Electronic devices containing organic layers

Abstract

Electronic device comprising at least one organic layer, wherein the organic layer comprises one or more compounds of formula (I) or (II), wherein the symbols appearing are defined as follows: E is a divalent group chosen from S=O and S(=O)2; W, X are the same or different in each occurrence N, P or CR 1 ; Y is the same or different in each occurrence NR 1 , PR 1 , O or S; Z is equal to C when a substituent is bonded, and is otherwise the same or different in every occurrence. 1 or N; R 1 is the same or different in each occurrence H, D, F, Cl, Br, I, C(=O)R 2 , CN, Si(R 2 )3, N(R 2 )2, NO2, P(=O)(R 2 )2, S(=O)R 2 , S(=O)2R 2, 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 are each linked to one or more R groups 2 can be substituted and where one or more CH2 groups in the above-mentioned groups are replaced by -R 2 C=CR 2 -, -C=C-, Si(R 2 )2, C=O, C=S, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 2 ), -O-, -S-, SO or SO2 may be replaced and wherein 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 with 5 to 30 aromatic ring atoms, each of which is replaced by one or more R groups 2may be substituted, or an aryloxy or heteroaryloxy group with 5 to 30 aromatic ring atoms, separated by one or more R groups 2 can be substituted, with two or more residues R 1 can be linked together and form a ring; where the group R 1 , which is bonded to group E, is selected from aromatic or heteroaromatic ring systems with 5 to 30 aromatic ring atoms, each of which is bonded to one or more R groups 2 They may be substituted; R 2 is the same or different in each occurrence H, D, F, Cl, Br, I, C(=O)R 3 , CN, Si(R 3 )3, N(R 3 )2 , NO2, P(=O)(R 3 )2, S(=O)R 3 , S(=O)2R 3, 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 are each linked to one or more R groups 3 can be substituted and where one or more CH2 groups in the above-mentioned groups are replaced by -R 3 C=CR 3 -, -C≡C-, Si(R 3 )2, C=O, C=S, C=NR 3 , -C(=O)O-, -C(=O)NR 3 -, NR 3 , P(=O)(R 3 ), -O-, -S-, SO or SO2 may be replaced and wherein 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 with 5 to 30 aromatic ring atoms, each of which is replaced by one or more R groups 3may be substituted, or an aryloxy or heteroaryloxy group with 5 to 30 aromatic ring atoms, separated by one or more R groups 3 can be substituted, with two or more residues R 2 can be linked together and form a ring; R 3 The compound is the same or different H, D, F, or an aliphatic, aromatic, or heteroaromatic organic residue with 1 to 20 C atoms, in which one or more H atoms may also be replaced by D or F; two or more substituents R may be present. 3 be linked together and form a ring.

Description

[0001] The present invention relates to an electronic device comprising one or more compounds of formula (I) or (II). Furthermore, the invention relates to the use of a compound of formula (I) or (II) in an electronic device, preferably in an organic electroluminescent device, particularly preferably as matrix material in an emitting layer. The invention further relates to certain compounds of formula (I) or (II) which are suitable for use in the device according to the invention.

[0002] The development of functional compounds for use in electronic devices is currently the subject of intensive research. One of the goals is to develop compounds that enable an improved property profile of the devices. Also of interest is the provision of alternative compounds for use in electronic devices.

[0003] According to the present invention, the term electronic device includes, inter alia, 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), organic plasmon-emitting diodes and organic electroluminescent devices (OLEDs).

[0004] The structure of the above-mentioned organic electroluminescent devices (OLEDs) is known to the person skilled in the art and is described, inter alia, in US 4539507, US 5151629, EP 0676461 and WO 1998 / 27136.

[0005] Regarding the performance data of organic electroluminescent devices, further improvements are still needed, especially with regard to widespread commercial use. Of particular importance in this context are the lifetime, efficiency, and operating voltage of the organic electroluminescent devices, as well as the achieved color values. There is potential for improvement regarding the lifetime of blue-emitting electroluminescent devices, in particular. Furthermore, it is desirable that the compounds for use as functional materials in electronic devices exhibit high thermal stability and a high glass transition temperature and be capable of sublimation without decomposition.

[0006] There is still a need for matrix materials, especially for phosphorescent emitters, that simultaneously deliver good efficiency, a long lifetime, and low operating voltage for electronic devices. There is also particular interest in providing matrix materials for green-emitting phosphorescent dopants. The properties of the matrix materials are often limiting the lifetime and efficiency of the organic electroluminescent device. Matrix materials for phosphorescent emitters should preferably exhibit a high T1 level (triplet level). This is particularly relevant for matrix materials for blue-emitting phosphorescent emitters.

[0007] Furthermore, the development of new electron-transport materials is desirable, as the properties of the electron-transport material have a significant influence on the aforementioned properties of the organic electroluminescent device. In particular, there is a need for electron-transport materials that simultaneously offer good efficiency, a long lifetime, and low operating voltage.

[0008] According to the state of the art, carbazole derivatives, e.g., bis(carbazolyl)biphenyl, are frequently used as matrix materials for phosphorescent emitters. Ketones (WO 2004 / 093207), phosphine oxides, sulfones (WO 2005 / 003253), and triazine compounds such as triazinylspirobifluorene (cf. WO 2010 / 015306) are also used in this function.

[0009] The use of benzimidazole compounds substituted with aryl groups in OLEDs is known in the prior art (WO 2004 / 080975). Benzoxazole and benzothiazole compounds are also known for this use (WO 2010 / 027181).

[0010] In US 2009 / 184633, JP 2008 / 130754 and JP 2006 / 156847, benzimidazole compounds substituted with an electron-deficient heteroaryl group are disclosed for use in OLEDs.

[0011] Benzimidazole compounds substituted with a sulfoxide or sulfone are also disclosed in the following prior art: - Korshak et al. : Synthesis and investigation of poly(benzimidazole imides) based on new di-imidodicarboxylic acids, Polymer Science USSR 1980, Vol. 22, No 6, pp. 1325-1333 - Jouanneau et al. : Synthesis and characterization of ionic conducting sulfonated polybenzimidazoles, J. Polym. Sci. Part A, 2010, Vol. 48, No. 8, pp. 1732-1742 - Korshak et al. : Two-stage synthesis of poly(N-phenylbenzimidazoles, Macromolecules 1972, Vol. 5, No. 6, pp. 807-812, and - WO 2011 / 076323 A1.

[0012] The present invention is therefore based on the technical object of providing alternative compounds which are suitable for use in electronic devices such as OLEDs, and which can be used in particular as matrix materials for phosphorescent emitters and / or as electron transport materials.

[0013] Within the scope of the present invention, it has now been found that compounds of the formula (I) or (II) given below are excellently suitable for use in electronic devices, in particular as matrix materials for phosphorescent emitters and / or as electron transport materials.

[0014] The invention thus relates to an electronic device comprising at least one organic layer, wherein the organic layer comprises one or more compounds of a formula (I) or (II), wherein the symbols appearing are: E is a divalent group chosen from S=O and S(=O)2; W, X are the same or different at each occurrence N, P or CR 1 ; Y is the same or different at each occurrence NR 1 , PR 1 , O or S; Z is equal to C if a substituent is attached, and is otherwise the same or different at each occurrence CR 1 or N; R 1 is the same or different at each occurrence: H, D, F, Cl, Br, I, C(=O)R 2 , CN, Si(R 2 )3, N(R 2 )2, NO2, P(=O)(R 2 )2, S(=O)R 2 , S(=O)2R 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, wherein the above-mentioned groups are each substituted by one or more radicals R 2 may be substituted and wherein one or more CH2 groups in the above-mentioned groups are substituted by -R 2 C=CR 2 -, -C≡C- , Si(R 2 )2, C=O, C=S, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 2 ), -O-, -S-, SO or SO2 and where one or more H atoms in the above-mentioned groups can be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 2may be substituted, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 2 may be substituted, where two or more radicals R 1 can be linked together to form a ring; where the group R 1 which is bonded to the group E, is selected from aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, each of which is bonded to one or more radicals R 2 can be substituted; R 2 is the same or different at each occurrence: H, D, F, Cl, Br, I, C(=O)R 3 , CN, Si(R 3 )3, N(R 3 )2, NO2, P(=O)(R 3 )2, S(=O)R 3 , S(=O)2R 3, 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, wherein the above-mentioned groups are each substituted by one or more radicals R 3 may be substituted and wherein one or more CH2 groups in the above-mentioned groups are substituted by -R 3 C=CR 3 -, -C≡C- , Si(R 3 )2, C=O, C=S, C=NR 3 , -C(=O)O-, -C(=O)NR 3 -, NR 3 , P(=O)(R 3 ), -O-, -S-, SO or SO2 and where one or more H atoms in the above-mentioned groups can be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 3may be substituted, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 3 may be substituted, where two or more radicals R 2 can be linked together and form a ring; R 3 is, identically or differently at each occurrence, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by D or F; two or more substituents R 3 be linked together and form a ring.

[0015] The following general definitions apply in this application: An aryl group within the meaning of this invention contains 6 to 60 aromatic ring atoms; a heteroaryl group within the meaning of 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 represents the basic definition. If other preferences are stated in the description of the present invention, for example with regard to the number of aromatic ring atoms or the heteroatoms contained, these apply.

[0016] 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 fused (fused) aromatic or heteroaromatic polycycle, for example, naphthalene, phenanthrene, quinoline, or carbazole. A fused (fused) aromatic or heteroaromatic polycycle, for the purposes of the present application, consists of two or more simple aromatic or heteroaromatic cycles fused together. Such a group is also referred to as a fused aryl group or heteroaryl group in the context of the present invention.

[0017] An aryl or heteroaryl group, which may be substituted by the above-mentioned radicals and which may be linked to the aromatic or heteroaromatic ring via any desired positions, is understood to mean, 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, 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.

[0018] An aryloxy group, as defined in the present invention, is understood to mean an aryl group, as defined above, which is bonded via an oxygen atom. An analogous definition applies to heteroaryloxy groups.

[0019] An aromatic ring system within the meaning of this invention contains 6 to 60 C atoms in the ring system. A heteroaromatic ring system within the meaning of this invention contains 5 to 60 aromatic ring atoms, of which at least one is a heteroatom. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system within the meaning of this invention is to be understood as a system which does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be replaced by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as, for example, a sp 3 -hybridized C, Si, N or O atom, a sp 2-hybridized C or N atom or an sp-hybridized C atom. For example, systems such as 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are also to be understood as aromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are connected, 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 to be understood as aromatic or heteroaromatic ring systems within the meaning of this invention, for example systems such as biphenyl, terphenyl, or diphenyltriazine.

[0020] An aromatic or heteroaromatic ring system with 5 - 60 aromatic ring atoms, which may each be substituted by radicals as defined above and which may be linked to the aromatic or heteroaromatic ring via any position, is understood to mean 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, 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.,

[0021] In the context of the present invention, a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, in which individual H atoms or CH2 groups can also be substituted by the groups mentioned above in the definition of the radicals, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, 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 are understood.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.

[0022] For the purposes of this application, the phrase "two or more residues can form a ring" is understood to mean, among other things, that the two residues are linked by a chemical bond. This is illustrated by the following scheme:

[0023] Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring. This is illustrated by the following scheme:

[0024] The following preferred embodiments apply to the compounds of formula (I) and (II).

[0025] Preferably, E is S(=O)2.

[0026] The group E can be bonded at any position on the six-membered ring and is preferably bonded in the meta- or para-position to the group Y.

[0027] Preferably, W is the same or different at each occurrence, N or CR 1 . Particularly preferably, W is equal to N.

[0028] Preferably, X is the same or different at each occurrence and is N or CR 1 . Particularly preferably, X is CR 1 .

[0029] Preferably Y is the same or different at each occurrence NR 1 , O or S, particularly preferably NR 1 .

[0030] Very particularly preferred is an embodiment in which W is N, X is CR 1 and Y equals NR 1 is.

[0031] The compound of formula (I) or (II) preferably does not contain a condensed aryl group with more than 13 aromatic ring atoms. It has been found that, without the presence of a condensed aryl group with more than 13 aromatic ring atoms in the compound, OLEDs with significantly improved properties with regard to efficiency and lifetime can be obtained. This applies in particular to OLEDs comprising the compound in a layer containing one or more phosphorescent emitters. The compound of formula (I) or (II) particularly preferably does not contain a condensed aryl group with more than 10 aromatic ring atoms.

[0032] Preferably, in the case that no substituent is bonded to a group Z, this group Z is CR 1 . Furthermore, it is preferred that 0, 1 or 2 groups Z per aromatic six-membered ring are N and the remaining groups Z to which no substituent is bonded are CR 1Furthermore, it is preferred that no more than two adjacent Z groups are equal to N.

[0033] Preferred is R 1 at each occurrence, identical or different, H, D, F, CN, Si(R 2 )3, N(R 2 )2, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, wherein the above-mentioned groups are each substituted by one or more radicals R 2 may be substituted and wherein in the above-mentioned groups one or more CH2 groups are substituted by -C=C-, -R 2 C=CR 2 -, Si(R 2 )2, C=O, C=NR 2 , -NR 2 -, -O-, -S-, -C(=O)O- or -C(=O)NR 2 - may be replaced, or an aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, where two or more radicals R 1can be linked together to form a ring; where the group R 1 which is bonded to the group E, is selected from aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, each of which is bonded to one or more radicals R 2 may be substituted. The group R is preferred 1 , which is bonded to the group E, selected from aromatic ring systems with 6 to 18 aromatic ring atoms, which are bonded to one or more radicals R 2 can be substituted.

[0034] Preferred is R 2 at each occurrence, identical or different, H, D, F, CN, Si(R 3 )3, N(R 3 )2, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, wherein the above-mentioned groups are each substituted by one or more radicals R 3may be substituted and wherein in the above-mentioned groups one or more CH2 groups are substituted by -C≡C-, -R 3 C=CR 3 -, Si(R 3 )2, C=O, C=NR 3 , -NR 3 -, -O-, -S-, -C(=O)O- or -C(=O)NR 3 - may be replaced, or an aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms, each of which is substituted by one or more radicals R 3 may be substituted, where two or more radicals R 2 can be linked together and form a ring.

[0035] Preferably, at least one group selected from aromatic ring systems having 6 to 18 aromatic ring atoms, preferably 12 to 18 aromatic ring atoms, and heteroaromatic ring systems having 5 to 18 aromatic ring atoms, which are each substituted with one or more radicals R 2 can be substituted.

[0036] The compound of formula (I) or (II) particularly preferably contains at least one group R 1 , which is chosen from - Heteroaryl groups with 5 to 20 aromatic ring atoms, which are substituted by one or more radicals R 2 may be substituted and which contain at least one heteroaromatic five-membered ring with two or more heteroatoms selected from N, O and S; - Heteroaryl groups with 5 to 20 aromatic ring atoms, which are substituted by one or more radicals R 2 may be substituted and which contain at least one heteroaromatic six-membered ring with one or more heteroatoms selected from N, O and S; and - Carbazole derivatives which are substituted with one or more radicals R 2 can be substituted.

[0037] For the purposes of the present invention, carbazole derivatives also include carbazole derivatives with fused groups, such as indenocarbazoles or indolocarbazoles, as well as carbazole derivatives in which one or more carbon atoms in the aromatic six-membered rings are replaced by nitrogen.

[0038] Preferred embodiments of the compound according to formula (I) correspond to the following formula, where the definitions given above apply to the groups occurring and m is 0 or 1 at each occurrence, the sum of the indices m being 1. Preference is given to the preferred embodiments of the groups occurring. With particular preference, Z is CR 1 or C. Furthermore, E is preferably S(=O)2.

[0039] Preferred embodiments of the compound according to formula (II) correspond to the following formulas, where the definitions given above apply to the groups occurring. The preferred embodiments of the groups occurring are preferred. Z is particularly preferably CR 1 Furthermore, E is preferably S(=O)2.

[0040] A particularly preferred embodiment of the compound according to formula (I) corresponds to the following formula:wherein the above-mentioned definitions apply to the groups occurring and m is equal to 0 or 1 at each occurrence, where the sum of the indices m is equal to 1, and p is 0, 1 or 2; and Ar 2 represents an aryl or heteroaryl group having 5 to 10 aromatic ring atoms, which is reacted with one or more radicals R 2 can be substituted, and Het represents a group of the formula (Het-a) where T is N or CR 2where at least one group T is N, and the dashed line indicates the bond to the rest of the compound, or Het represents a group of the formula (Het-b) or (Het-c) where the symbols appearing are as defined above and the dashed line indicates the bond to the rest of the compound, or Het represents a group of the formula (Het-d) or (Het-e) where T is N or CR 2 and at least one group T is N, and the dashed line indicates the bond to the rest of the compound.

[0041] A further particularly preferred embodiment of the compound according to formula (I) corresponds to the following formula:wherein the definitions given above apply to the groups occurring.

[0042] A particularly preferred embodiment of the compound according to formula (II) corresponds to the following formula:wherein the above-mentioned definitions apply to the groups occurring.

[0043] A particularly preferred embodiment of the compound according to formula (II) corresponds to the following formula: where the definitions given above apply to the groups occurring.

[0044] A particularly preferred embodiment of the compound according to formula (II) corresponds to the following formula:wherein the above-mentioned definitions apply to the groups occurring.

[0045] A particularly preferred embodiment of the compound according to formula (II) corresponds to the following formula:wherein the above-mentioned definitions apply to the groups occurring.

[0046] A particularly preferred embodiment of the compound according to formula (II) corresponds to the following formula:wherein the above-mentioned definitions apply to the groups occurring.

[0047] A particularly preferred embodiment of the compound according to formula (II) corresponds to the following formula:wherein the definitions given above apply to the groups occurring.

[0048] Preferably, for compounds of the formula (I-1-a), (II-1-b), (II-1-a), (II-1-b), (II-2-a), (II-2-b), (II-3-a) and (II-3-b) Z is CR 1 and E is S(=O)2. Preferably, p is 0.

[0049] Preferably, in groups of the formula (Het-a), two or three groups T are equal to N. Particularly preferred groups (Het-a) are selected from pyrimidyl, pyridazinyl, pyrazinyl and triazinyl, which can optionally be substituted with radicals R 2 can be substituted.

[0050] The compounds of formula (I-1-a), (II-1-b), (II-1-a), (II-1-b), (II-2-a), (II-2-b), (II-3-a) and (II-3-b) are as such the subject of the present invention.

[0051] The following compounds are examples of compounds according to formula (I) or (II). 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82

[0052] The compounds according to formula (I) and (II) can be prepared by a suitable combination of organic reactions known to the person skilled in the art, for example Buchwald coupling and condensation reactions between amines and aldehydes.

[0053] Exemplary reaction routes for preparing the compounds are shown below. The skilled person may, within the scope of his or her general technical knowledge, deviate from or modify these reaction routes to prepare further compounds falling within the scope of formulas (I) and (II). Ar: aryl or heteroaryl group R: organic residue L: Leaving group, for example halide, tosylate or mesylate

[0054] According to the reaction pathway shown in Scheme 1, a thio-substituted benzimidazole group is prepared from a 1,2-diaminobenzene containing a thio group via a condensation reaction with an aldehyde. The corresponding sulfoxide derivative is then prepared via an oxidation reaction. The free NH group of the benzimidazole is then substituted with an aryl or heteroaryl group, for example, via a Buchwald coupling. Ar: aryl or heteroaryl group R: organic residue L: Leaving group, for example halide, tosylate or mesylate

[0055] Scheme 2 shows an analogous reaction pathway for the preparation of derivatives of formula (II). The reactions correspond to those discussed in Scheme 1.

[0056] The invention thus relates to a process for the preparation of compounds of (I-1-a), (I-1-b), (II-1-a), (II-1-b), (II-2-a), (II-2-b), (II-3-a) and (II-3-b), characterized in that at least one condensation reaction between an aldehyde and an aryl compound which contains at least one amino group is involved.

[0057] The process preferably further comprises at least one oxidation reaction. The process also preferably further comprises at least one transition metal-catalyzed coupling reaction, preferably a Buchwald coupling reaction.

[0058] The above-described compounds of the invention, particularly compounds substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid, or boronic esters, can be used as monomers to produce corresponding oligomers, dendrimers, or polymers. Suitable reactive leaving groups include, for example, bromine, iodine, chlorine, boronic acids, boronic esters, amines, alkenyl or alkynyl groups with a terminal CC double bond or CC triple bond, oxiranes, oxetanes, groups that undergo cycloaddition, for example, a 1,3-dipolar cycloaddition, such as dienes or azides, carboxylic acid derivatives, alcohols, and silanes.

[0059] The invention therefore further relates to oligomers, polymers or dendrimers comprising one or more compounds according to formula (I-1-a), (I-1-b), (II-1-a), (II-1-b), (II-2-a), (II-2-b), (II-3-a) and (II-3-b), wherein the bond(s) to the polymer, oligomer or dendrimer are at any R 1 or R 2substituted positions. Depending on the linkage of the compound according to the invention, the compound is part of a side chain of the oligomer or polymer or part of the main chain. An oligomer within the meaning of this invention is understood to be a compound composed of at least three monomer units. A polymer within the meaning of the invention 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 the linearly linked structures, the units according to the above-mentioned formulas can be directly linked to one another, or they can be linked to one another via a bivalent group, for example, via a substituted or unsubstituted alkylene group, via a heteroatom, or via a bivalent aromatic or heteroaromatic group. In branched and dendritic structures, for example, three or more units according to the above-mentioned formulas can be linked to form a branched or dendritic oligomer or polymer via a trivalent or higher-valent group, for example, via a trivalent or higher-valent aromatic or heteroaromatic group.

[0060] The same preferences apply to the repeating units in oligomers, dendrimers and polymers as described above for the compounds according to the invention.

[0061] To produce the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. Suitable and preferred comonomers are selected from fluorenes (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 typically contain additional 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.

[0062] The polymers, oligomers and dendrimers according to the invention have advantageous properties, in particular long lifetimes, high efficiencies and good color coordinates.

[0063] The polymers and oligomers according to the invention are generally prepared by polymerizing one or more types of monomers, at least one of which leads to repeating units of the above-mentioned formulas in the polymer. Suitable polymerization reactions are known to the person skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions that lead to CC or CN linkages are the following: (A) SUZUKI polymerization; (B) YAMAMOTO polymerization; (C) STILLE polymerization; and (D) HARTWIG-BUCHWALD polymerization.

[0064] How the polymerization can be carried out by these methods and how the polymers can then be separated from the reaction medium and purified is known to the person skilled in the art and is described in detail in the literature, for example in WO 2003 / 048225, WO 2004 / 037887 and WO 2004 / 037887.

[0065] The present invention therefore also relates to a process for preparing the polymers, oligomers and dendrimers according to the invention, which is characterized in that they are prepared by polymerization according to SUZUKI, polymerization according to YAMAMOTO, polymerization according to STILLE or polymerization according to HARTWIG-BUCHWALD. The dendrimers according to the invention can be prepared by processes known to the person skilled in the art or analogously thereto. Suitable processes are described in the literature, for example 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.

[0066] For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention are required. These formulations can be, for example, solutions, dispersions, or miniemulsions. It may be preferable to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-, or p-xylene, methyl benzoate, dimethylanisole, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, or mixtures of these solvents.

[0067] The invention therefore further provides a formulation, in particular a solution, dispersion or miniemulsion, comprising at least one compound according to formula (I-1-a), (I-1-b), (II-1-a), (II-1-b), (II-2-a), (II-2-b), (II-3-a) and (II-3-b) or at least one polymer, oligomer or dendrimer comprising at least one unit according to these formulas and at least one solvent, preferably an organic solvent. How such solutions can be prepared is known to the person skilled in the art and is described, for example, in WO 2002 / 072714, WO 2003 / 019694 and the literature cited therein.

[0068] The compounds according to formula (I) or (II) are suitable for use in electronic devices, particularly in organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds are used in different functions and in different layers of the organic electroluminescent device.

[0069] In general, the use of the compounds in an electron-transporting layer or in an emitting layer is preferred.

[0070] The invention therefore further relates to the use of the compounds according to formula (I) or (II) in electronic devices. The electronic devices are preferably selected from the group consisting of 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), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), organic plasmon-emitting diodes, and particularly preferably organic electroluminescent devices (OLEDs).

[0071] The organic electroluminescent device according to the invention preferably contains an anode, a cathode, and one or more organic layers, wherein at least one organic layer contains one or more compounds of formula (I) or (II). The organic electroluminescent device preferably further contains at least one electroluminescent layer. The electroluminescent layer may contain a compound of formula (I) or (II), but the compound of formula (I) or (II) may also be present exclusively in another layer of the device, for example, in an electron-transport layer.

[0072] These other layers, which can optionally be present in the organic electroluminescent device according to the invention, 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 (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.It should be noted, however, that not every one of these layers necessarily has to be present and the choice of layers always depends on the compounds used and, in particular, on whether the electroluminescent device is fluorescent or phosphorescent.

[0073] The organic electroluminescent device can also contain multiple emitting layers. In this case, these emitting layers particularly preferably have a total of multiple emission maxima between 380 nm and 750 nm, resulting in overall white emission. This means that different emitting compounds that can fluoresce or phosphoresce and that emit blue, yellow, orange, or red light are used in the emitting layers. Systems with three emitting layers are particularly preferred, with the three layers exhibiting blue, green, and orange or red emission (for the basic structure, see, for example, WO 2005 / 011013). Emitters that have broadband emission bands and thus exhibit white emission are also suitable for white emission.

[0074] It is preferred that the device according to the invention comprises one or more phosphorescent dopants. Furthermore, the compound may also comprise one or more fluorescent dopants. According to one possible embodiment, the device according to the invention comprises at least one phosphorescent dopant and at least one fluorescent dopant. However, the device according to the invention may also comprise exclusively one or more fluorescent dopants.

[0075] Particularly suitable as phosphorescent dopants (= triplet emitters) are compounds which, upon suitable excitation, emit light, preferably in the visible range, and which also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are used as phosphorescent emitters, in particular compounds containing iridium, platinum, or copper.

[0076] For the purposes of the present invention, all luminescent iridium, platinum or copper complexes are considered to be phosphorescent compounds.

[0077] In a preferred embodiment of the present invention, the compounds according to the invention are used as matrix material in combination with one or more dopants, preferably phosphorescent dopants.

[0078] In a system containing a matrix material and a dopant, a dopant is understood to be the component whose proportion in the mixture is the 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 the larger.

[0079] The proportion of the matrix material in the emitting layer is typically between 50.0 and 99.9 vol.%, preferably between 80.0 and 99.5 vol.%, and particularly preferably for fluorescent emitting layers between 92.0 and 99.5 vol.%, and for phosphorescent emitting layers between 85.0 and 97.0 vol.%. 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 for fluorescent emitting layers between 0.5 and 8.0 vol.%, and for phosphorescent emitting layers between 3.0 and 15.0 vol.%.

[0080] An emitting layer of an organic electroluminescent device can also contain systems comprising multiple matrix materials (mixed-matrix systems) and / or multiple dopants. Mixed-matrix systems are preferably used in phosphorescent organic electroluminescent devices. Even in the case of mixed-matrix systems, the dopants are generally the materials whose proportion is the smaller in the system, and the matrix materials are the materials whose proportion is the larger in the system. In individual cases, however, the proportion of a single matrix material in the system can be smaller than the proportion of a single dopant.

[0081] In a preferred embodiment of the invention, the compounds according to the invention 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 is a material with electron-transporting properties. The compounds according to the invention preferably represent the material with electron-transporting properties.

[0082] 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.

[0083] The mixed-matrix systems can comprise one or more dopants. According to the invention, the dopant compound(s) together comprise a proportion of 0.1 to 50.0 vol.% of the total mixture, and preferably a proportion of 0.5 to 20.0 vol.% of the total mixture. Accordingly, the matrix components together comprise a proportion of 50.0 to 99.9 vol.% of the total mixture, and preferably a proportion of 80.0 to 99.5 vol.% of the total mixture.

[0084] 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 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. 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. B. according to WO 2005 / 111172, azaboroles or boronate esters, e.g.according to WO 2006 / 117052, triazine derivatives, e.g. according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, aluminum complexes, e.g. BAlq, diazasilole and tetraazasilole derivatives, e.g. according to WO 2010 / 054729, diazaphosphole derivatives, e.g. according to WO 2010 / 054730 and aluminum complexes, e.g. BAlQ.

[0085] For phosphorescent dopants for use in mixed-matrix systems, the same preferences apply as stated above.

[0086] In a further preferred embodiment of the invention, the compounds according to the invention are used as electron-transport material in an electron-transport or electron-injection layer. The emitting layer can contain fluorescent and / or phosphorescent emitters. If the compounds are used as electron-transport material, it may be preferred if they are doped, for example with alkali metal complexes, such as Liq (lithium hydroxyquinolinate). The combination of the compound according to the invention in an electron-transport layer with an electron-injection layer is also suitable. Suitable materials for the electron-injection layer include, for example, alkali or alkaline earth fluorides, such as LiF.

[0087] In yet another preferred embodiment of the invention, the compounds according to the invention are used as hole-blocking material in a hole-blocking layer. A hole-blocking layer is understood to be a layer that directly adjoins an emitting layer on the cathode side.

[0088] The materials preferably used in the electronic devices according to the invention for the respective functions are listed below.

[0089] Preferred fluorescent dopants are selected from the class of arylamines. An arylamine or an aromatic amine within the meaning of this invention is understood to be a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, particularly preferably with at least 14 aromatic ring atoms. Preferred examples are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to be a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position.An aromatic anthracenediamine is understood to be a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably in the 9,10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, with the diarylamino groups on the pyrene preferably bonded in the 1-position or 1,6-position, respectively.

[0090] Preferred phosphorescent dopants can be found in applications WO 2000 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 2005 / 033244, WO 2005 / 019373, and US 2005 / 0258742. In general, all phosphorescent complexes used in the prior art for phosphorescent OLEDs and known to those skilled in the art in the field of organic electroluminescent devices are suitable.

[0091] Preferred matrix materials for fluorescent dopants are selected from the classes of oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthylanthracene), in particular oligoarylenes containing condensed aromatic groups, oligoarylenevinylenes (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), atropisomers (e.g. according to WO 2006 / 048268), boronic acid derivatives (e.g. according to WO 2006 / 117052) or 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, oligoarylenevinylenes, ketones, phosphine oxides, and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzphenanthrene, and / or pyrene, or atropisomers of these compounds. An oligoarylene, within the meaning of this invention, is understood to mean a compound in which at least three aryl or arylene groups are bonded to one another.

[0092] Preferred matrix materials for phosphorescent dopants, for use as single matrix or mixed matrix, were given above.

[0093] Suitable charge transport materials which can be used in the hole injection or hole transport layer or electron blocking layer or in the electron transport layer of the organic electroluminescent 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 which are used in these layers according to the prior art.

[0094] Examples of preferred hole transport materials that can be used in a hole transport, hole injection or electron blocking layer in the electroluminescent device according to the invention are indenofluorenamines and derivatives (e.g. according to WO 06 / 122630 or WO 06 / 100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (e.g. according to WO 01 / 049806), amine derivatives with condensed aromatics (e.g. according to US 5,061,569), the amine derivatives disclosed in WO 95 / 09147, monobenzoindenofluorenamines (e.g. according to WO 08 / 006449) or dibenzoindenofluorenamines (e.g. according to WO 07 / 140847). Further suitable hole transport and hole injection materials are derivatives of the compounds shown above, as disclosed in JP 2001 / 226331, EP 676461, EP 650955, WO 01 / 049806, US 4780536, WO 98 / 30071, EP 891121, EP 1661888, JP 2006 / 253445, EP 650955, WO 06 / 073054 and US 5061569.

[0095] Metals with low work functions, metal alloys, or multilayer structures composed of different metals are preferred as the cathode of the organic electroluminescent device, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys composed of an alkali or alkaline earth metal and silver, for example, an alloy of magnesium and silver, are also suitable. In multilayer structures, in addition to the metals mentioned, other metals with a relatively high work function, such as Ag or Al, can also be used. Combinations of the metals, such as Ca / Ag, Mg / Ag, or Ba / Ag, are then generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor.Suitable materials for this purpose include alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Lithium quinolinate (LiQ) can also be used. The thickness of this layer is preferably between 0.5 and 5 nm.

[0096] Materials with a high work function are preferred as anodes. The anode preferably has a work function greater than 4.5 eV vs. vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Metal / metal oxide electrodes (e.g., Al / Ni / NiO) can also be used. x , Al / PtO x) may be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to enable either irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Also preferred are conductive, doped organic materials, especially conductive doped polymers.

[0097] The device is structured, contacted and finally sealed accordingly (depending on the application), since the lifetime of the devices according to the invention is shortened in the presence of water and / or air.

[0098] 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 sublimated in vacuum sublimation systems at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6 mbar. However, it is also possible that the initial pressure is even lower, for example less than 10 -7 mbar.

[0099] Also preferred is an organic electroluminescent 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 sublimated at a pressure between 10 -5mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (e.g., BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0100] Also preferred is an organic electroluminescent device, characterized in that one or more layers are produced from solution, such as by spin coating, or by any printing process, such as screen printing, flexographic printing, gravure printing (engraving), slot-die printing, slot-die coating, nozzle printing, or offset printing, but particularly preferably LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. Soluble compounds according to formula (I) or formula (II) are required for this purpose. High solubility can be achieved by suitable substitution of the compounds.

[0101] It is further preferred that, to produce an organic electroluminescent device according to the invention, one or more layers are applied from solution and one or more layers are applied by a sublimation process.

[0102] According to the invention, the electronic devices comprising one or more compounds according to formula (I) or (II) can be used in displays, as light sources in lighting applications and as light sources in medical and / or cosmetic applications (e.g. light therapy).

[0103] The devices according to the invention preferably have one or more of the advantages listed below: - when using the compounds according to formula (I) or (II) in the devices, in particular as matrix materials for phosphorescent emitters, a high power efficiency and a low operating voltage of the devices can be achieved - when using the compounds according to formula (I) or (II), a long service life of the electronic device is obtained. - the compounds according to formula (I) or (II) have significantly better solubility and film-forming properties compared to materials known in the prior art, in particular compared to carbazole-based matrix materials

[0104] The invention is explained in more detail by the following exemplary embodiments. The invention is not limited to the scope of the explicitly disclosed examples. Working examples: 15.7 g (90.8 mmol) of 5-chloro-2-nitroaniline and 10.2 g (90.8 mmol) of sodium tert-butoxide are added to a solution of 23.8 g (86.5 mmol) of 4-(9H-carbazol-9-yl)-benzenethiol in 600 ml of propanol and heated to boiling for 4 h. The mixture is poured into 1000 ml of water, the beige precipitate is filtered off with suction, washed with water, and dried. The product content is 1H-NMR approx. 97% with a total yield of 33.8 g (95%). 56.4 g (323.2 mmol) of Na2S2O4 were added portionwise to a solution of 33.2 g (80.8 mmol) of 5[(4-N-carbazolphenyl)thio]-2-nitrobenzenamine in 1200 ml of ethanol and 300 ml of water, and then heated to boiling for 4 h. The ethanol was distilled off in vacuo, and the mixture was extracted with ethyl acetate. The organic phase was washed with 4 x 50 mL H2O, dried over MgSO4, and the solvents were removed in vacuo. The pure product was obtained by recrystallization. The product content is 98% according to HPLC, with a total yield of 30.2 g (98%). 5 g (50 mmol) of benzaldehyde is added dropwise to 19 g (50 mmol) of 5[(4-N-carbazolphenyl)thio]-1,2-benzenediamine in 300 ml of DMF and 10 ml of concentrated sulfuric acid and stirred for 2 h at room temperature. The mixture is poured onto 500 g of ice and extracted with dichloromethane.The organic phase is washed with 4 x 50 mL H2O, dried over MgSO4, and the solvents are removed in vacuo. The pure product is obtained by recrystallization. The product content according to HPLC is 98%, with a total yield of 11.4 g (49%).

[0105] Under protective gas, 22.9 g (49 mmol) of 5[(2-phenyl-1H-benzimidazol-5-yl)thio]-9-phenyl-N-carbazole are placed in 0.3 L of glacial acetic acid. 33 mL (619 mmol) of 30% H2O2 solution are added dropwise to this solution and stirred overnight. Na2SO3 solution is added to the mixture, the phases are separated, and the solvent is removed in vacuo. The product content is 1H-NMR approx. 98% with a total yield of 23.2 g (95%). 14.3 g (28.2 mmol) of 5[(2-phenyl-1H-benzimidazol-5-yl)sulfonyl]-9-phenyl-N-carbazole were dissolved in 225 mL of dimethylformamide under a protective gas atmosphere, and 1.5 g of NaH, 60% in mineral oil (37.5 mmol) were added. After 1 h at room temperature, a solution of 2-chloro-4,6-diphenyl-[1,3,5]-triazine (8.5 g, 31.75 mmol) in 75 mL of dimethylformamide was added dropwise. The reaction mixture was then stirred at room temperature for 12 h. After this time, the reaction mixture was poured onto ice and extracted three times with dichloromethane. The combined organic phases were dried over Na2SO4 and concentrated. The residue is extracted with hot toluene and recrystallized in toluene, then sublimed under high vacuum. The purity is 99.9%. The yield is 17.36 g (23.7 mmol, 83%). 2) Syntheses of precursors analogous to step 3 in Example 1 reactant reactant product yield 2a 46% 3a 46% 4a 53% 15.6 g (50 mmol) of 2,2-dibromo-1,1-biphenyl are dissolved in 500 mL of toluene. 2.3 g (2.5 mmol) of tris(dibenzylideneacetone)-dipalladium(0), 10 mL of 1M t-Bu3P in toluene, and 11.5 g (120 mmol) of sodium tert-butoxide are then added. 19.9 g (40 mmol) of 4-(2-phenyl-3H-benzimidazole-5-sulfonyl)-phenylamine are then added. The mixture is heated to 110 °C for 20 h, then cooled to room temperature, and 400 mL of water is added. The mixture is extracted with ethyl acetate, then the combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The residue is recrystallized from toluene and dichloromethane / isopropanol. The yield is 12.8 g (25.6 mmol), corresponding to 45% of theory. 6.6 g (42.12 mmol) of bromobenzene, 23.4 g (47 mmol) of 9-[4-(2-phenyl-3H-benzimidazole-5-sulfonyl)-phenyl]-9H-carbazole, and 29.2 g of Rb2CO3 are suspended in 250 mL of p-xylene. 0.95 g (4.2 mmol) of Pd(OAc)2 and 12 are added to this suspension.6 ml of a 1M tri-tert-butylphosphine solution are added. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated, washed three times with 200 mL of water, and then evaporated to dryness. The residue is extracted hot with toluene, recrystallized from toluene, and finally sublimed under high vacuum. The purity is 99.9%. Yield: 19.4 g (33 mmol), 72% of theory. 4) Synthesis of compound 5

[0106] Analogously to the last step in Example 1, the following compound 5 can be obtained: e.g. reactant reactant product yield 5 57% 5) Synthesis of Compound 6: 13.5 g (42.12 mmol) of 3-bromo-9-phenyl-9H-carbazole, 23.3 g (47 mmol) of 5[(2-phenyl-1H-benzimidazol-5-yl)sulfonyl]-9-phenyl-N-carbazole, and 29.2 g of Rb2CO3 were suspended in 250 mL of p-xylene. 0.95 g (4.2 mmol) of Pd(OAc)2 and 12.6 mL of a 1M tri-tert-butylphosphine solution were added to this suspension. The reaction mixture was heated under reflux for 16 h. After cooling, the organic phase was separated, washed three times with 200 mL of water, and then evaporated to dryness. The residue was extracted hot with toluene, recrystallized from toluene, and finally sublimed under high vacuum; the purity was 99.9%. Yield: 26 g (35 mmol), 75% of theory. 6) Syntheses of compounds 2, 4, 7, 8 and 9

[0107] Analogous to the step described above, the following compounds can be obtained: e.g. reactant reactant product yield 2 46% 4 48% 7 72% 8 47% 9 39% 7) Synthesis of the compound: 1033 g (120 mmol) of 5-phenylsulfonyl-1H-benzoimidazol-2-ylamine in 300 ml of MeOH are treated with 12.1 g (100 mmol) of phenylboronic acid. 0.78 g (5.5 mmol) of Cu2O is added to this solution, and the mixture is stirred at room temperature for 4 h. The mixture is then cooled to room temperature, and 400 ml of water is added. The mixture is extracted with ethyl acetate, then the combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The residue is recrystallized from toluene. The yield is 28 g (80 mmol), corresponding to 67% of theory.

[0108] According to the first step of the synthesis of compound 3, compound 10 is obtained from intermediate 10b: e.g. reactant reactant product yield 10 54% 8) Synthesis of compound 11

[0109] According to the first step of the synthesis of compound 3, compound 11 can be obtained: e.g. reactant reactant product yield 11 46%

[0110] The following reference materials are used: Example 9: Solutions and compositions containing matrix materials and TEG1 for OLEDs

[0111] Solutions Ref and A to K, as summarized in Table 1, are prepared as follows: First, 200 mg of TMM and 50 mg of TEG1 are dissolved in 10 mL of chlorobenzene and stirred until the solution is clear. The solution is filtered using a Millipore Millex LS, Hydrophobic PTFE 5.0 µm filter. Table 1: Composition of the solutions composition Ratio (based on weight) concentration Solution-Ref TMM1 + TEG1 75% : 25% 15 mg / ml Solution A 1 + TEG1 75% : 25% 25 mg / ml Solution B 5 + TEG1 75% : 25% 25 mg / ml Solution C 6 + TEG1 75% : 25% 25 mg / ml Solution D 7 + TEG1 75% : 25% 25 mg / ml Solution E 2 + TEG1 75% : 25% 25 mg / ml Solution F 4 + TEG1 75% : 25% 25 mg / ml Solution G 8 + TEG1 75% : 25% 25 mg / ml Solution H 9 + TEG1 75% : 25% 25 mg / ml Solution I 10 + TEG1 75% : 25% 25 mg / ml Solution J 11 + TEG1 75% : 25% 25 mg / ml Solution K 3 + TEG1 75% : 25% 25 mg / ml

[0112] The solutions are used to coat the emitting layer of OLEDs. The corresponding solid composition can be obtained by evaporating the solvent from the solutions. This can be used to prepare further formulations. Example 10: Manufacturing the OLEDs

[0113] OLED-Ref and the inventive OLED-A to OLED-K, which all have the IOT / PEDOT / Interlayer / EML / Cathode structure, are manufactured using the corresponding solutions, as summarized in Table 2, according to the following procedure: 1) Spin-coating of 80 nm PEDOT (Baytron P Al 4083) onto an ITO-coated glass substrate and annealing at 180°C for 10 minutes. 2) Coating of a 20 nm interlayer by spin-coating a toluene solution of HIL-012 (Merck KGaA) (concentration 0.5 wt%) in a glove box. 3) Bake the interlayer at 180 °C for 1 h in a glove box. 4) Coating of an 80 nm emitting layer by spin coating a corresponding solution according to Table 1. 5) Bake the device at 180 °C for 10 min. 6) Evaporation of a Ba / Al cathode (3 nm + 150 nm). 7) Encapsulation of the device. Example 11: Measurements and comparison of results

[0114] The resulting OLEDs are characterized using standard methods. The following properties are measured: UIL characteristics, electroluminescence spectrum, color coordinates (CIEx and CIEy), efficiency, and operating voltage. The results are summarized in Table 3, with OLED-Ref serving as a comparison according to the state of the art. In Table 3, U on for the threshold voltage, and U(100) for the voltage at 100 cd / m 2 . Table 3: Measurement results with OLED-Ref and OLED-A to OLED-K Max. Eff. [cd / A] Uon [V] U(100) [V] CIEx @ 100 cd / m 2 CIEy @ 100 cd / m 2 OLED Ref 8,2 3,8 6,5 0,33 0,62 OLED-A 27,0 3,0 4,5 0,33 0,62 OLED-B 24,5 2,5 3,6 0,33 0,62 OLED-C 32,3 2,6 4,0 0,34 0,62 OLED-D 29,2 2,6 3,7 0,33 0,62 OLED-E 16,4 2,9 4,6 0,33 0,62 OLED-F 30,3 2,6 4,0 0,35 0,62 OLED-G 30,4 2,6 4,0 0,34 0,62 OLED-H 27,0 2,7 4,2 0,34 0,61 OLED-I 18,7 3,3 5,6 0,34 0,62 OLED-J 28,8 2,7 3,8 0,33 0,62 OLED-K 32,7 2,7 4,9 0,35 0,61

[0115] As can be seen from Table 3, significantly improved phosphorescent OLEDs with respect to operating voltage and efficiency are obtained using the matrix materials of the invention. All OLEDs exhibit comparable color coordinates.

[0116] It is also possible (not explicitly shown) to use the compounds according to the invention as triplet matrix materials in combination with another matrix material (mixed matrix).

[0117] Furthermore, the use with other triplet emitters than TEG1 also produces good results.

Claims

[1] Electronic device containing at least one organic layer, wherein the organic layer comprises one or more compounds of a formula (I) or (II), wherein the symbols appearing are: E is a divalent group chosen from S=O and S(=O)2; W, X are the same or different at each occurrence N, P or CR 1 ; Y is the same or different at each occurrence NR 1 , PR 1 , O or S; Z is equal to C if a substituent is attached, and is otherwise the same or different at each occurrence CR 1 or N; R 1 is the same or different at each occurrence: H, D, F, Cl, Br, I, C(=O)R 2 , CN, Si(R 2 )3, N(R 2 )2, NO2, P(=O)(R 2 )2, S(=O)R 2 , S(=O)2R 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, wherein the above-mentioned groups are each substituted by one or more radicals R 2 may be substituted and wherein one or more CH2 groups in the above-mentioned groups are substituted by -R 2 C=CR 2 -, -C=C-, Si(R 2 )2, C=O, C=S, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 2 ), -O-, -S-, SO or SO2 and where one or more H atoms in the above-mentioned groups can be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 2may be substituted, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 2 may be substituted, where two or more radicals R 1 can be linked together to form a ring; where the group R 1 which is bonded to the group E, is selected from aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, each of which is bonded to one or more radicals R 2 can be substituted; R 2 is the same or different at each occurrence: H, D, F, Cl, Br, I, C(=O)R 3 , CN, Si(R 3 )3, N(R 3 )2 , NO2, P(=O)(R 3 )2, S(=O)R 3 , S(=O)2R 3, 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, wherein the above-mentioned groups are each substituted by one or more radicals R 3 may be substituted and wherein one or more CH2 groups in the above-mentioned groups are substituted by -R 3 C=CR 3 -, -C≡C-, Si(R 3 )2, C=O, C=S, C=NR 3 , -C(=O)O-, -C(=O)NR 3 -, NR 3 , P(=O)(R 3 ), -O-, -S-, SO or SO2 and where one or more H atoms in the above-mentioned groups can be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 3may be substituted, or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 3 may be substituted, where two or more radicals R 2 can be linked together and form a ring; R 3 is, identically or differently at each occurrence, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by D or F; two or more substituents R 3 be linked together and form a ring. [2] Electronic device according to claim 1, characterized by that E is equal to S(=O)2. [3] Electronic device according to claim 1 or 2, characterized by that the group E is bound in meta- or para-position to the group Y. [4] Electronic device according to one or more of claims 1 to 3, characterized by that W equals N. [5] Electronic device according to one or more of claims 1 to 4, characterized by that X equals CR 1 is. [6] Electronic device according to one or more of claims 1 to 5, characterized by that Y equals NR 1 is. [7] Electronic device according to one or more of claims 1 to 6, characterized by that the compound of formula (I) or (II) contains at least one group R 1 contains, which is selected from - Heteroaryl groups with 5 to 20 aromatic ring atoms, which are substituted by one or more radicals R 2 may be substituted and which contain at least one heteroaromatic five-membered ring with two or more heteroatoms selected from N, O and S; - Heteroaryl groups with 5 to 20 aromatic ring atoms, which are substituted by one or more radicals R 2may be substituted and which contain at least one heteroaromatic six-membered ring with one or more heteroatoms selected from N, O and S; and - Carbazole derivatives which are substituted with one or more radicals R 2 can be substituted. [8] Electronic device according to one or more of claims 1 to 7, characterized by that the device 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), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), organic plasmon-emitting diodes and organic electroluminescent devices (OLEDs). [9] Electronic device according to one or more of claims 1 to 8, characterized by that the compound according to formula (I) or (II) is contained as matrix material in an emitting layer or is contained as electron transport material in an electron transport layer or an electron injection layer.