< groups, which may be identical or different from each other.

[0048] In a particularly preferred embodiment, the present invention relates to a compound of the general formula (8), wherein the symbols used are such that R 1< is the same in every occurrence and is a straight-chain alkyl group with 1 to 5 C atoms, preferably a methyl group or ethyl group, wherein said group may be substituted with one or more R 4< groups or is a phenyl, biphenyl, pyridyl group, each of which may be substituted by one or more R 4< groups, wherein the two alkyl groups after R 1< may be linked together and may form a ring, such that a spiro compound is formed at position 9 of the fluorene, excluding spirobifluorenes; R 2< equals H, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the groups may be substituted by one or more R 4< residues, an aromatic ring system with 6 to 30 aromatic ring atoms, which may be substituted by one or more R 4< residues;R3< is equal to H or an aromatic ring system with 6 to 30 aromatic ring atoms, each of which may be substituted by one or more R4< groups, wherein R3< is equal to H is particularly preferred; B' is a single bond; Ar1<, Ar2<, whether identical or different in each occurrence, are a biphenyl, terphenyl, or quarterphenyl group, which may be substituted by one or more R6< groups, which may be identical or different from each other, wherein the rings in Ar1< and Ar2< are unbridged, Ar1< and Ar2< are particularly preferred, and Ar1< and Ar2< are a biphenyl group, which may be substituted by one or more R6< groups, which may be identical or different from each other.

[0049] In a particularly preferred embodiment, the present invention relates to compounds of the general formula (1) characterized in that they are monoamine compounds.

[0050] The compounds according to the invention can be synthesized using methods known to those skilled in the art. For example, they can be produced by halogenation, Buchwald coupling, and Suzuki coupling.

[0051] The following reaction scheme shows a preferred synthetic route for the preparation of the compounds of formula (1) according to the invention. For the synthesis of the compounds according to the invention, the fluorene compound A is reacted in a Buchwald coupling with an amine B of the formula Ar 1< -NH-Ar 2<. the above definitions apply to the symbols and indices used, and where X a< 0 , X b< 0 are the same or different at each occurrence, R 3< and X c< 1 are equal to -B'-Y, where Y is a leaving group, for example halogen.

[0052] Another preferred synthetic route for the preparation of the compounds according to the invention is presented in the following reaction scheme. The synthetic route comprises two coupling reactions: first, the fluorene compound is A in a first Buchwald coupling with an amine B The formula Ar 1< -NH 2 is implemented. Finally, a second Buchwald coupling takes place with a compound D, for example with a bromoaryl compound. where Y is again a leaving group, for example halogen; and where XX a< 0 , XX b< 0 equal or different at each occurrence equal to R 3< and XX c< 1 equal to -B'-NH-Ar 1< is.

[0053] The following scheme shows another preferred synthetic route for the preparation of compounds according to the invention, wherein fluorenes according to the invention, having the amine in position 1 of the fluorene, are prepared analogously. For this purpose, benzochromenones are used. Eas a starting point. The addition of an organometallic reagent, for example Grignard or organolithium reagent, and subsequent acid-catalyzed cyclization of the intermediate alcoholate leads to the corresponding 4-hydroxy fluorenes. F. The hydroxyl group is then converted into a leaving group Y or -B'-Y(=X a< 1), for example into a triflate (TfO) or a halide (preferably Br or Cl), and further reacted to give the compounds according to the invention using a method known to those skilled in the art (CC coupling such as Zusuki, Negishi, Yamamoto, Grignard-Cross, Stille, Heck coupling, etc.; CN coupling such as Buchwald coupling), wherein a Buchwald coupling or a Suzuki coupling is preferred. In the case of X a< 1, of course, only Y is the leaving group. where the indices used are defined as above and B stands for a boron atom.

[0054] This allows the synthesis of fluorenes that have the amine in the preferred position 4.

[0055] Boronic acid esters with the R groups used in Suzuki couplings are well known to experts.

[0056] Synthesis pathways for the starting compounds A, B, C, D, E The substances and compounds used in the synthesis of the compounds according to the invention are familiar to those skilled in the art. Furthermore, some explicit synthesis methods are described in detail in the exemplary embodiments.

[0057] Preferred coupling reactions for producing the compound of general formula (1) are Buchwald couplings.

[0058] Preferred compounds according to the invention are listed by way of example in the following table.

[0059] The compounds of formula (1) described above can be substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid, or boronic esters. These can be used as monomers to generate 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 terminal C-C double or C-C triple bonds, oxiranes, oxetanes, groups that undergo a cycloaddition, such as a 1,3-dipolar cycloaddition, like dienes or azides, carboxylic acid derivatives, alcohols, and silanes.

[0060] A further aspect of the invention is therefore oligomers, polymers, or dendrimers containing one or more compounds according to formula (1), wherein the bond(s) to the polymer, oligomer, or dendrimer can be located at any position possible in formula (1). Depending on the linkage of the compound according to formula (1), the compound is either a component of a side chain of the oligomer or polymer or a component of the main chain. For the purposes of this invention, an oligomer is understood to be a compound composed of at least three monomer units. For the purposes of this invention, a polymer is understood to be a compound 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 linearly linked structures, the units according to formula (1) can be directly linked to one another, or they can be linked via a bivalent group, for example, a substituted or unsubstituted alkylene group, a heteroatom, or a bivalent aromatic or heteroaromatic group. In branched and dendritic structures, for example, three or more units according to formula (1) can be linked via a trivalent or higher-valent group, for example, a trivalent or higher-valent aromatic or heteroaromatic group, to form a branched or dendritic oligomer or polymer.

[0061] The same preferences apply to the repeating units according to formula (1) in oligomers, dendrimers and polymers as described above for compounds according to formula (1).

[0062] To produce the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with further monomers. Suitable and preferred comonomers are selected from fluorenes (e.g., according to EP 842208 or WO 2000 / 22026), spirobifluorenes (e.g., according to EP 707020, EP 894107 or WO 2006 / 061181), paraphenylenes (e.g., according to WO 1992 / 18552), carbazoles (e.g., according to WO 2004 / 070772 or WO 2004 / 113468), thiophenes (e.g., according to EP 1028136), dihydrophenanthrenes (e.g., according to WO 2005 / 014689 or WO 2007 / 006383), cis- and trans-indenofluorenes (e.g., according to WO 2004 / 041901 or WO 2004 / 113412), ketones (e.g., according to WO 2005 / 040302), phenanthrenes (e.g., according to WO 2005 / 104264 or WO 2007 / 017066), or several of these units. The polymers, oligomers, and dendrimers usually contain further units, for example, emitting (fluorescent or phosphorescent) units, such as vinyltriarylamines (e.g.,according to WO 2007 / 068325) or phosphorescent metal complexes (e.g. according to WO 2006 / 003000), and / or charge transport units, in particular those based on triarylamines.

[0063] The polymers, oligomers and dendrimers according to the invention have advantageous properties, in particular long lifetimes, high efficiencies and good color coordinates.

[0064] The polymers and oligomers according to the invention are generally produced by polymerization of one or more types of monomers, at least one of which leads to repeating units of formula (1) in the polymer. Suitable polymerization reactions are known to those 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: (A) SUZUKI polymerization; (B) YAMAMOTO polymerization; (C) STILLE polymerization; and (D) HARTWIG-BUCHWALD polymerization.

[0065] 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 skilled person and is described in detail in the literature, for example in WO 2003 / 048225, WO 2004 / 037887 and WO 2004 / 037887.

[0066] The present invention therefore also relates to a process for the production of the polymers, oligomers, and dendrimers according to the invention, characterized in that they are produced by polymerization according to Suzuki, polymerization according to Yammoto, polymerization according to Stille, or polymerization according to Hartwig-Buchwald. The dendrimers according to the invention can be produced according to processes known to those skilled in the art or by analogy thereto. Suitable processes are described in the literature, such as in Frechet, Jean MJ; Hawker, Craig J., "Hyperbranched polyphenylene and hyperbranched polyesters: new soluble, three-dimensional, reactive polymers", Reactive & Functional Polymers (1995), 26(1-3), 127-36; Janssen, HM; Meijer, EW, "The synthesis and characterization of dendritic molecules", Materials Science and Technology (1999), 20 (Synthesis of Polymers), 403-458; Tomalia, Donald A., "Dendrimer molecules", Scientific American (1995), 272(5), 62-6; WO 2002 / 067343 A1 and WO 2005 / 026144 A1.

[0067] The compounds, polymers, oligomers, and dendrimers according to the invention can be used as compositions with other organically functional materials used in electronic devices. A multitude of possible organically functional materials are known to those skilled in the art. The present invention therefore also relates to a composition comprising one or more compounds of formula (1) according to the invention, or at least one polymer, oligomer, or dendrimer according to the invention, and at least one further organically functional material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole guide materials, hole injection materials, electron blocking materials, and hole blocking materials.

[0068] For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes, formulations of the compounds according to the invention are required. These formulations can be, for example, solutions, dispersions, or miniemulsions. 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, dimethylanisole, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, or mixtures of these solvents.

[0069] The invention therefore further relates to a formulation, in particular a solution, dispersion or miniemulsion, containing at least one compound according to formula (1) or at least one polymer, oligomer or dendrimer containing at least one unit according to formula (1) and at least one solvent, preferably an organic solvent. How such solutions can be prepared is known to those skilled in the art and is described, for example, in WO 2002 / 072714, WO 2003 / 019694 and the literature cited therein.

[0070] The compounds according to the invention are suitable for use in electronic devices, in particular in organic electroluminescent devices (e.g., OLEDs or OLECs). Depending on the substitution, the compounds are used in different functions and layers.

[0071] A further object of the present invention is therefore the use of the compound according to formula (1) in electronic devices, as well as electronic devices themselves which contain one or more compounds according to formula (1). The electronic devices are preferably selected from the group consisting of organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), and particularly preferably organic electroluminescent devices (OLEDs and OLECs).

[0072] The invention relates, as already explained above, to electronic devices comprising at least one compound according to formula (1). The electronic devices are preferably selected from the devices mentioned above. Organic electroluminescent devices (OLEDs) comprising an anode, a cathode, and at least one emitting layer are particularly preferred, characterized in that at least one organic layer, which may be an emitting layer, a hole transport layer, or another layer, contains at least one compound according to formula (1).

[0073] In addition to the cathode, anode, and emitting layer, the organic electroluminescent 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 (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and / or organic or inorganic p / n junctions.However, it should be noted that not every one of these layers is necessarily required and the choice of layers always depends on the compounds used and, in particular, on whether it is a fluorescent or phosphorescent electroluminescence device.

[0074] The organic electroluminescent device according to the invention can contain several emitting layers. Particularly preferably, these emission layers exhibit several emission maxima between 380 nm and 750 nm, resulting in overall white emission. This means that different emitting compounds are used in the emitting layers, which can fluoresce or phosphoresce and emit blue, yellow, orange, or red light. Three-layer systems are particularly preferred, i.e., systems with three emitting layers, wherein the three layers exhibit blue, green, and orange or red emission (for the basic structure, see, e.g., WO 2005 / 011013). The compounds according to the invention can be present in such devices in a hole transport layer, an emitting layer, and / or in another layer.It should be noted that for the generation of white light, instead of several color-emitting emitter compounds, a single emitter compound which emits in a broad wavelength range may also be suitable.

[0075] According to the invention, it is preferred if the compound according to formula (1) is used in an electroluminescent device containing one or more phosphorescent dopants. The compound can be used in different layers, preferably in a hole transport layer, a hole injection layer, or an emitting layer. However, according to the invention, the compound according to formula (1) can also be used in an electronic device containing one or more fluorescent dopants.

[0076] The term phosphorescent dopants typically encompasses compounds in which light emission occurs through a spin-forbidden transition, for example, a transition from an excited triplet state or a state with a higher spin quantum number, such as a quintet state.

[0077] Suitable phosphorescent dopants (= triplet emitters) are compounds that, upon suitable excitation, emit light, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, and particularly preferably greater than 56 and less than 80. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are preferred as phosphorescent emitters, especially those containing iridium, platinum, or copper.

[0078] For the purposes of the present invention, all luminescent iridium, platinum or copper complexes are considered to be phosphorescent compounds.

[0079] Examples of the emitters described above can be found in applications WO 00 / 70655, WO 01 / 41512, WO 02 / 02714, WO 02 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 2005 / 033244, WO 2005 / 019373 and US 2005 / 0258742. In general, all phosphorescent complexes used in phosphorescent OLEDs according to the prior art and known to those skilled in the art in the field of organic electroluminescent devices are suitable. Furthermore, those skilled in the art can use other phosphorescent complexes in combination with the compounds according to formula (1) in organic electroluminescent devices without any inventive step.

[0080] Explicit examples of suitable phosphorescent emitter compounds can be found in the following table.

[0081] In a preferred embodiment of the invention, the compounds according to general formula (1) are used as hole transport material. The compounds are then preferably used in a hole transport layer and / or in a hole injection layer. A hole injection layer within the meaning of this invention is a layer directly adjacent to the anode. A hole transport layer within the meaning of this invention is a layer located between the hole injection layer and the emission layer. The hole transport layer can be directly adjacent to the emission layer. When the compounds according to formula (1) are used as hole transport material or as hole injection material, it may be preferred that they are doped with electron acceptor compounds (p-doping), for example with F₄-TCNQ, F₆-TNAP, or with compounds as described in EP 1476881 or EP 1596445.In a further preferred embodiment of the invention, a compound according to formula (I) is used as a hole transport material in combination with a hexaazatriphenylene derivative as described in US 2007 / 0092755. The hexaazatriphenylene derivative is particularly preferably used in a separate layer.

[0082] If the compounds are used as hole transport material in a hole transport layer according to the general formula (1), the compound can be used as pure material, i.e. in a proportion of 100%, in the hole transport layer, or it can be used in combination with one or more other compounds in the hole transport layer.

[0083] In a further embodiment of the present invention, the compounds of general formula (1) are used as emitting materials. For this purpose, the compounds are preferably used in an emission layer. In addition to at least one of the compounds according to general formula (1), the emission layer also contains at least one host material. A person skilled in the art can select the host material from the known host materials without difficulty and without inventiveness.

[0084] In a further embodiment of the present invention, the compounds of general formula (1) are used as a matrix material in combination with one or more dopants, preferably phosphorescent dopants.

[0085] In a system containing a matrix material and a dopant, a dopant is understood to be the component whose proportion in the mixture is smaller. Similarly, in a system containing a matrix material and a dopant, a matrix material is understood to be the component whose proportion in the mixture is larger.

[0086] In this case, the proportion of 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 92.0 and 99.5 vol.% for fluorescent emitting layers and between 85.0 and 97.0 vol.% for phosphorescent emitting layers.

[0087] Accordingly, the proportion of the dopant is between 0.1 and 50.0 vol. %, preferably between 0.5 and 20.0 vol. %, and particularly preferably between 0.5 and 8.0 vol. %, for fluorescent emitting layers and between 3.0 and 15.0 vol. %, for phosphorescent emitting layers.

[0088] An emitting layer of an organic electroluminescent device can also contain systems comprising multiple matrix materials (mixed-matrix systems) and / or multiple dopants. In this case, too, the dopants are generally those materials with the smaller proportion in the system, and the matrix materials are those materials with the larger proportion. In some cases, however, the proportion of a single matrix material in the system may be smaller than the proportion of a single dopant.

[0089] In a further preferred embodiment of the invention, the compounds according to general formula (1) are used as a component of mixed-matrix systems. 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. However, the desired electron-transporting and hole-transporting properties of the mixed-matrix components can also be combined mainly or completely in a single mixed-matrix component, with the further mixed-matrix component(s) fulfilling other functions.The 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. Mixed-matrix systems are preferably used in phosphorescent organic electroluminescent devices. More detailed information on mixed-matrix systems is contained, inter alia, in application WO 2010 / 108579.

[0090] The mixed-matrix systems can comprise one or more dopants, preferably one or more phosphorescent dopants. In general, mixed-matrix systems are preferably used in phosphorescent organic electroluminescence devices.

[0091] Particularly suitable matrix materials, which can be used in combination with the compounds according to the invention as matrix components of a mixed matrix system, are selected from the preferred matrix materials for phosphorescent dopants or the preferred matrix materials for fluorescent dopants listed below, depending on which type of dopant is used in the mixed matrix system.

[0092] Preferred phosphorescent dopants for use in mixed matrix systems are those listed in the table above.

[0093] The following is a list of the materials preferably used in the relevant functions of the devices according to the invention.

[0094] Preferred fluorescent dopants are selected from the class of arylamines. For the purposes of this invention, an arylamine or aromatic amine is understood to be a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen atom. Preferably, at least one of these aromatic or heteroaromatic ring systems is a condensed ring system, particularly preferably with at least 14 aromatic ring atoms. Preferred examples include aromatic anthracene amines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrenediamines, aromatic chrysene amines, or aromatic chrysenediamines. An aromatic anthracene amine is understood to be a compound in which a diarylamine group is directly bonded to an anthracene group, preferably at position 9.An aromatic anthracenediamine is defined as a compound in which two diarylamine groups are directly bonded to an anthracene group, preferably at the 9,10 position. Aromatic pyrenamines, pyrendiamines, chrysenamines, and chrysendiamines are defined analogously, wherein the diarylamine groups are preferably bonded to the pyrene at the 1-position or the 1,6-position, respectively.

[0095] In addition to the compounds according to the invention, materials from various classes of substances are suitable as matrix materials, preferably for fluorescent dopants. Preferred matrix materials are selected from the classes of oligoarylenes (e.g., 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthylanthracene), in particular oligoarylenes containing fused aromatic groups, oligoarylene vinylenes (e.g., DPVBi or Spiro-DPVBi according to EP 676461), polypodal metal complexes (e.g., according to WO 2004 / 081017), hole-conducting compounds (e.g., according to WO 2004 / 058911), electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (e.g., according to WO 2005 / 084081 and WO 2005 / 084082), and atropisomers (e.g., according to WO 2006 / 048268), the boronic acid derivatives (e.g. according to WO 2006 / 117052) or the benzanthracenes (e.g. according to WO 2008 / 145239).Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, oligoarylene vinylenes, ketones, phosphine oxides, and sulfoxides. Most particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzphenanthrene and / or pyrene or atropisomers of these compounds. For the purposes of this invention, an oligoarylene is understood to be a compound in which at least three aryl groups are bonded together.

[0096] Preferred matrix materials for phosphorescent dopants, besides the compounds according to the invention, are aromatic amines, in particular triarylamines, e.g. according to US 2005 / 0069729, carbazole derivatives (e.g. CBP, N,N-biscarbazolylbiphenyl) or compounds according to WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851, bridged carbazole derivatives, e.g. according to WO 2011 / 088877 and WO 2011 / 128017, indenocarbazole derivatives, e.g. according to WO 2010 / 136109 and WO 2011 / 000455, azacarbazole derivatives, e.g. B. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, indolocarbazole derivatives, e.g. according to WO 2007 / 063754 or WO 2008 / 056746, ketones, e.g. according to WO 2004 / 093207 or WO 2010 / 006680, phosphine oxides, sulfoxides and sulfones, e.g. according to WO 2005 / 003253, oligophenylenes, bipolar matrix materials, e.g. according to WO 2007 / 137725, silanes, e.g. according to WO 2005 / 111172, azaboroles or boron esters, e.g. B. according to WO 2006 / 117052, triazine derivatives, e.g. b.according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, aluminium complexes, e.g. BAlq, diazasilol and tetraazasilol derivatives, e.g. according to WO 2010 / 054729, diazaphosphol derivatives, e.g. according to WO 2010 / 054730 and aluminium complexes, e.g. BAIQ.

[0097] Suitable charge transport materials, such as those that can be used in the hole injection or hole transport layer or in the electron transport layer of the organic electroluminescence device according to the invention, are, in addition to the compounds according to the invention, for example the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010 or other materials such as are used in these layers according to the prior art.

[0098] Metals with low work functions, metal alloys, or multilayer structures of different metals are preferred as cathodes for organic electroluminescence devices. These include alkaline earth metals, alkali metals, main group metals, and lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys of an alkali or alkaline earth metal and silver are also suitable, for example, a magnesium-silver alloy. In multilayer structures, additional metals with relatively high work functions, such as Ag or Al, can be used, typically in combinations of these metals, such as Ca / Ag, Mg / Ag, or Ba / Ag. It may also be advantageous to insert a thin interlayer 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.

[0099] Materials with a high work function are preferred as anodes. Preferably, the anode 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. Alternatively, metal / metal oxide electrodes (e.g., Al / Ni / NiO₂, Al / PtO₂) may also be preferred. For some applications, at least one of the electrodes must be transparent or semi-transparent to allow either the irradiation of the organic material (organic solar cell) or the extraction of light (OLED, O-LASER). Conductive mixed metal oxides are preferred anode materials in this case. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Conductive doped organic materials, especially conductive doped polymers, are also preferred.

[0100] The device is structured, contacted and finally sealed accordingly (depending on the application), since the service life of the devices according to the invention is reduced in the presence of water and / or air.

[0101] In a preferred embodiment, the organic electroluminescent device according to the invention is characterized in that one or more layers are coated using a sublimation process. The materials are deposited in vacuum sublimation systems at an initial pressure of less than 10⁻⁵ mbar, preferably less than 10⁻⁶ mbar. However, it is also possible for the initial pressure to be even lower, for example less than 10⁻⁷ mbar.

[0102] A preferred method is also an organic electroluminescence device, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are applied at a pressure between 10⁻⁵ mbar and 1 bar. A special case of this method 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).

[0103] A further preferred organic electroluminescent device is characterized in that one or more layers are produced from solution, e.g., by spin coating, or by any printing process, e.g., 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 (1) are required for this purpose. High solubility can be achieved by suitable substitution of the compounds.

[0104] It is further preferred that, to produce an organic electroluminescence device according to the invention, one or more layers of solution and one or more layers are applied by a sublimation process.

[0105] According to the invention, the electronic devices containing one or more connections according to the general formula (1) can be used in displays, as light sources in lighting applications, and as light sources in medical and / or cosmetic applications (e.g., light therapy).

[0106] Devices containing the compounds of general formula (1) can be used in a wide variety of applications. For example, electroluminescent devices containing one or more compounds of general formula (1) can be used in displays for televisions, mobile phones, computers, and cameras. These devices can also be used in lighting applications. Furthermore, electroluminescent devices, such as those found in OLEDs or OLECs, containing at least one compound of general formula (1), can be used in medicine or cosmetics for phototherapy. This allows for the treatment of a variety of diseases (psoriasis, atopic dermatitis, inflammation, acne, skin cancer, etc.) or the prevention and reduction of wrinkles, redness, and skin aging. Additionally, these light-emitting devices can be used to keep beverages, food, or other food products fresh, or to illuminate devices (e.g., refrigerators, refrigerators, refrigerators, etc.).to sterilize medical devices).

[0107] The compounds or organic electroluminescence devices according to the invention are characterized by the following surprising advantages over the prior art: 1. The compounds according to the invention are very well suited for use in a hole transport layer or a hole injection layer in electronic devices, such as organic electroluminescent devices, particularly due to their high hole mobility. 2. The compounds according to the invention exhibit a relatively low sublimation temperature, high temperature stability, high oxidation stability, and a high glass transition temperature, which is advantageous both for processability, for example, from solution or from the gas phase, and for use in electronic devices. 3. The use of the compounds according to the invention in electronic devices, particularly as hole transport or hole injection material, leads to high efficiencies, low operating voltages, and long lifetimes.

[0108] It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Unless explicitly excluded, each feature disclosed in the present invention may be replaced by alternative features serving the same, an equivalent, or a similar purpose. Thus, unless otherwise stated, each feature disclosed in the present invention is to be considered as an example of a generic series or as an equivalent or similar feature.

[0109] All features of the present invention can be combined with one another in any way, unless certain features and / or steps are mutually exclusive. This applies in particular to preferred features of the present invention. Likewise, features of non-essential combinations can be used separately (and not in combination).

[0110] It should further be noted that many of the features, and in particular those of the preferred embodiments of the present invention, are themselves inventive and not merely to be considered part of the embodiments of the present invention. Independent protection for these features may be sought in addition to or as an alternative to any currently claimed invention.

[0111] The teaching on technical action disclosed in the present invention can be abstracted and combined with other examples.

[0112] The invention is further explained by the following examples, without thereby limiting it. Examples materials

[0113] * not according to the invention

[0114] The materials HIL1, HIL2 (EP 0676461), H1 (WO 2008 / 145239), H2 (WO 2010 / 136109), ETM1 (WO 2005 / 053055), SEB1 (WO 2008 / 006449), LiQ, Irpy, and NPB are well known to those skilled in the art. The compounds HTMV1 to HTMV6 are comparable compounds that can be produced analogously to the method described in Example 1. (9-2), (2-7) and (2-10) are according to the invention. Example 1 Synthesis of the compound bis-biphenyl-4-yl-(9,9-diphenyl-9H-fluoren-4-yl)-amine (1-1) and of compounds (1-2) to (1-12)

[0115] 4-Bromo-9,9-diphenyl-9H-fluorene

[0116] 37 g (152 mmol) of 2,2'-dibromobiphenyl are dissolved in 300 mL of dried THF in a heated flask. The reaction mixture is cooled to -78°C. At this temperature, 75 mL of a 15% solution of n-BuLi in hexane (119 mmol) are slowly added dropwise (duration: approx. 1 hour). The mixture is stirred for 1 hour at -70°C. Subsequently, 21.8 g of benzophenone (119 mmol) are dissolved in 100 mL of THF and added dropwise at -70°C. After the addition is complete, the reaction mixture is slowly warmed to room temperature, quenched with NH₄Cl, and then concentrated using a rotary evaporator. The concentrated solution is carefully treated with 510 mL of acetic acid, followed by the addition of 100 mL of fuming HCl. The mixture is heated to 75°C and held at this temperature for 4 hours. A white solid precipitates out. The mixture is then cooled to room temperature, the precipitated solid is filtered off, and the mixture is washed with methanol. The residue is dried under vacuum at 40°C.The yield is 33.2 g (83 mmol) (70% of the theory).

[0117] Similarly, the following brominated compounds are produced: Reagent 1 Reagent 2 product yield 78% 70% 82% 85% 80% 85% 77% Bis-biphenyl-4-yl-(9,9-diphenyl-9H-fluoren-4-yl)amine (1-1)

[0118] 17 g of bis-biphenyl-4-ylamine (53 mmol) and 23.1 g of 4-bromo-9,9-diphenyl-9H-fluorene (58 mmol) are dissolved in 500 mL of toluene. The solution is degassed and saturated with nitrogen. It is then treated with 5.3 mL (5.3 mmol) of a 1 M tri-tert-butylphosphine solution and 0.6 g (2.65 mmol) of palladium(II) acetate. Subsequently, 12.7 g of sodium tert-butoxide (132.23 mmol) are added. The reaction mixture is heated to boiling for 3 h under a protective atmosphere. The mixture is then separated between toluene and water, the organic phase is washed three times with water, dried over sodium 2SO4, and rotated. After filtration of the crude product through silica gel with toluene, the remaining heptane / toluene residue is recrystallized and finally sublimed under high vacuum. The purity is 99.9%. The yield is 29 g (87% of theory).

[0119] Similarly, the following connections (1-2) until (1-17) manufactured. Reagent 1 Reagent 2 product yield 78 % 83% 92% 88% 77% 75% 80% 77% 71% 70% 75% 77% 75% 85% 79% 72% Example 2 Synthesis of the compound biphenyl-3-yl-biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-3-yl)-amine (2-1) and of compounds (2-2) to (2-10)

[0120] 3-Bromo-9,9-dimethyl-9H-fluorene

[0121] 29.5 g (120 mmol) of 3-bromo-9H-fluorene (Tetrahedron Letters, 51, 37, 4894-4897; 2010) are dissolved in 220 mL of dried DMSO in a heated flask. At room temperature, 34.7 g (361 mmol) of NaO t< Bu is added. The suspension is brought to an internal temperature of 65°C. At this temperature, a solution of 22.5 mL (361 mmol) of iodomethane in DMSO (50 mL) is added dropwise, ensuring that the internal temperature does not exceed 65°C (duration: approx. 30 min). The mixture is maintained at an internal temperature of 65°C for a further 30 min, and then poured onto 400 mL of an ice-cold aqueous NH₄OH solution (1:1, v / v) and stirred for approx. 20 min. The precipitated solid is filtered off and washed successively with approx. 200 mL of H₂O and methanol. Yield: 31 g (114 mmol) (95% of theory).

[0122] Similarly, the following brominated compounds are produced: Reagent 1 Reagent 2 product yield H3CI 78 % 85%

[0123] Biphenyl-3-yl-biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-3-yl)amine (2-1)30 g of biphenyl-3-yl-biphenyl-4-ylamine (93.4 mmol) and 25.5 g of 3-bromo-9,9-dimethyl-9H-fluorene (93.4 mol) are dissolved in 600 mL of toluene. The solution is degassed and saturated with nitrogen. It is then treated with 3.2 g (3.73 mmol) of tri-tert-butylphosphine and 0.42 g (1.87 mmol) of palladium(II) acetate. Subsequently, 13.9 g of sodium tert-butoxide (140 mmol) are added. The reaction mixture is heated to boiling for 5 h under a protective atmosphere. The mixture is then separated between toluene and water, the organic phase is washed three times with water, dried over sodium 2SO4, and rotated. After filtration of the crude product over silica gel with toluene, the remaining heptane / toluene residue is recrystallized and finally sublimed under high vacuum; purity is 99.9%. The yield is 37.8 g (79% of theory).

[0124] Similarly, the following connections ( 2-2 ) until ( 2-10 ) manufactured: Reagent 1 Reagent 2 product yield 78 % 82% 80% 92% 75% 67% 73% 70% 66% Example 3 Synthesis of the compound biphenyl-2-yl-biphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)-amine (3-1) and of compounds (3-2) to (3-5)

[0125] 3-Bromo-9,9-diphenyl-9H-fluorene

[0126] 50 g (193 mmol) of 3-bromo-9H-fluorenone (tetrahedron, 51.7, 2039-54; 1995) are dissolved in 500 mL of dried THF in a heated flask. The clear solution is cooled to -10°C, and then 70.7 mL (212 mmol) of a 3 M phenylmagnesium bromide solution are added. The reaction mixture is slowly heated to room temperature and then quenched with 500 mL of NH₄Cl. The mixture is then separated between ethyl acetate and water, the organic phase is washed three times with water, dried over Na₂SO₄, and rotated. The crude product is recrystallized from heptane / toluene. The residue is treated with 400 mL of benzene. The mixture is heated to 50°C, and then 18.6 mL of trifluoromethanesulfonic acid are added dropwise. After 30 minutes, the reaction mixture is cooled to room temperature and poured onto 1 L of water. The mixture is dispersed between toluene and water, the organic phase is washed three times with water, dried over Na₂SO₄, and rotated.After filtration of the crude product over silica gel with (heptane:acetic esters, 1:1) 55.6 g (135 mmol) (70% of the theory) is obtained.

[0127] Similarly, the following brominated compounds are produced: Reagent 1 Reagent 2 Reagent 3 product yield 75% 65%

[0128] Biphenyl-2-yl-biphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)amine (3-1)12 g of biphenyl-2-yl-biphenyl-4-yl-amine (37 mmol) and 16.3 g of 3-bromo-9,9-diphenyl-9H-fluorene (41 mol) are dissolved in 360 mL of toluene. The solution is degassed and saturated with nitrogen. It is then treated with 3.7 mL (3.7 mmol) of a 1 M solution of tri-tert-butylphosphine and 0.42 g (1.87 mmol) of palladium(II) acetate. Subsequently, 9.0 g of sodium tert-butoxide (93.3 mmol) are added. The reaction mixture is heated to boiling for 3 h under a protective atmosphere. The mixture is then separated between toluene and water, the organic phase is washed three times with water, dried over sodium 2SO4, and rotated. After filtration of the crude product through silica gel with toluene, the remaining heptane / toluene residue is recrystallized and finally sublimed under high vacuum; purity is 99.9%. The yield is 20 g (85% of theory).

[0129] Similarly, the following connections ( 3-2 ) until ( 3-5 ) manufactured: Reagent 1 Reagent 2 product yield 78% 80% 85% 80% Example 4 Synthesis of the compound bis-biphenyl-4-yl-[4-(9,9-diphenyl-9H-fluoren-4-yl)-phenyl]amine (4-1) and of compounds (4-2) to (4-7)

[0130] 4-(4-Chloro-phenyl)-9,9-diphenyl-9H-fluorene

[0131] 7.9 g (50 mmol) of 4-chlorobenzeneboronic acid, 20 g (50 mmol) of 4-bromo-9,9-diphenyl-9H-fluorene, and 55 mL of an aqueous 2 M NaHCO₃ solution (111 mmol) are suspended in 400 mL of dimethoxyethane. 1.45 g (1.26 mmol) of tetrakis(triphenyl)phosphine palladium(0) are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated, filtered over silica gel, washed three times with 300 mL of water, and then concentrated to dryness. After filtration of the crude product over silica gel with heptane / acetic acid ester (20:1) 18.4 g (85%) of 4-(4-chlorophenyl)-9,9-diphenyl-9H-fluorene is obtained.

[0132] Similarly, the following chlorinated compounds are produced: Reagent 1 Reagent 2 product yield 79% 70% 72%

[0133] Bis-biphenyl-4-yl-[4-(9,9-diphenyl-9H-fluoren-4-yl)phenyl]amine (4-1) 13.60 g of bis-biphenyl-4-ylamine (43 mmol) and 18.2 g of 4-chloro-9,9-diphenyl-9H-fluorene (43 mmol) are dissolved in 400 mL of toluene. The solution is degassed and saturated with nitrogen. It is then treated with 1.04 g (2.55 mmol) of Sphosylene and 1.94 g (2.1307 mmol) of palladium(II) dba. Subsequently, 10 g of sodium tert-butoxide (106 mmol) are added. The reaction mixture is heated to boiling for 3 h under a protective atmosphere. The mixture is then dispersed between toluene and water, the organic phase is washed three times with water, dried over Na₂SO₄, and rotated. After filtration of the crude product through silica gel with toluene, the remaining heptane / toluene residue is recrystallized and finally sublimed under high vacuum. The purity is 99.9%. The yield is 23 g (77% of the theoretical value).

[0134] Similarly, the following connections are established: Reagent 1 Reagent 2 product yield 78% 70% 75% 88% 73% 73% Example 5 Synthesis of the compound bis-biphenyl-4-yl-[9,9-dimethyl-1-(9-phenyl-9H-carbazol-3-yl)-9H-fluoren-4-yl]-amine (5-1) and of compounds (5-2) to (5-5)

[0135]

[0136] Bis-biphenyl-4-yl-(1-bromo-9,9-dimethyl-9H-fluoren-4-yl)amine 15.0 g (29 mmol) of bis-biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-4-yl)-amines are dissolved in 150 mL of acetonitrile and, at room temperature, 5.2 g (29 mmol) of N-bromsuccinimide are added portionwise. After complete reaction, water and ethyl acetate are added, the organic phase is separated, dried, and concentrated. The crude product is then stirred several times while hot with MeOH / heptane (1:1). Yield: 13.5 g (80%) of the product.

[0137] Similarly, the following brominated compounds are produced: Reagent 1 product yield 85% 81% Bis-biphenyl-4-yl-[9,9-dimethyl-1-(9-phenyl-9H-carbazol-3-yl)-9H-fluoren-4-yl]amine (5-1)

[0138] 6.3 g (22 mmol) of N-phenylcarbazol-3ylboronic acid and 13 g (22 mmol) of bis-biphenyl-4-yl-(1-bromo-9,9-dimethyl-9H-fluoren-4-yl)amines are suspended in 200 mL of dimethoxyethane and 30 mL of 2 M Na₂CO₃ solution. 0.6 g (2.0 mmol) of palladium tetrakis(triphenylphosphine) is added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the reaction mixture is diluted with ethyl acetate, the organic phase is removed, the mixture is washed three times with 100 mL of water, and then concentrated to dryness. Filtration of the crude product over silica gel with heptane / acetic acid ester (20:1) yields 15 g (90%) of bis-biphenyl-4-yl-[9,9-dimethyl-1-(9-phenyl-9H-carbazol-3-yl)-9H-fluoren-4-yl]-amine ( 5-1 ).

[0139] Similarly, the connections ( 5-2 ) until ( 5-5 ) manufactured: Reagent 1 Reagent 2 product yield 85% 81% 88% 85% Example 6 Synthesis of the compound biphenyl-4-yl-(4-dibenzofuran-4-yl-phenyl)-[4-(9,9-diphenyl-9H-fluoren-4-yl)-phenyl]-amine (7-1) and of compounds (6-2) to (6-5)

[0140] Biphenyl-4-yl-(4-chloro-phenyl)-(4-dibenzofuran-4-yl-phenyl)-amine

[0141] 30.0 g of biphenyl-4-yl-(4-dibenzofuran-4-yl-phenyl)amine (CAS: 955959-89-4) (73 mmol) and 17.4 g of 1-chloro-2-iodobenzene (73 mmol) are dissolved in 460 mL of toluene. The solution is degassed and saturated with nitrogen. It is then treated with 2.9 mL (2.9 mmol) of a 1 M tri-tert-butylphosphine solution and 0.33 g (1.46 mmol) of palladium(II) acetate. Subsequently, 10.5 g of sodium tert-butoxide (109 mmol) are added. The reaction mixture is heated to boiling for 3 h under a protective atmosphere. The mixture is then separated between toluene and water, the organic phase is washed three times with water, dried over sodium 2SO4, and rotated. After filtration of the crude product through silica gel with toluene, the remaining heptane / toluene residue is recrystallized and finally sublimed under high vacuum. The purity is 99.9%. The yield is 30 g (80% of theory).

[0142] Similarly, the following connections are established: Reagent 1 Reagent 2 product yield 83% 80% 79% Biphenyl-4-yl-(4-dibenzofuran-4-yl-phenyl)-[4-(9,9-diphenyl-9H-fluoren-4-yl)-phenyl]-amine (6-1)

[0143] 20.0 g (45 mmol) of (9,9-diphenyl-9H-fluoren-4-yl)-pinacolboron ester and 23.5 g (45 mmol) of biphenyl-4-yl-(4-chlorophenyl)-(4-dibenzofuran-4-yl-phenyl)-amine are suspended in 400 mL of dioxane and 13.7 g (90 mmol) of cesium fluoride. 4.0 g (5.4 mmol) of palladium dichloride bis(tricyclohexylphosphine) are added to this suspension, and the reaction mixture is heated under reflux for 18 h. After cooling, the organic phase is separated, filtered over silica gel, washed three times with 80 mL of water, and then concentrated to dryness. After filtration of the crude product over silica gel with toluene, the remaining heptane / toluene residue is recrystallized and finally sublimed under high vacuum; purity is 99.9%. The yield is 25 g (80% of theory).

[0144] Similarly, the following compounds (6-2) to (6-5) are made: Reagent 1 Reagent 2 product yield 65% 69% 75% 65% Example 7 Synthesis of the compound bis-biphenyl-4-yl-(7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-yl)-amine (7-1) and of compounds (7-2) to (7-5)

[0145] 8-Dibenzofuran-4-yl-benzo[c]chromen-6-one

[0146] 30.0 g (142 mmol) of dibenzofuran-4-boronic acid, 32 g (142 mmol) of 8-chlorobenzo[c]chromen-6-one (CAS: 742058-81-7), and 43 g (283 mmol) of cesium fluoride are suspended in 800 mL of dioxane. To this suspension, 12.5 g (17 mmol) of palladium dichloride bis(tricyclohexylphosphine) are added, 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 100 mL of water, and then concentrated to dryness. After filtration of the crude product through silica gel with toluene, the remaining residue is recrystallized from heptane / toluene. The yield is 45 g (88% of theory).

[0147] Similarly, the following connections are established: Reagent 1 Reagent 2 product yield 84% 90% 85% 76% 7-Dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-ol

[0148] 25.4 g (70 mmol) of 8-dibenzofuran-4-yl-benzo[c]chromen-6-one are dissolved in 340 mL of dried THF in a heated flask. The solution is saturated with N₂. The clear solution is cooled to -10°C, and then 70 mL (210 mmol) of a 3M phenylmagnesium bromide solution are added. The reaction mixture is slowly heated to room temperature and then quenched with acetic anhidrite (70 mmol). The mixture is then dispersed between ethyl acetate and water, the organic phase is washed three times with water, dried over Na₂SO₄, and rotated. The rotated solution is carefully treated with 310 mL of acetic acid, followed by the addition of 70 mL of fuming HCl. The mixture is heated to 75°C and held at this temperature for 4 h. A white solid precipitates. The mixture is then cooled to room temperature, the precipitated solid is filtered off, and the mixture is washed with methanol. The residue is dried under vacuum at 40°C.After filtration of the crude product over silica gel with (heptane:acetic esters, 1:1) 26 g are obtained (75% of the theory).

[0149] Similarly, the following brominated compounds are produced: Reagent 1 Reagent 2 product yield 72% 80% 77% CH 3 MgBr 72% Bis-biphenyl-4-yl-(7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-yl)amine (7-1)

[0150] 25 g (50 mmol) of 7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-ol are dissolved in 300 mL of dried THF in a heated flask. The solution is saturated with N₂. The clear solution is cooled to 5°C, and then 20 mL (150 mmol) of triethylamine, 122 mg of 4-dimethylaminopyridines, and 8.65 mL of trifluoromethanesulfonic anhydride are added. The reaction mixture is slowly warmed to room temperature. The reaction mixture is then diluted with heptane, rotated, and water is distributed. The organic phase is washed three times with water, dried over Na₂SO₄, and rotated. After filtration of the crude product through silica gel with a heptane:ethyl acetate solution (1:1), 30 g (98% of theory) are obtained.

[0151] 18.9 g of the triflate (30 mmol) and 8.16 g of bis-4-biphenylamine (25 mmol) are dissolved in 240 mL of toluene. The solution is degassed and saturated with nitrogen. It is then treated with 0.74 g (1.79 mmol) of Sphos and 1.36 g of palladium-dba (1.49 mmol). Subsequently, 5.7 g of sodium tert-butoxide (59.7 mmol) are added. The reaction mixture is heated to 85°C for 3 h under a protective atmosphere. The mixture is then dispersed between toluene and water, the organic phase is washed three times with water, dried over Na₂SO₄, and rotated. After filtration of the crude product through silica gel with toluene, the remaining heptane / toluene residue is recrystallized. The purity is 99.9%. The yield is 15 g (65% of theory).

[0152] Similarly, the following connections are established: Reagent 1 Reagent 2 product yield 73% 80% 69% 75% Example 8 Synthesis of the compound N*2*,N*5*,N*5*-Tris-biphenyl-4-yl-N*2*-biphenyl-2-yl-9,9-diphenyl-9H-fluorene-2,5-diamine (8-1)

[0153] 8-(Biphenyl-4-yl-biphenyl-2-yl-amino)-benzo[c]chromen-6-one

[0154] 19.0 g of biphenyl-2-yl-biphenyl-4-ylamine (59 mmol) and 16.3 g of 8-bromobenzo[c]chromen-6-one (59 mmol) are dissolved in 400 mL of toluene. The solution is degassed and saturated with nitrogen. It is then treated with 2.36 mL (2.36 mmol) of a 1 M tri-tert-butylphosphine solution and 0.27 g (1.18 mmol) of palladium(II) acetate. Subsequently, 11.6 g of sodium tert-butoxide (109 mmol) are added. The reaction mixture is heated to boiling for 3 h under a protective atmosphere. The mixture is then separated between toluene and water, the organic phase is washed three times with water, dried over sodium 2SO4, and rotated. After filtration of the crude product through silica gel with toluene, the remaining residue is heptane / toluene. The yield is 27 g (90% of theory).

[0155] Similarly, the following connections are established: Reagent 1 Reagent 2 product yield 85% 75% 7-(Biphenyl-4-yl-biphenyl-2-yl-amino)-9,9-diphenyl-9H-fluoren-4-ol

[0156] Analogous to 7-Dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-ol, the following compounds are prepared: Reagent 1 Reagent 2 product yield 88% 73% CH 3 MgBr 76% N*2*,N*5*,N*5*-Tris-biphenyl-4-yl-N*2*-biphenyl-2-yl-9,9-diphenyl-9H- fluorene-2,5-diamine (8-1)

[0157] Analogous to bis-biphenyl-4-yl-(7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-yl)-amine compound (7-1), compound (8-1) is prepared: Example 9 Synthesis of the compound bis-biphenyl-4-yl-(4-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-1-yl)-amine (9-1) and of compounds (9-2) and (9-3)

[0158] Reagent 1 Reagent 2 product yield 74%

[0159] 24.4 g (37 mmol) of 1-(Bis-biphenyl-4-yl-amino)-9,9-diphenyl-9H-fluoren-4-ol are dissolved in 210 mL of dried THF in a heated flask. The solution is saturated with N₂. The clear solution is cooled to 5°C, and then 15.5 mL (112 mmol) of triethylamine, 100 mg of 4-dimethylaminopyridine, and 6.45 mL of trifluoromethanesulfonic anhydride are added. The reaction mixture is slowly warmed to room temperature. The reaction mixture is then diluted with heptane, rotated, and water is distributed. The organic phase is washed three times with water, dried over Na₂SO₄, and rotated. After filtration of the crude product through silica gel with a heptane:ethyl acetate solution (1:1), 26.7 g (91% of theory) are obtained.

[0160] 17.2 g (22 mmol) of 1-(Bis-biphenyl-4-yl-amino)-9,9-diphenyl-9H-fluoren-4-ol, 6.9 g (33 mmol) of 4-bibenzofuranboronic acid, 9.0 g of sodium metaborate octahydrate (32.9 mmol), and 0.03 mL of hydrazinium hydroxide (0.657 mmol) are suspended in 200 mL of THF. To this suspension, 0.3 g (0.44 mmol) of palladium dichloride bis(triphenylphosphine) is added, and the reaction mixture is heated to 70°C for 18 h. After cooling, the mixture is separated between ethyl acetate and water, the organic phase is washed three times with water, dried over 4 g of Na₂SO₄, and then concentrated to dryness. After filtration of the crude product over silica gel with toluene, the remaining heptane / toluene residue is recrystallized and then sublimed. The yield is 12 g (70% of theory).

[0161] Similarly, the following connections are established: Reagent 1 Reagent 2 product yield 74% 73% 76% Example 10 Characterization of the compounds

[0162] The production of OLEDs according to the invention as well as OLEDs according to the prior art is carried out according to a general method according to WO 04 / 058911, which is adapted to the conditions described here (layer thickness variation, materials).

[0163] The following examples V1 to V13 and E1 to E43 (see Tables 1, 3 and 2, 4) present the data for various OLEDs. Glass platelets coated with 50 nm thick structured ITO (indium tin oxide) are used as substrates. The OLEDs have the following layer structure: substrate / optional hole injection layer (HIL1) / hole transport layer (HTL) / hole injection layer (HIL2) / electron blocking layer (EBL) / emission layer (EML) / electron transport layer (ETL) / optional 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 can be found in Tables 1 and 3. The materials required for the fabrication of the OLEDs are disclosed above.

[0164] All materials are thermally vapor-deposited in a vacuum chamber. The emission layer always consists of at least one matrix material (host material) and an emitting dopant, which is added to the matrix material(s) by cover vapor deposition in a specific volume fraction. A specification such as H1:SEB1 (95%:5%) means that material H1 is present in the layer at a volume fraction of 95% and SEB1 at a volume fraction of 5%. Similarly, the electron transport layer can also consist of a mixture of two materials.

[0165] The OLEDs are characterized according to standard procedures. This includes determining the electroluminescence spectra, current efficiency (measured in cd / A), power efficiency (measured in imp / W), and external quantum efficiency (EQE, measured in percent) as a function of luminance, calculated from current-voltage-luminance curves (IUL curves) assuming a Lambertian emission characteristic, as well as the lifetime. The electroluminescence spectra are determined at a luminance of <1000 cd / m², and the CIE 1931 x and y color coordinates are calculated from them. The specification EQE @ 1000 cd / m²< denotes the external quantum efficiency at an operating luminance of <1000 cd / m². LD80 @ 6000 cd / m²< is the lifetime until the OLED, at a brightness of 6000 cd / m²<, has decreased to 80% of its initial intensity, i.e., to 4800 cd / m²<. The data for the various OLEDs are summarized in Tables 2 and 4. Use of compounds according to the invention as hole transport materials in OLEDs

[0166] In particular, compounds according to the invention are suitable as HIL, HTL or EBL in OLEDs. They are suitable as a single layer, but also as a mixed component as HIL, HTL, EBL or within the EML.

[0167] Compared with NPB reference components (V1, V8), the samples with the compounds according to the invention show both higher efficiencies and significantly improved lifetimes in both singlet blue and triplet green.

[0168] In comparison to the reference material HTMV1 (V2, V9), the compound according to the invention ( 1-1 ) (E1, E7) significantly better lifespans in blue and green.

[0169] In comparison to the reference material HTMV2 - HTMV6 (V3 - V7 and V9 - V13), the materials according to the invention show (9-2), (2-7) and (2-10) Better lifespans in blue and / or green. Use of compounds according to the invention as hole transport materials in fluorescent and phosphorecing OLEDs

[0170] In particular, compounds according to the invention are suitable as HIL, HTL or EBL in OLEDs. They are suitable as a single layer, but also as a mixed component as HIL, HTL, EBL or within the EML.

[0171] Compared with NPB reference components (V1), all samples with the compounds according to the invention show both higher efficiencies and significantly improved lifetimes in singlet blue and triplet green. Table 1: Structure of OLEDs (Layer structure: Substrate / HIL1 / HTL / HIL2 / EBL / EML / ETL / EIL(1 nm LiQ) / Cathode) Example. HIL1 HTL HIL2 EBL EML ETL thickness / nm thickness / nm thickness / nm thickness / nm thickness / nm thickness / nm V1 HIL1 HIL2 HIL1 NPB H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V2 HIL1 HIL2 HIL1 HTMV1 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V3 HIL1 HIL2 HIL1 HTMV2 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V4 HIL1 HIL2 HIL1 HTMV3 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V5 HIL1 HIL2 HIL1 HTMV4 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V6 HIL1 HIL2 HIL1 HTMV5 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V7 HIL1 HIL2 HIL1 HTMV6 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E1 HIL1 HIL2 HIL1 ( 1-1 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E2 HIL1 HIL2 HIL1 ( 1-4 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E3 HIL1 HIL2 HIL1 ( 1-7 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E4 HIL1 HIL2 HIL1 ( 5-1 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E5 HIL1 HIL2 HIL1 ( 4-1 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E6 HIL1 HIL2 HIL1 ( 1-12 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E7 HIL1 HIL2 HIL1 ( 1-13 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E8 HIL1 HIL2 HIL1 ( 1-14 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E9 HIL1 HIL2 HIL1 ( 1-15 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E10 HIL1 HIL2 HIL1 ( 6-3 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E11 HIL1 HIL2 HIL1 ( 6-2 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E12 HIL1 HIL2 HIL1 ( 6-1 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E13 HIL1 HIL2 HIL1 ( 6-4 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E14 HIL1 HIL2 HIL1 ( 6-5 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E15 HIL1 HIL2 HIL1 ( 8-1 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E16 HIL1 HIL2 HIL1 ( 7-1 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E17 HIL1 HIL2 HIL1 ( 7-2 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E18 HIL1 HIL2 HIL1 ( 9-2 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E19 HIL1 HIL2 HIL1 ( 2-7 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E20 HIL1 HIL2 HIL1 ( 2-8 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E21 HIL1 HIL2 HIL1 ( 2-10 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E22 HIL1 HIL2 HIL1 ( 2-9 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E23 HIL1 HIL2 HIL1 ( 1-17 ) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm Tabelle 2: Daten der OLEDs Bsp. EQE @ 1000 cd / m2 LD80 @ 6000 cd / m 2< CIE % [h] X y V1 4.8 70 0.14 0.17 V2 6.8 160 0.14 0.14 V3 6.9 115 0.14 0.14 V4 6.8 115 0.14 0.14 V5 6.5 130 0.14 0.15 V6 6.6 100 0.14 0.14 V7 6.9 135 0.13 0.14 E1 7.0 180 0.14 0.15 E2 6.9 175 0.13 0.15 E3 7.0 165 0.13 0.15 E4 6.7 150 0.14 0.15 E5 6.9 170 0.14 0.13 E6 7.0 145 0.14 0.14 E7 7.0 155 0.14 0.14 E8 7.8 120 0.14 0.14 E9 6.9 135 0.13 0.14 E10 6.9 150 0.14 0.14 E11 7.0 135 0.14 0.13 E12 7.0 180 0.14 0.15 E13 7.0 150 0.14 0.14 E14 7.2 170 0.14 0.14 E15 7.0 150 0.14 0.14 E16 6.9 160 0.14 0.14 E17 6.9 155 0.14 0.15 E18 6.9 170 0.14 0.14 E19 6.9 135 0.14 0.14 E20 7.0 115 0.14 0.14 E21 7.0 150 0.14 0.14 E22 7.0 135 0.14 0.14 E23 7.0 140 0.14 0.14 Tabelle 3: Aufbau der OLEDs (Layer structure: Substrate / HTL / HIL2 / EBL / EML / ETL / Cathode) Bsp. HTL HIL2 EBL EML ETL Dicke / nm Dicke / nm Dicke / nm Dicke / nm Dicke / nm V8 HIL2 HIL1 NPB H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V9 HIL2 HIL1 HTMV1 H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V10 HIL2 HIL1 HTMV2 H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V11 HIL2 HIL1 HTMV3 H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V12 HIL2 HIL1 HTMV5 H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V13 HIL2 HIL1 HTMV6 H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E24 HIL2 HIL1 ( 1-1 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E25 HIL2 HIL1 ( 1-4 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E26 HIL2 HIL1 ( 1-7 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E27 HIL2 HIL1 ( 5-1 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E28 HIL2 HIL1 ( 4-1 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E29 HIL2 HIL1 ( 1-12 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E30 HIL2 HIL1 ( 1-13 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E31 HIL2 HIL1 ( 1-14 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E32 HIL2 HIL1 ( 1-3 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E33 HIL2 HIL1 ( 1-15 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E34 HIL2 HIL1 ( 6-2 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E35 HIL2 HIL1 ( 6-1 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E36 HIL2 HIL1 ( 6-4 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E37 HIL2 HIL1 ( 7-2 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E38 HIL2 HIL1 ( 9-2 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E39 HIL2 HIL1 ( 2-7 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E40 HIL2 HIL1 ( 2-8 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E41 HIL2 HIL1 ( 2-10 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E42 HIL2 HIL1 ( 2-9 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E43 HIL2 HIL1 ( 1-17 ) H2(88%): Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm Tabelle 4: Daten der OLEDs Bsp. Effizienz @ 1000 cd / m2 LD80 @ 8000 cd / m 2< CIE % [h] x Y V8 13.4 85 0.36 0.61 V9 16.3 140 0.35 0.62 V10 16.0 130 0.36 0.61 V11 16.7 155 0.36 0.61 V12 16.4 150 0.37 0.60 V13 17.0 170 0.35 0.62 E24 17.2 210 0.35 0.61 E25 17.2 200 0.36 0.61 E26 17.5 190 0.36 0.61 E27 16.7 190 0.37 0.60 E28 17.4 200 0.35 0.61 E29 17.0 180 0.37 0.61 E30 17.0 180 0.37 0.61 E31 17.5 220 0.37 0.61 E32 17.3 170 0.37 0.61 E33 17.2 200 0.37 0.61 E34 17.3 210 0.37 0.61 E35 17.2 220 0.37 0.61 E36 17.2 190 0.37 0.61 E37 17.2 200 0.37 0.61 E38 16.9 220 0.37 0.61 E39 16.9 160 0.37 0.61 E40 170 170 0.37 0.61 E41 17.0 195 0.37 0.61 E42 17.0 180 0.37 0.61 E43 17.1 190 0.37 0.61

Claims

1. Compound of the general formula (1) where the following applies to the symbols and indices used: R1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(=O)R4, CN, Si(R4)3, NO2, P(=O)(R4)2, S(=O)R4, S(=O)2R4, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may in each case be substituted by one or more radicals R4 and where one or more CH2 groups in the above-mentioned groups may be replaced by -R4C=CR4-, -C≡C-, Si(R4)2, C=O, C=S, C=NR4, -C(=O)O-, -C(=O)NR4-, P(=O)(R4), -O-, -S-, SO or SO2 and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R4, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R4, or an aralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R4, where the two radicals R1 may be linked to one another and may form a ring, so that a spiro compound forms in position 9 of the fluorene, where spirobifluorenes are excluded; R2, R3 are on each occurrence, identically or differently, preferably identically, H, D, F, Cl, Br, I, C(=O)R4, CN, Si(R4)3, NO2, P(=O)(R4)2, S(=O)R4, S(=O)2R4, N(R4)2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may in each case be substituted by one or more radicals R4 and where one or more CH2 groups in the above-mentioned groups may be replaced by -R4C=CR4-, -C≡C-, Si(R4)2, C=O, C=S, C=NR4, -C(=O)O-, -C(=O)NR4-, P(=O)(R4), -O-, -S-, SO or SO2 and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R4; R4 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(=O)R5, CN, Si(R5)3, NO2, P(=O)(R5)2, S(=O)R5, S(=O)2R5, N(R5)2, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may in each case be substituted by one or more radicals R5 and where one or more CH2 groups in the above-mentioned groups may be replaced by -R5C=CR5-, -C≡C-, Si(R5)2, C=O, C=S, C=NR5, -C(=O)O-, -C(=O)NR5-, P(=O)(R5), -O-, -S-, SO or SO2 and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R5; R5 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by D or F, where two or more adjacent substituents R5 may form a mono- or polycyclic, aliphatic ring system with one another; r is 1; p, q are 0; Za0, Zb0 are, identically or differently on each occurrence, equal to R3; Zc1 is equal to B' is a single bond, an aryl group having 6 to 30 ring atoms or a mono- or bicyclic heteroaryl group having 5 to 30 ring atoms, which may in each case be substituted by one or more radicals R4, where, if B' is a single bond, the nitrogen atom is bonded directly to the fluorene; Ar1, Ar2 are selected on each occurrence, identically or differently, from the following groups of the formulae (37) to (66), (69) to (72) and (76) to (96), which may be substituted by one or more radicals R6, R6 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(=O)R5, CN, Si(R5)3, NO2, P(=O)(R5)2, S(=O)R5, S(=O)2R5, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may in each case be substituted by one or more radicals R5 and where one or more CH2 groups in the above-mentioned groups may be replaced by -R5C=CR5-, -C≡C-, Si(R5)2, C=O, C=S, C=NR5, -C(=O)O-, -C(=O)NR5-, P(=O)(R5), -O-, -S-, SO or SO2 and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2.

2. Compound according to Claim 1, characterised in that it has the general formula (5) where the definitions from Claim 1 apply to the symbols used.

3. Compound according to Claim 1 or 2, characterised in that it has the general formula (8) where the definitions from Claim 1 apply to the symbols used.

4. Compound according to one or more of Claims 1 to 3, characterised in that both R1 are identical.

5. Compound according to one or more of Claims 1 to 4, characterised in that B' is a single bond or a phenylene, biphenylene, terphenylene, naphthylene, pyridinylene, pyrimidinylene, pyrazinylene, pyridazinylene, triazinylene, dibenzofuranylene or dibenzothiophenylene group, which may be substituted by one or more radicals R4.

6. Compound according to one or more of Claims 1 to 5, characterised in that B' is a single bond or a phenylene, biphenylene, terphenylene, naphthylene, dibenzofuranylene or dibenzothiophenylene group, which may be substituted by one or more radicals R4.

7. Compound according to one or more of Claims 1 to 6, characterised in that the compound is selected from one of the following compounds 8. Compound according to one or more of Claims 1 to 7, characterised in that B' is a single bond.

9. Compound according to one or more of Claims 1 to 8, characterised in that it is a monoamine compound.

10. Process for the preparation of a compound according to one or more of Claims 1 to 9 by means of one-step Buchwald coupling by reaction of a fluorene derivative containing a leaving group with Ar2-NH-Ar1.

11. Process for the preparation of a compound according to one or more of Claims 1 to 9 by means of two-step Buchwald coupling by stepwise reaction of a fluorene derivative containing a leaving group with (1) Ar2-NH2 and (2) NH2-Ar1.

12. Process for the preparation of a compound according to one or more of Claims 1 to 9, characterised in that the compound is prepared from a benzochromen-6-one.

13. Process according to Claim 12, comprising the following steps: a) addition of an organometallic compound onto a benzochromen-6-one and subsequent b) acid-catalysed cyclisation to give a 4-hydroxyfluorene derivative and subsequent c) conversion of the hydroxyl group in position 4 of the fluorene into a leaving group and subsequent d) conversion of the fluorene into the desired product.

14. Oligomer, polymer or dendrimer containing one or more compounds according to one or more of Claims 1 to 9, where the bond(s) to the polymer, oligomer or dendrimer may be localised at any desired positions in formula (1) that are substituted by R1 to R6.

15. Composition comprising one or more compounds according to one or more of Claims 1 to 9 or one or more polymers, oligomers or dendrimers according to Claim 14 and at least one further organofunctional material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electrontransport materials, electron-injection materials, hole-conductor materials, hole-injection materials, electron-blocking materials and holeblocking materials.

16. Formulation comprising at least one compound according to one or more of Claims 1 to 9 or at least one polymer, oligomer or dendrimer according to Claim 14 or at least one composition according to Claim 15 and at least one solvent.

17. Electronic device containing at least one compound according to one or more of Claims 1 to 9 or at least one polymer, oligomer or dendrimer according to Claim 14 or at least one composition according to Claim 15.

18. Electronic device according to Claim 17, characterised in that it is selected from organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs).

19. Electronic device according to Claim 17 or 18 which is selected from the group of organic electroluminescent devices, in particular an organic light-emitting diode (OLED), characterised in that the compound according to one or more of Claims 1 to 9 or the polymer, oligomer or dendrimer according to Claim 14 or a composition according to Claim 15 is employed in one or more of the following functions: - as hole-transport material in a hole-transport or hole-injection layer, - as matrix material in an emitting layer, - as electron-blocking material, - as exciton-blocking material, where the use as hole-transport material in a hole-transport or hole-injection layer is preferred.