Materials for organic electroluminescence devices

Abstract

Compound according to formula (10a), where the following applies to the symbols and indices used: X is B, P or P=O; Ar 2 In each occurrence, the group is either the same or different: an aryl group with 6 to 10 aromatic ring atoms, which may be substituted with one or more R groups, or a heteroaryl group with 5 to 13 aromatic ring atoms, which may be substituted with one or more R groups; R is selected in each instance, either the same or different, from the group consisting of H, D, F, CN, a straight-chain alkyl group with 1 to 10 C atoms, or a branched or cyclic alkyl group with 3 to 10 C atoms, each with one or more R substituents. 2 may be substituted, with one or more H atoms being replaced by D or F, or an aromatic or heteroaromatic ring system with 5 to 18 aromatic ring atoms, each with one or more R groups 2can be substituted, with optionally two or more adjacent substituents R forming a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which can be combined with one or more R groups 2 may be substituted; R 1 is the same or different R in each occurrence; two groups R can be used 1 , if n = 2, they also form a ring together; R 2 is selected in each occurrence, either the same or different, from the group consisting of H, D, F, a straight-chain alkyl group with 1 to 40 C atoms, or a branched or cyclic alkyl group with 3 to 40 C atoms, where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each with one or more R groups 3can be substituted, optionally with two or more adjacent substituents R 2 can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may contain one or more R groups 3 may be substituted; R 3 is selected from the group consisting of H, D, F, CN or an aliphatic hydrocarbon residue with 1 to 20 C atoms, either the same or different in each occurrence; n is 0 if X represents B or P=O, and is 0 or 2 if X represents P.

Description

[0001] The present invention relates to materials for use in electronic devices, in particular in organic electroluminescent devices, and to electronic devices, in particular organic electroluminescent devices, containing these materials.

[0002] The design of organic electroluminescent devices (OLEDs) that utilize organic semiconductors as functional materials is described, for example, in US 4539507, US 5151629, EP 0676461, and WO 98 / 27136. Increasingly, organometallic complexes exhibiting phosphorescence rather than fluorescence are used as emitting materials (MA Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6). Due to quantum mechanical reasons, using organometallic compounds as phosphor emitters allows for up to four times the energy and power efficiency. However, there is still room for improvement in OLEDs, particularly those exhibiting triplet emission (phosphorescence), for example, regarding efficiency, operating voltage, and lifetime. This is especially true for OLEDs emitting in the shorter wavelength range, such as green light.

[0003] The properties of phosphorescent OLEDs are not solely determined by the triplet emitters used. Other materials employed, such as matrix materials, hole-blocking materials, electron transport materials, and electron / exciton blocking materials, are also of particular importance. Improvements to these materials can therefore lead to significant enhancements in the OLED properties. There is also room for improvement in these materials for fluorescent OLEDs.

[0004] According to the prior art, ketones (e.g., according to WO 2004 / 093207 or WO 2010 / 006680) or phosphine oxides (e.g., according to WO 2005 / 003253) are used, among other things, as matrix materials for phosphorescent emitters. However, when using these matrix materials, as with other matrix materials, there is still room for improvement, particularly with regard to the efficiency and lifetime of the device.

[0005] According to the current state of the art, carbazole derivatives, e.g., according to WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, or WO 2008 / 086851, and indolocarbazole derivatives, e.g., according to WO 2007 / 063754 or WO 2008 / 056746, are still used as matrix materials for phosphorescent emitters in organic electroluminescence devices. These are often very sensitive to oxidation, which affects the production, purification, and storage of the materials, as well as the long-term stability of solutions containing them. Further improvements are desirable in these areas, as well as with regard to the efficiency, lifetime, and thermal stability of the materials.

[0006] Compounds are known from C. Camacho-Chamacho et al. (Phosphorus, Sulfur and Silicon and the Related Elements 1994, Vol. 91, pp. 189-203) and A. Murillo et al. (Phosphorus, Sulfur and Silicon and the Related Elements 1990, Vol. 53, pp. 87-101) in which a phosphorus atom bears an organic substituent that bonds to the phosphorus atom via two oxygen atoms and one nitrogen atom. Compounds are known from C. Camacho-Chamacho et al. (Eur. J. Inorg. Chem. 1999, pp. 1021-1027) in which a boron atom bears an organic substituent that bonds to the boron atom via two oxygen atoms and one nitrogen atom. From US 2007 / 0177893 and US 2007 / 0113967 polymeric compounds are known containing structural elements in which a silicon atom or an aluminum atom carries an organic substituent which is bonded to the silicon or aluminum atom via two oxygen atoms and a nitrogen atom.

[0007] The object of the present invention is to provide compounds suitable for use in a fluorescent or phosphorescent OLED, in particular a phosphorescent OLED, especially as a matrix material or as a hole transport / electron blocking material or exciton blocking material. In particular, it is an object of the present invention to provide matrix materials suitable for blue, green, and / or red phosphorescent OLEDs.

[0008] Surprisingly, it was found that certain compounds, described in more detail below, solve this problem and lead to significant improvements in organic electroluminescent devices, particularly with regard to lifetime, efficiency, and / or operating voltage. This applies to red, green, and partially also blue phosphorescent electroluminescent devices, especially when the compounds according to the invention are used as matrix materials. These compounds, as well as electronic devices, particularly organic electroluminescent devices containing such compounds, are therefore the subject of the present invention.

[0009] The present invention relates to a compound according to the following formula (10a), wherein the symbols and indices used are as follows: X is B, P or P=O; Ar 2In each occurrence, the group is either the same or different: an aryl group with 6 to 10 aromatic ring atoms, which may be substituted with one or more R groups, or a heteroaryl group with 5 to 13 aromatic ring atoms, which may be substituted with one or more R groups; R is selected in each instance, either the same or different, from the group consisting of H, D, F, CN, a straight-chain alkyl group with 1 to 10 C atoms, or a branched or cyclic alkyl group with 3 to 10 C atoms, each with one or more R substituents. 2 may be substituted, with one or more H atoms being replaced by D or F, or an aromatic or heteroaromatic ring system with 5 to 18 aromatic ring atoms, each with one or more R groups 2can be substituted, with optionally two or more adjacent substituents R forming a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which can be combined with one or more R groups 2 may be substituted; R 1 is the same or different R in each occurrence; two groups R can be used 1 , if n = 2, they also form a ring together; R 2 is selected in each occurrence, either the same or different, from the group consisting of H, D, F, a straight-chain alkyl group with 1 to 40 C atoms or a branched or cyclic alkyl group with 3 to 40 C atoms, where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each with one or more R groups 3 can be substituted, optionally with two or more adjacent substituents R2 can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may contain one or more R groups 3 may be substituted; R 3 is selected from the group consisting of H, D, F, CN or an aliphatic hydrocarbon residue with 1 to 20 C atoms, either the same or different in each occurrence; n is 0 if X represents B or P=O, and is 0 or 2 if X represents P.

[0010] An aryl group according to this invention contains 6 to 60 carbon atoms; a heteroaryl group according to this invention contains 2 to 60 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from nitrogen, oxygen, and / or sulfur. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e., benzene, or a simple heteroaromatic cycle, for example, pyridine, pyrimidine, thiophene, etc., or a fused (fused) aryl or heteroaryl group, for example, naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatics linked together by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but rather as aromatic ring systems.

[0011] 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 2 to 60 carbon atoms and at least one heteroatom in the ring system, provided that the sum of carbon atoms and heteroatoms is at least 5. 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, such as a carbon, nitrogen, or oxygen atom. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ethers, stilbene, etc., are also considered to be of this kind.as aromatic ring systems within the meaning of this invention, and also systems in which two or more aryl groups are connected, for example, by a short alkyl group.

[0012] Within the scope of the present invention, the following are preferably used as the groupings of an aliphatic hydrocarbon residue or an alkyl group or an alkenyl or alkynyl group, which may contain 1 to 40 carbon atoms and in which individual hydrogen atoms or CH2 groups may also be substituted by the groups mentioned above: methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neo-pentyl, cyclopentyl, n-hexyl, neo-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, Cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentinyl, hexynyl, heptynyl or octynyl.Unter einer Alkoxygruppe mit 1 bis 40 C-Atomen werden 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 und 2,2,2-Trifluorethoxy verstanden. Unter einer Thioalkylgruppe mit 1 bis 40 C-Atomen werden insbesondere 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.In general, alkyl, alkoxy or thioalkyl groups according to the present invention can be straight-chain, branched or cyclic, wherein one or more non-adjacent CH2 groups can be replaced by the groups mentioned above; furthermore, one or more H atoms can also be replaced by D, F, Cl, Br, I, CN or NO2, preferably F, Cl or CN, more preferably F or CN, particularly preferably CN.

[0013] An aromatic or heteroaromatic ring system with 5–60 aromatic ring atoms, each further compounded with the aforementioned R groups. 2or a hydrocarbon residue, and which can be linked via any position on the aromatic or heteroaromatic compound, are understood to include in particular groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, Isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole,Quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, 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 or groups derived from combinations of these systems.

[0014] In a preferred embodiment of the invention, X represents P or P=O.

[0015] All groups Y are still preferred to be chosen equally.

[0016] Preferred Groups Ar 2 are selected from benzene, 1- or 2-naphthalene, pyrrole, furan, thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, benzofuran, benzothiophene, indole, dibenzofuran, dibenzothiophene and carbazole or combinations of these residues, each of which may be substituted by one or more residues R.

[0017] Preferred residues R, which attach to Ar 2 Binding groups include H and aromatic ring systems. Particularly favored are R-substituted groups Ar. 2 are benzene, biphenyl, ortho-, meta- or para-terphenyl or ortho-, meta-, para- or branched quaterphenyl as well as pyrimidine, phenylpyrimidine, diphenylpyrimidine, 1,3,5-triazine and diphenyl-1,3-5-triazine.

[0018] For compounds processed by vacuum evaporation, the alkyl groups preferably have no more than five carbon atoms, particularly preferably no more than four carbon atoms, and most preferably no more than one carbon atom. For compounds processed from solution, compounds substituted with alkyl groups of up to ten carbon atoms or substituted with oligoarylene groups, for example ortho-, meta-, para-, or branched terphenyl or quaterphenyl groups, are also suitable.

[0019] The preferred embodiments mentioned above can be combined with one another as desired. In a particularly preferred embodiment of the invention, the above-mentioned advantages occur simultaneously.

[0020] When the compounds of formula (1) or the preferred embodiments are used as electron transport material, it is preferred if the group X stands for B or P=O and / or if at least one of the residues is R and / or Ar. 2 for an electron-deficient heteroaromatic ring system. Electron-deficient heterocycles according to the invention are five-membered heterocycles with at least two heteroatoms or six-membered heterocycles, to which one or more aromatic or heteroaromatic groups may be fused, such as substituted or unsubstituted imidazoles, pyrazoles, thiazoles, oxazoles, oxadiazoles, triazoles, pyridines, pyrazines, pyrimidines, pyridazines, triazines, imidazoles, etc.

[0021] When the compounds of formula (1) or the preferred embodiments are used as a matrix material for a phosphorescent emitter, it is preferred if the group X stands for P or P=O and if the substituents R and Ar2 do not contain any fused aryl or heteroaryl groups in which more than two six-membered rings are directly fused to one another. In particular, it is preferred if the R and Ar groups are 2 do not contain a condensed aryl or heteroaryl group in which two or more six-membered rings are directly condensed together.

[0022] When the compounds of formula (1) or the preferred embodiments are used as hole transport material, it is preferred if the group X stands for P.

[0023] Examples of preferred connections according to the embodiments listed above are the connections of the following structures. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 31 32 33 34 35 36 37 38 41 42 43 44 45 46 47 48 51 53 54 55 56 57 58

[0024] The compounds of formula (10a) or the preferred embodiments can be prepared according to synthesis steps known to those skilled in the art (Scheme 1). Other aromatic or heteroaromatic amines can be used in place of the phenylamines shown, in a completely analogous manner.

[0025] Scheme 1 (the embodiment with Si is not the subject of the invention):

[0026] According to the method shown in Scheme 2, unsymmetrical triamines can be produced which can then be converted to the corresponding unsymmetrical compounds according to the invention, as described in Scheme 1. Scheme 2:

[0027] Another object of the present invention is therefore a method for producing a compound according to formula (10a), comprising the reaction steps: a) Representation of a triamine; b) triple deprotonation of the triamine with a base; and c) Reaction of the deprotonated triamine with an electrophile bearing three leaving groups.

[0028] The compounds according to the invention are suitable for use in an electronic device, in particular in an organic electroluminescence device.

[0029] Another object of the present invention is therefore the use of a compound according to the invention in an electronic device, in particular in an organic electroluminescence device.

[0030] A further object of the present invention is an electronic device comprising at least one connection according to the invention.

[0031] The electronic device according to the present invention is a device which contains at least one layer containing at least one organic compound. However, the component may also contain inorganic materials or layers which are composed entirely of inorganic materials.

[0032] The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs), 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), dye-sensitized organic solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and "organic plasmon emitting devices" (DM Koller et al., Nature Photonics 2008, 1-4), but preferably organic electroluminescent devices (OLEDs), particularly preferably phosphorescent OLEDs.

[0033] The organic electroluminescent device contains a cathode, an anode, and at least one emitting layer. In addition to these layers, it may contain further layers, such as one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generation layers. Interlayers, which may, for example, have an exciton-blocking function, may also be introduced between two emitting layers. It should be noted, however, that not every one of these layers is necessarily present. The organic electroluminescent device may contain a single emitting layer, or it may contain multiple emitting layers.If multiple emission layers are present, these preferably exhibit several emission maxima between 380 nm and 750 nm, resulting in overall white emission; that is, different emitting compounds capable of fluorescence or phosphorescence are used in the emitting layers. Systems with three emitting layers are particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission (for the basic structure, see, for example, WO 2005 / 011013).

[0034] The compound according to the embodiments described above can be used in different layers, depending on the precise structure. A preferred application is an organic electroluminescent device containing a compound according to formula (10a) or the preferred embodiments described above as a matrix material for fluorescent or phosphorescent emitters, particularly for phosphorescent emitters, and / or in a hole-blocking layer and / or in an electron transport layer and / or in an electron-blocking or exciton-blocking layer and / or in a hole transport layer, depending on the precise substitution.

[0035] In a further embodiment of the invention, the organic electroluminescent device contains the compound according to formula (10a) or the preferred embodiments described above in an optical coupling layer. An optical coupling layer is understood to be a layer that is not located between the anode and the cathode, but is applied to an electrode outside the actual device, for example between an electrode and a substrate, in order to improve optical coupling.

[0036] In a preferred embodiment of the invention, the compound according to formula (10a) or the preferred embodiments described above is used as a matrix material for a fluorescent or phosphorescent compound, in particular for a phosphorescent compound, in an emitting layer. The organic electroluminescent device can contain one emitting layer, or it can contain several emitting layers, wherein at least one emitting layer contains at least one compound according to the invention as a matrix material.

[0037] When the compound according to formula (10a) or the preferred embodiments described above is used as a matrix material for an emitting compound in an emitting layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). For the purposes of this invention, phosphorescence is understood to mean luminescence from an excited state with a higher spin multiplicity, i.e., a spin state > 1, in particular from an excited triplet state. For the purposes of this application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum, and copper complexes, are to be considered phosphorescent compounds.

[0038] The mixture of the compound according to formula (10a) or the preferred embodiments described above and the emitting compound contains between 99 and 1 vol.%, preferably between 98 and 10 vol.%, particularly preferably between 97 and 60 vol.%, and especially between 95 and 80 vol.% of the compound according to formula (10a) or the preferred embodiments described above, based on the total mixture of emitter and matrix material. Similarly, the mixture contains between 1 and 99 vol.%, preferably between 2 and 90 vol.%, and especially between 3 and 40 vol.%, and particularly between 5 and 20 vol.% of the emitter, based on the total mixture of emitter and matrix material.

[0039] Another preferred embodiment of the present invention is the use of the compound according to formula (10a) or the preferred embodiments described above as a matrix material for a phosphorescent emitter in combination with another matrix material. Particularly suitable matrix materials that can be used in combination with the compounds according to formula (10a) or the preferred embodiments described above are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g. according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triarylamines, carbazole derivatives, etc. B. CBP (N,N-Biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851, indolocarbazole derivatives, e.g. according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, e.g. according to WO 2010 / 136109 or WO 2011 / 000455, azacarbazole derivatives, e.g.according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, e.g. according to WO 2007 / 137725, silanes, e.g. according to WO 2005 / 111172, azaborols or boron esters, e.g. according to WO 2006 / 117052, triazine derivatives, e.g. according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877, zinc complexes, e.g. B. according to EP 652273 or WO 2009 / 062578, diazasilol or tetraazasilol derivatives, e.g. according to WO 2010 / 054729, diazaphosphole derivatives, e.g. according to WO 2010 / 054730, bridged carbazole derivatives, e.g. according to WO 2011 / 042107, WO 2011 / 060867 and WO 2011 / 088877. Likewise, another phosphorescent emitter, which emits at a shorter wavelength than the actual emitter, may be present as a co-host in the mixture.

[0040] Suitable phosphorescent compounds (= triplet emitters) are, in particular, compounds that emit light, preferably in the visible range, upon suitable excitation and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, and especially preferably greater than 56 and less than 80, particularly a metal with this atomic number. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are preferred as phosphor emitters, especially compounds containing iridium or platinum.

[0041] Examples of the emitters described above can be found in applications WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 2005 / 033244, WO 2005 / 019373, US 2005 / 0258742 and WO 2010 / 086089. 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 electroluminescence are suitable, and those skilled in the art can use other phosphorescent complexes without inventive effort.

[0042] In a further embodiment of the invention, the organic electroluminescent device according to the invention does not contain a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer; i.e., the emitting layer is directly adjacent to the hole injection layer or the anode, and / or the emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051. Furthermore, it is possible to use a metal complex that is identical or similar to the metal complex in the emitting layer directly adjacent to the emitting layer as a hole transport or hole injection material, as described, for example, in WO 2009 / 030981.

[0043] In a further preferred embodiment of the invention, the compound according to formula (10a) or the preferred embodiments described above is used as an electron transport material in an electron transport or electron injection layer. The emitting layer can be fluorescent or phosphorescent. When the compound is used as an electron transport material, it is preferred that it be doped, for example with alkali metal complexes such as LiQ (lithium hydroxyquinolinate).

[0044] In yet another preferred embodiment of the invention, the compound according to formula (10a) or the preferred embodiments described above are used in a hole-blocking layer. A hole-blocking layer is understood to be a layer that is directly adjacent to an emitting layer on the cathode side.

[0045] It is also possible to use the compound according to formula (10a) or the preferred embodiments described above both in a hole-blocking layer or electron transport layer and as a matrix in an emitting layer.

[0046] In yet another embodiment of the invention, the compound according to formula (10a) or the preferred embodiments described above are used in a hole transport layer or in an electron blocking layer or exciton blocking layer.

[0047] In the further layers of the organic electroluminescent device according to the invention, all materials commonly used in the prior art can be employed. Therefore, without any inventive effort, a person skilled in the art can use all materials known for organic electroluminescent devices in combination with the compounds according to formula (10a) or the preferred embodiments described above.

[0048] A further preferred organic electroluminescence device is characterized in that one or more layers are coated using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6 The initial pressure is vapor-deposited at mbar. However, it is also possible that the initial pressure is even lower, for example less than 10 mbar. -7 mbar.

[0049] A preferred option is an organic electroluminescence device, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or with the aid of carrier gas sublimation. The materials are coated at a pressure between 10 -5 mbar and 1 bar are applied. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (e.g., BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0050] 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, offset printing, LITI (light-induced thermal imaging, thermal transfer printing), inkjet printing, or nozzle printing. Soluble compounds are required for this purpose, which can be obtained, for example, by suitable substitution.

[0051] Hybrid processes are also possible, in which, for example, one or more layers of solution are applied and one or more further layers are vapor-deposited.

[0052] These methods are generally known to those skilled in the art and can be applied by them without inventive effort to organic electroluminescent devices containing the compounds according to the invention.

[0053] The compounds and 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, or compounds according to formula (10a), or the preferred embodiments described above, when used as matrix materials for fluorescent or phosphorescent emitters, lead to very high efficiencies and long lifetimes. This is particularly true when the compounds are used as matrix materials for a phosphorescent emitter. 2. The compounds according to the invention or compounds according to formula (10a) or the preferred embodiments described above are suitable not only as a matrix for red phosphorescent compounds, but also for green and optionally also for blue phosphorescent compounds.

[0054] These advantages mentioned above do not come at the expense of other electronic properties.

[0055] The invention is further explained by the following examples, without being intended to limit it. A person skilled in the art can implement the invention in its entire disclosed scope from the descriptions and, without inventive effort, create further connections according to the invention and use them in electronic devices or apply the method according to the invention. Examples:

[0056] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be obtained from Aldrich or ABCR. The numbers given for non-commercially available starting materials are the corresponding CAS numbers. Example 1: Bis-(4-(3-phenylamino))biphenyl)amine

[0057] A solution of 32.1 g (100 mmol) bis-(4-biphenyl)amine in 1000 ml THF is added dropwise at 10 °C with stirring to ensure the temperature does not exceed 20 °C. After addition, the mixture is stirred for 3 h at room temperature, the THF is removed under vacuum, the residue is dissolved in 500 ml ethyl acetate, and the organic phase is washed five times with 300 ml water and once with 300 ml saturated sodium chloride solution. It is then dried over magnesium sulfate. After removal of the ethyl acetate under vacuum, the oily residue is recrystallized from ethanol, optionally with the addition of a small amount of ethyl acetate. Yield: 41.7 g (87 mmol), 87%; purity: approx. 99% by NMR.

[0058] 500 ml of toluene are mixed with 3 ml (3 mmol) of tri-tert-butylphosphine (1 M in toluene), 500 mg (2 mmol) of palladium(II) acetate, and, after stirring for 5 min, with 47.9 g (100 mmol) of bis-(4-(3-bromobiphenyl))amine, 20.5 g (220 mmol) of aniline, and 33.6 g (350 mmol) of sodium tert-butoxide. The mixture is heated under reflux for 6 h. After cooling, 150 ml of saturated ammonium chloride solution and 40 ml of glacial acetic acid are added while stirring. The aqueous phase is separated, the organic phase is washed twice with 150 ml of saturated sodium chloride solution each time, dried over magnesium sulfate, the toluene is removed under vacuum, and the remaining oil is recrystallized from approximately 100 ml of methanol. Yield: 40.3 g (80 mmol), 80%; Purity: approx. 98% by NMR. Example 2: General synthesis procedure

[0059] A solution of 50.3 g (100 mmol) bis-(4-(3-phenylamino)biphenyl))amine in 500 ml diethyl ether is mixed dropwise with 84.0 ml (210 mmol) n-butyllithium (2.5 M in hexane) while stirring at room temperature, ensuring the temperature does not exceed 30 °C. After the addition is complete, stirring continues for 1 h, then a solution of 100 mmol of the corresponding electrophile in 200 ml diethyl ether is added dropwise, and stirring continues for 12 h at room temperature. The diethyl ether is removed under vacuum, 200 ml methanol is added, the mixture is stirred while hot, and after cooling, the solid is filtered by suction. It is washed twice with 100 ml of methanol each time and dried under vacuum. The solid is dissolved in 500 ml of dichloromethane, filtered over Alox (basic, activity level 1), the solid obtained after removal of the dichloromethane is recrystallized three times from toluene / ethanol, and finally sublimed twice in a fractional manner under high vacuum. Purity: 99.7–99.9% by HPLC. Example. Electrophile product yield 3 34 % 5 51 % 6 64 % 7 31 % 8 34 % Example 28: Fabrication and characterization of organic electroluminescence devices

[0060] Electroluminescence devices according to the invention can be represented as generally described, for example, in WO 2005 / 003253. Here, the results of various OLEDs are compared. The basic structure, the materials used, the doping level, and their layer thicknesses are identical for better comparability.

[0061] OLEDs with the compounds 3, 4, 6 and 8 according to the invention are described as host material in a mixed host system with host 1 in the following layer structure: Hole injection layer (HIL) 20 nm 2,2',7,7'-Tetrakis(di-para-tolyl-amino)spiro-9,9'-bifluorene Hole transport layer (HTL) 5 nm NPB (N-naphthyl-N-phenyl-4,4'-diaminobiphenyl) Electron blocking layer (EBL) 15 nm EBL (9,9-bis-(3,5-diphenylamino-phenyl)fluorene) Emission Layer (EML): Host: 40 nm see Table 1, proportions in vol.% doping: 10 vol.% doping, fac-Tris(2-phenylpyridine)iridium (IrPPy) or Tris(1-phenylisoquinoline)iridium (IrPIQ) or fac-Tris(2-(4-cyano-5-fluorophenylpyridine)iridium (IrF-CN-PPy) Electron conductor (ETL) cathode 20 nm BAlq1 nm LiF, followed by 100 nm Al.

[0062] For the sake of clarity, the structures of EBL and the dodones are shown below.

[0063] To characterize these OLEDs, the electroluminescence spectra and the external quantum efficiency (measured in %) as a function of brightness, calculated from current-voltage-brightness characteristics (IUL characteristics), are determined. Table 1: Device Results Device example Mixed Host / Dotand EQE at 1000cd / m 2 % Spannungbei 1000cd / m 2 [V] CIEx / y 12 Example 3, 60%Host 1, 30%IrPPy 13.9 4.3 0.36 / 0.62 14 Example 6, 50%Host 1, 40%IrPPy 15.8 3.9 0.36 / 0.62 15 Example 8, 50%Host 1, 40%IrPPy 12.7 4.4 0.35 / 0.63 16 Example 6, 40%Host 1, 50%IrPIQ 8.7 5.0 0.68 / 0.31 17 Example 6, 60%Host 1, 30%IrF-CN-PPy 16.1 7.9 0.16 / 0.25

[0064] Furthermore, OLEDs are manufactured using the compound from Example 5 as a hole injection material in the following layer structure: Hole injection layer (HIL) 40 nm Example 5 Hole transport layer (HTL) 5 nm NPB (N-naphthyl-N-phenyl-4,4'-diaminobiphenyl) Emission layer (EML) 40 nm Host: 4,4'-N,N'-Dicarbazolylbiphenyl (CBP) Dotand: 10 vol.% doping, Tris(1-phenylisoquinoline)iridium (IrPIQ) Electron conductor (ETL) 20 nm Alq; cathode 1 nm LiF, then 100 nm Al.

[0065] To characterize these OLEDs, the electroluminescence spectra and the external quantum efficiency (measured in %) as a function of brightness, calculated from current-voltage-brightness characteristics (IUL characteristics), are determined. Table 2: Device Results Device example EQE at 1000cd / m 2 [%] Spannungbei 1000cd / m 2 [V] CIEx / y 17 13.0 3.8 0.68 / 0.31

Claims

[1] Compound according to formula (10a), where the symbols and indices used are: X is B, P or P=O; Ar 2 In each occurrence, the group is either the same or different: an aryl group with 6 to 10 aromatic ring atoms, which may be substituted with one or more R groups, or a heteroaryl group with 5 to 13 aromatic ring atoms, which may be substituted with one or more R groups; R is selected in each instance, either the same or different, from the group consisting of H, D, F, CN, a straight-chain alkyl group with 1 to 10 C atoms, or a branched or cyclic alkyl group with 3 to 10 C atoms, each with one or more R substituents. 2 may be substituted, with one or more H atoms being replaced by D or F, or an aromatic or heteroaromatic ring system with 5 to 18 aromatic ring atoms, each with one or more R groups 2can be substituted, with optionally two or more adjacent substituents R forming a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which can be combined with one or more R groups 2 may be substituted; R 1 is the same or different R in each occurrence; two groups R can be used 1 , if n = 2, they also form a ring together; R 2 is selected in each occurrence, either the same or different, from the group consisting of H, D, F, a straight-chain alkyl group with 1 to 40 C atoms, or a branched or cyclic alkyl group with 3 to 40 C atoms, where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each with one or more R groups 3can be substituted, optionally with two or more adjacent substituents R 2 can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may contain one or more R groups 3 may be substituted; R 3 is selected from the group consisting of H, D, F, CN or an aliphatic hydrocarbon residue with 1 to 20 C atoms, either the same or different in each occurrence; n is 0 if X represents B or P=O, and is 0 or 2 if X represents P. [2] Compound according to claim 1, characterized by that all groups Y are chosen in the same way. [3] Method for producing a compound according to claim 1 or 2, comprising the reaction steps: a) Representation of a triamine; b) triple deprotonation of the triamine with a base; and c) Reaction of the deprotonated triamine with an electrophile bearing three leaving groups. [4] Use of a compound according to claim 1 or 2 in an electronic device, in particular in an organic electroluminescent device. [5] Electronic device comprising at least one compound according to claim 1 or 2, in particular selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitized organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon-emitting devices. [6] Electronic device according to claim 5, which is an organic electroluminescence device, characterized by , that the compound according to claim 1 or 2 is used as a matrix material for fluorescent or phosphorescent emitters and / or in a hole-blocking layer and / or in an electron transport layer and / or in an electron-blocking or exciton-blocking layer and / or in a hole transport layer.