Organic electronic device

Abstract

The invention relates to an organic electronic device, in particular an organic light-emitting device, comprising an organic layer containing a compound of formula (1) as OLED material and a second compound of formula (2) as OLED material, and to a mixture or formulation containing compounds of formulae (1) and (2), wherein the compound of formula (1) is selected from compounds containing two pyrimidine or triazine units, and the compound of formula (2) is selected from indolocarbazoles.

Description

TECHNICAL FIELD

[0001] The present application relates to an organic electronic device, in particular an organic light emitting device, which contains an organic layer comprising a first compound of formula (1) and a second compound of formula (2), and to a mixture or formulation containing compounds of formula (1) and (2), wherein the compound of formula (1) is selected from the class of compounds containing two pyrimidine or triazine units, and the compound of formula (2) is selected from the class of indolocarbazoles. BACKGROUND

[0002] The construction of organic electronic devices, including electroluminescent devices such as OLEDs - organic light emitting diodes or OLECs - organic light emitting electrochemical cells, which use organic semiconductors as functional materials, has long been known. In addition to fluorescent emitters, the light emitting materials used here are increasingly organic metal complexes which exhibit phosphorescence rather than fluorescence. For quantum mechanical reasons, the use of organic metal compounds as phosphorescent emitters makes it possible to increase the energy and power efficiency by a factor of up to four. However, in general, OLEDs, and in particular also OLEDs which exhibit triplet light emission (phosphorescence), still need to be improved, for example with regard to efficiency, operating voltage and lifetime. The performance of a device does not only depend on the triplet light emitter used. More particularly, other materials used, such as matrix materials, are also of particular importance here. Therefore, improvements in these materials can also lead to a significant improvement in the performance of OLEDs.

[0003] Host materials used in organic electronic devices are well known to the person skilled in the art. The term "matrix material" is also frequently used in the prior art when referring to host materials for phosphorescent emitters. This use of the term is also applicable to the present application. At present, a large number of host materials have been developed for both fluorescent and phosphorescent electronic devices.

[0004] A further way of improving the performance data of electronic devices, in particular of organic electroluminescent devices, is the use of combinations of two or more materials, in particular combinations of host materials or matrix materials.

[0005] KR 20100131745 A, WO 2012048779 A1, JP 2015106658 A, WO 2015169412 A1, WO 2015014434 A1, US 2016329502 A, WO 17178311 A1, CN 108250189 A, WO 19132545 A1, WO 19066315 A2, WO 19231210 A1, US 2019312215 A, US 2019198780 A1, WO 20235976 A1, WO 2021052921 A1, WO 20032428 A1, KR 20200141385 A, KR 20200145270 A, KR 20200145198 A, US 2023172055 A1 disclose bistriazine compounds as host material, which can also be used in combination with other host materials.

[0006] US 6229012 and US 20140299192 disclose bistriazine compounds as electron transport material or host material.

[0007] These materials, especially when used as matrix material, often still need to be improved. It was therefore an object of the present application to provide a matrix material suitable for use in organic electronic devices, especially for use in fluorescent or phosphorescent OLEDs, and to cause good device properties, especially in terms of improved lifetime, and to provide corresponding electronic devices. This is especially the case when used in combination with low to medium emitter concentrations, i.e. in the order of 3% to 20%, especially 3% to 15%, more preferably 4% to 10%, most preferably 4% to 8%, since the device lifetime is particularly limited here.

[0008] It has now been found that the electronic devices below containing compounds of formula (1) and (2) are improved compared to the prior art, especially when the compounds are used as matrix material for phosphorescent dopants.

[0009] It has also been found that the object is achieved and the disadvantages of the prior art are eliminated by the combination of at least one compound of formula (1) as first host material and at least one compound of formula (2) as second host material in the light-emitting layer of an organic electronic device, especially an organic electroluminescent device. The use of this material combination for the production of a light-emitting layer in an organic electronic device results in very good properties of these devices, especially in terms of lifetime, especially at equal or improved operating voltage and comparable efficiency. SUMMARY

[0010] The present application first provides an organic electronic device, comprising an anode, a cathode and at least one organic layer comprising at least one compound of formula (1) and at least one compound of formula (2), formula (1), formula (2), wherein the symbols and indices used are as follows: X is independently N or CR 8 wherein at least one X is N; Z is selected from the group consisting of divalent radicals Z-1 to Z-23, wherein the radicals Z-1 to Z-23 can be substituted by one or more substituents R 7 and wherein the dotted bonds are each bonded to L1or L2; W is O or S; Ar1, Ar2, Ar3, Ar4are the same or different and are independently an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which can be substituted by one or more R 7 groups; Ar5is in each case the same or different and is independently an aromatic or electron-rich heteroaromatic ring system having 5 to 40 ring atoms and which can be substituted by one or more R 7 groups, with the exception of indolocarbazolyl as electron-rich heteroaromatic ring system; R 6 are the same or different in each case and are D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group can in each case be substituted by one or more R 7 groups and where one or more non-adjacent CH2groups can be replaced by Si(R 7)2, C=0, NR 7 , O, S or CONR 7 instead, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which can in each case be substituted by one or more R 7 groups; R 7 are identical or different in each case and are D, F, CI, Br, I, N(R 8 )2, CN, N02, OR 8 , SR 8 , Si(R 8 )3, B(OR 8 )2, C(=0)R 8 , P(=0)(R 8 )2, S(=0)R 8 , S(=0)2R 8 , OS02R 8 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl groups can in each case be substituted by one or more R 8 groups, where one or more non-adjacent CH2 groups can be replaced by Si(R 8 )2, C=0, NR 8 , O, S or CONR 8 instead, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which can in each case be substituted by one or more R 8 groups; furthermore, two or more R 7 groups together can form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; preferably, the R 7 groups do not form any such ring system; R 8 are identical or different in each case and are H, D, F or an aliphatic, aromatic or heteroaromatic organic group, in particular a hydrocarbon group, having 1 to 20 carbon atoms, where one or more hydrogen atoms can also be replaced by F; s are identical or different in each case and are 0, 1, 2, 3 or 4; u are identical or different in each case and are 0, 1 or 2, where the compound of formula (2) contains at least one deuterium.

[0011] The application also provides a method for producing an organic electronic device, preferably an electroluminescent device, as described above or as described below, preferably, the organic layers are applied by vapor deposition or from solution.

[0012] The application also provides a mixture comprising at least one compound of formula (1) as described above or as later preferred, and at least one compound of formula (2) as described above or as later preferred, and optionally with further compounds selected from phosphorescent emitters, fluorescent emitters and / or emitters showing TADF (thermally activated delayed fluorescence), and / or solvents.

[0013] The respective preferred embodiments as described hereinafter likewise form part of the subject matter of the present application. Surprising and advantageous effects are achieved by specific selection of the compounds of formula (1) and the compounds of formula (2). DETAILED DESCRIPTION

[0014] In the present patent application, "D" or "D atom" means deuterium.

[0015] The organic electronic device of the present application is preferably selected from the group consisting of organic integrated circuits (OICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors, and organic photoreceptors.

[0016] The organic electronic device of the present application is more preferably an organic electroluminescent device.

[0017] The organic electroluminescent device of the present application, or synonymously organic electroluminescent device or organic light emitting device, is for example an organic light emitting transistor (OLET), an organic field-quench device (OFQD), an organic light emitting electrochemical cell (OLEC), an organic laser diode (O-laser) or an organic light emitting diode (OLED). The organic electroluminescent device of the present application is especially an organic light emitting diode or an organic light emitting electrochemical cell. The device of the present application is more preferably an OLED.

[0018] In one embodiment of the present application, the organic layer of the organic electronic device of the present application comprises an emitting layer comprising at least one compound of formula (1) and a compound of formula (2) as described above or as later preferred.

[0019] The organic layers of the inventive device, the light-emitting layer containing a combination of materials comprising at least one compound of formula (1 ) as described above or below and at least one compound of formula (2), preferably comprise, in addition to the light-emitting layer (EML), a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), an exciton blocking layer, an electron blocking layer and / or a charge generation layer. The inventive device can also comprise two or more layers from this group, which are preferably selected from the group consisting of EML, HIL, HTL, ETL, EIL and HBL. An intermediate layer with, for example, exciton blocking function can likewise be introduced between two light-emitting layers.

[0020] If there are multiple light-emitting layers, it is preferred that these light-emitting layers together have multiple emission peaks between 380 nm and 750 nm, so that the overall result is white emission; in other words, multiple fluorescently or phosphorescently emitting compounds are used in the light-emitting layer. Two or more fluorescent and / or phosphorescent compounds can also be present in the light-emitting layer. Particularly preferred are systems with three light-emitting layers, which display blue, green and orange or red emission. As an alternative to the combinations as described above, the light-emitting layer can also display yellow emission. Such combinations are known to the person skilled in the art. The organic electroluminescent device according to the application can also be a tandem electroluminescent device, in particular for white-emitting OLEDs.

[0021] The device can also comprise further layers of inorganic materials, or be formed entirely from inorganic materials.

[0022] The light-emitting layer comprising at least one compound of formula (1 ) and at least one compound of formula (2) preferably comprises at least one further compound selected from the group consisting of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0023] Particularly preferred is a light-emitting layer containing at least one compound of formula (1 ) and at least one compound of formula (2), which is a phosphorescent layer, characterized in that, in addition to the host material combination of compounds of formula (1 ) and formula (2) as described above, at least one phosphorescent emitter is also comprised. Suitable emitter selection and preferred emitters are described below.

[0024] Aryl groups in the context of the present application contain 6 to 40 ring atoms, preferably carbon atoms. Heteroaryl groups in the context of the present application contain 5 to 40 ring atoms, wherein the ring atoms include carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms adds up to at least 5. The heteroatoms are preferably selected from N, O and / or S. Herein, aryl groups or heteroaryl groups refer to: simple aromatic rings, i.e. phenyl groups, derived from benzene; or simple heteroaromatic rings, e.g. derived from pyridine, pyrimidine or thiophene; or fused aryl or heteroaryl groups, e.g. derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline. Thus, aryl groups having 6 to 18 carbon atoms are preferably phenyl, naphthyl, phenanthryl or triphenylenyl, without restriction on the attachment of the aryl group as a substituent. Aryl or heteroaryl groups in the context of the present application can carry one or more groups, wherein suitable groups are described below. If no such groups are described, the aryl group or heteroaryl group is unsubstituted.

[0025] Aromatic ring systems in the context of the present application contain 6 to 60 or 6 to 40 ring atoms, preferably carbon atoms, in the ring system. Aromatic ring systems also include aryl groups as described above.

[0026] Aromatic ring systems having 6 to 18 carbon atoms are preferably selected from phenyl, biphenyl, naphthyl, phenanthryl and triphenylenyl.

[0027] Heteroaromatic ring systems in the context of the present application contain 5 to 40 ring atoms and at least one heteroatom. Preferred heteroaromatic ring systems have 9 to 40 ring atoms and at least one heteroatom. Heteroaromatic ring systems also include heteroaryl groups as described above. The heteroatoms in the heteroaromatic ring system are preferably selected from N, O and / or S.

[0028] Aromatic or heteroaromatic ring systems in the context of the present application refer to systems which do not necessarily contain only aryl or heteroaryl groups, but in which also a plurality of aryl or heteroaryl groups can be interrupted by non-aromatic units, preferably less than 10% of non-H atoms, such as carbon or oxygen atoms or carbonyl groups. For example, systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diaryl ether, stilbene, etc. should thus also be regarded as aromatic or heteroaromatic ring systems in the context of the present application, as are systems in which two or more aryl groups are interrupted by, for example, linear or cyclic alkyl groups or by silyl groups. Furthermore, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, such as biphenyl, terphenyl, quaterphenyl or bipyridine, are likewise encompassed in the definition of aromatic or heteroaromatic ring systems.

[0029] Aromatic or heteroaromatic ring systems having 5 to 40 or 6 to 60 ring atoms and which can be attached via any position in the aromatic or heteroaromatic system mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzo-fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, binaphthyl, terphenyl, binitophenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydro-pyrene, tetrahydro-pyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, triindene, isotriindene, spirotrindene, spiroisotriindene, 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, phenoxazine, phenothiazine, pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenoxazine, phenothiazine, fluorubin, naphthidine, azacarbazole, benzocarbolin, 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.

[0030] Electron-rich heteroaromatic ring systems are characterized in that they contain at least one electron-rich heteroaryl group and, in particular, do not have electron-deficient heteroaryl groups.

[0031] Electron-deficient heteroaryl groups are six-membered heteroaryl groups having at least one nitrogen atom or five-membered heteroaryl groups having at least two heteroatoms, one of which is a nitrogen atom and the other of which is an oxygen, sulfur or substituted nitrogen atom, where in each case further aryl or heteroaryl groups can also be fused on these groups. Conversely, electron-rich heteroaryl groups are five-membered heteroaryl groups having exactly one heteroatom selected from oxygen, sulfur and substituted nitrogen, which can fuse further aryl groups and / or further electron-rich five-membered heteroaryl groups. Examples of electron-rich heteroaryl groups are thus pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene or indenocarbazole. Electron-rich heteroaryl groups are also referred to as electron-rich heteroaromatic groups.

[0032] The abbreviations Ar1, Ar2, Ar3and Ar4are in each case identical or different and denote an aromatic or electron-rich heteroaromatic ring system having 5 to 40 ring atoms and which can be substituted by one or more R 7 groups or substituents R 7 groups or substituents R 7 are as described above or below. Preferred definitions of Ar1and Ar2and Ar3and Ar4are as described below.

[0033] The abbreviation Ar5is in each case identical or different and is an aromatic or electron-rich heteroaromatic ring system having 5 to 40 ring atoms and which can be substituted by one or more R 7 groups or substituents R 7 groups or substituents R 7 are as described above or below. Preferred definitions of Ar5are as described below.

[0034] In the context of the present specification, the expression that two or more groups together can form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system is to be understood, inter alia, to mean that the two groups are connected to one another by a chemical bond in the formal elimination of two hydrogen atoms. This is illustrated by the following scheme: .

[0035] However, in addition, the above expression is also to be understood to mean that, if one of the two groups is hydrogen, the second group is bonded to the position of the hydrogen atom, thereby forming a ring. This is illustrated by the following scheme: .

[0036] Cyclic alkyl groups in the context of the present application are to be understood to mean monocyclic, bicyclic or polycyclic groups.

[0037] In the context of the present application, linear, branched or cyclic C1- to C 20- an alkyl group is for example a methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1 -methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1 -methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1 -bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1 -dimethyl-n-hex-1 -yl, 1,1 -dimethyl-n-hept-1 -yl, 1,1 -dimethyl-n-oct-1 -yl, 1,1 -dimethyl-n-dec-1 -yl, 1,1 -dimethyl-n-dodec-1 -yl, 1,1 -dimethyl-n-tetradec-1 -yl, 1,1 -dimethyl-n-hexadec-1 -yl, 1,1 -dimethyl-n-octadec-1 -yl, 1,1 -diethyl-n-hex-1 -yl, 1,1 -diethyl-n-hept-1 -yl, 1,1 -diethyl-n-oct-1 -yl, 1,1 -diethyl-n-dec-1 -yl, 1,1 -diethyl-n-dodec-1 -yl, 1,1 -diethyl-n-tetradec-1 -yl, 1,1 -diethyl-n-hexadec-1 -yl, 1,1 -diethyl-n-octadec-1 -yl, 1 -(n-propyl)-cyclohex-1 -yl, 1 -(n-butyl)-cyclohex-1 -yl, 1 -(n-hexyl)-cyclohex-1 -yl, 1 -(n-octyl)-cyclohex-1 -yl and 1 -(n-decyl)-cyclohex-1 -yl group.

[0038] An alkenyl group is an alkyl group as described above containing at least one double bond.

[0039] An alkynyl group is an alkyl group as described above containing at least one triple bond.

[0040] A phosphorescent emitter in the context of the present application is a compound which exhibits luminescence from an excited state with a higher spin multiplicity, i.e. spin state > 1, in particular from an excited triplet state. In the context of the present application, all luminescent complexes with transition metals or lanthanides are to be regarded as phosphorescent emitters. A more precise definition is given below.

[0041] When the host material of the light-emitting layer comprising at least one compound of formula (1) as described above or as preferably described below and at least one compound of formula (2) as described above or as preferably described below is used for a phosphorescent emitter, it is preferred that its triplet energy is not significantly lower than the triplet energy of the phosphorescent emitter. In terms of triplet energy levels, the case where T1(emitter) - T1(host) < 0.2 eV, more preferably < 0.15 eV, most preferably < 0.1 eV is preferred. Here T1(host) is the triplet energy level of the host material in the light-emitting layer, this condition applies to each of the two host materials, and T1(emitter) is the triplet energy level of the phosphorescent emitter. If the light-emitting layer contains more than two host materials, the above-mentioned relationship preferably also applies to each of the other host materials.

[0042] When the host material of the light-emitting layer comprising at least one compound of formula (1) as described above or as preferably described below and at least one compound of formula (2) as described above or as preferably described below is used for a phosphorescent emitter, it is preferred that the HOMO (highest occupied molecular orbital) energy of the hole-transport material of formula (2) as described above or as preferably described below, calculated by the method described in the experimental part, below abbreviated hTMM-HOMO(calc), satisfies the following condition: hTMM-HOMO(calc) is > -5.50 eV, preferably > -5.37 eV, more preferably > -5.27 eV.

[0043] When the host material of the light-emitting layer comprising at least one compound of formula (1) as described above or as preferably described below and at least one compound of formula (2) as described above or as preferably described below is used for a phosphorescent emitter, it is preferred that the HOMO (highest occupied molecular orbital) energy of the hole-transport material of formula (2) as described above or as preferably described below, hTMM-HOMO(calc), and the HOMO energy of the phosphorescent emitter as preferably described below, below abbreviated emitter-HOMO(calc), satisfy the following condition: emitter-HOMO(calc) - hTMM-HOMO(calc) < 0.35 eV, preferably < 0.23 eV, more preferably < 0.15 eV.

[0044] The following describes preferred embodiments of the compounds of formula (1) and their presence in the devices of the application. The preferred embodiments also apply to the mixtures of the application or to the formulations of the application.

[0045] Preferred compounds of formula (1) are the compounds of formulae (1a), (1b) and (1c), formula (1a), Formula (1 b), Formula (1 c), wherein R 8 , Z, Ar1, Ar2, Ar3and Ar4have the definitions given above or preferably given below.

[0046] Rin the pyrimidine group of the compounds of formula (1 b) and (1 c) is in each case identical or different and is preferably H, D, F, a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms and in each case can be substituted by F or D, an aromatic ring system having 6 to 20 carbon atoms and in each case can be substituted by F or D. 8 Rin the pyrimidine group of the compounds of formula (1 b) and (1 c) is in each case identical or different and is preferably H, D, F, a linear alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms and in each case can be substituted by F or D, an aromatic ring system having 6 to 20 carbon atoms and in each case can be substituted by F or D. 8 Rin the pyrimidine group of the compounds of formula (1 b) and (1 c) is in each case identical or different and is more preferably D, a deuterated linear alkyl group having 1 to 20 carbon atoms or a deuterated branched or cyclic alkyl group having 3 to 20 carbon atoms or a deuterated aromatic ring system having 6 to 20 carbon atoms. 8 Rin the pyrimidine group of the compounds of formula (1 b) and (1 c) is in each case identical or different and is more preferably D, CD3, C6D6or C 12 D 12 .

[0047] The compounds of formula (1 a) are a particularly preferred embodiment of the compounds of formula (1 ), wherein Z, Ar1, Ar2, Ar3and Ar4have the definitions given above or preferably given below.

[0048] In a preferred embodiment of the compounds of formula (1 ), (1 a), (1 b) and (1 c), the compounds are partially or completely deuterated, wherein the degree of deuteration of the compounds of formula (1 ), (1 a), (1 b) and (1 c) is preferably at least 10% to 100%, more preferably 20% to 80%, most preferably 30% to 70%. The degree of deuteration is reported in units of mol%.

[0049] In one embodiment of the compounds of formula (1 ), (1 a), (1 b) and (1 c), the bivalent Z group is preferably a bivalent group Z-1 to Z-15, wherein W and R 7 have the definitions given above or preferably given below, preferably Z-1, Z-4, Z-5, Z-7, Z-9, Z-10 and Z-1 1. In one embodiment, the bivalent Z group is preferably selected from Z-1 to Z-10, wherein W and R 7has the definition given above or preferably given below. In one embodiment, the divalent Z group is alternatively preferably selected from Z-1, Z-4, Z-5, Z-7, Z-9 and Z-10, wherein W and R 7 has the definition given above or preferably given below. In this embodiment, the divalent Z group is alternatively more preferably selected from Z-1, Z-4, Z-7 and Z-9, wherein W and R 7 has the definition given above or preferably given below. Z-1 is very particularly preferred. Z-9 is very particularly preferred.

[0050] In the compounds of the formula (1 ), (1 a), (1 b) or (1 c) as described above or as preferably described, W is preferably O.

[0051] In one embodiment of the compounds of the formula (1 ), (1 a), (1 b) and (1 c), the divalent Z group is preferably a divalent group Z-16 to Z-23, wherein R 7 has the definition given above or preferably given below. In this embodiment, the divalent Z group is alternatively more preferably selected from Z-16, Z-18 and Z-23, wherein R 7 has the definition given above or preferably given below.

[0052] R in the divalent groups Z-1 to Z-23 7 are identical or different in each case and are preferably D, F, CN or an aromatic ring system having 6 to 20 carbon atoms and in each case can be substituted by D or F. R in the divalent groups Z-1 to Z-23 of the compounds of the formula (1 ), (1 a), (1 b) and (1 c) 7 are identical or different in each case and are more preferably D or a deuterated aromatic ring system having 6 to 20 carbon atoms. R in the divalent groups Z-1 to Z-23 of the compounds of the formula (1 ), (1 a), (1 b) and (1 c) 7 are identical or different in each case and are more preferably D, C6D6 or C 12 D 12 , most preferably D.

[0053] Si(R 8 )3, R 8 are preferably identical and are an aromatic ring system having 6 to 20 ring atoms and can be substituted by one or more D or F groups, more preferably by D. In Si(R 8 )3, R 8 are more preferably selected from non-deuterated, partially deuterated or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl.

[0054] In the compounds of the formula (1), (1a), (1b) and (1c) or preferably of the formula (1), (1a), (1b) and (1c), Ar1, Ar2, Ar3and Ar4are identical or different and are preferably an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which can be substituted by one or more R 7 groups, wherein R 7 has the definition given or preferably given above.

[0055] In the compounds of the formula (1), (1a), (1b) and (1c) or preferably of the formula (1), (1a), (1b) and (1c), Ar1, Ar2, Ar3and Ar4are identical or different and are preferably an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which can be substituted by one or more R , wherein Y 3 are identical or different in each case and are O, S, NAr or C(R)2, R is methyl or phenyl, R 3 is H or R 7 ; the dotted bond denotes a bond to the remainder of the formula (1), (1a), (1b) and (1c); and when Ar occurs, Ar is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which can be substituted by D; m is 0 or 1, where m = 0 means that no Ar group is present, and R 7 has the definition given above.

[0056] Y 3 preferably O, S, NAr or C(CH3)2. Y 3 more preferably O or S, most preferably O.

[0057] Ar is preferably a divalent phenyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl, mesityl, dibenzofuranyl or dibenzothiophenyl, which can be partially or completely deuterated. Ar is more preferably phenyl, 1,2-biphenyl, 1,3-biphenyl or 1,4-biphenyl, which can be partially or completely deuterated.

[0058] In structures Ar-1 to Ar-28, the substituents R 3 are preferably identical or different in each case and are selected from H, D, F, CN or an aromatic ring system having 6 to 30 ring atoms, which can be deuterated. In structures Ar-1 to Ar-28, the substituents R 3 are more preferably identical or different in each case and are selected from H, D, non-deuterated or partially or completely deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl. In structures Ar-1 to Ar-28, the substituents R 3 are most preferably identical or different in each case and are selected from H and D.

[0059] In the compounds of the formulae (1), (1a), (1b) and (1c) or preferably of the formulae (1), (1a), (1b) and (1c), Ar1, Ar2, Ar3and Ar4are identical or different in each case and are preferably selected from Ar-1 to Ar-4 and Ar-12 to Ar-16 as described above, wherein Y 3 , Ar, m, R 3 have the definitions given or preferably given above.

[0060] In one embodiment of the application, Ar1in the compounds of the formula (1), (1a), (1b) or (1c) is a group Ar-1 to Ar-3 or Ar-12 to Ar-16 as described above, wherein Y 3 is O or S, Ar, when it occurs, is phenyl, 1,2-biphenyl, 1,3-biphenyl or 1,4-biphenyl, which can be partially or completely deuterated, and m and R 3 have the definitions given or preferably given above. More preferably, Ar, when it occurs, is phenylidene, which can be partially or completely deuterated.

[0061] In one embodiment of the application, Ar2in the compounds of the formula (1), (1a), (1b) or (1c) is a group Ar-1 to Ar-34 or Ar-12 to Ar-16 as described above, wherein Y3 is O or S, and when Ar occurs, Ar is phenyl, 1,2-biphenyl, 1,3-biphenyl or 1,4-biphenyl, which can be partially or completely deuterated, and m and R 3 have the definitions given or preferably given above.

[0062] In one embodiment of the present application, Ar3 in the compounds of the formulae (1 ), (1 a), (1 b) or (1 c) is an Ar-1 to Ar-3 or Ar-12 to Ar-16 radical as described above, wherein Y 3 is O or S, and when Ar occurs, Ar is phenyl, 1,2-biphenyl, 1,3-biphenyl or 1,4-biphenyl, which can be partially or completely deuterated, and m and R 3 have the definitions given or preferably given above.

[0063] In one embodiment of the present application, Ar4 in the compounds of the formulae (1 ), (1 a), (1 b) or (1 c) is an Ar-1 to Ar-3 or Ar-12 to Ar-16 radical as described above, wherein Y 3 is O or S, and when Ar occurs, Ar is phenyl, 1,2-biphenyl, 1,3-biphenyl or 1,4-biphenyl, which can be partially or completely deuterated, and m and R 3 have the definitions given or preferably given above.

[0064] In one embodiment of the present application, at least Ar1 or at least Ar3 in one of the formulae (1 ), (1 a), (1 b) and (1 c) is an Ar-2 or Ar-13 radical, wherein R 3 have the definitions given or preferably given above.

[0065] In one embodiment of the present application, it is particularly preferred that at least one substituent selected from Ar1 to Ar4 has a different definition than the remaining substituents selected from Ar1 to Ar4.

[0066] In one embodiment of the present application, it is particularly preferred that at least two substituents selected from Ar1 to Ar4 have a different definition than the remaining substituents selected from Ar1 to Ar4.

[0067] In one embodiment of the present application, it is very particularly preferred that at least one substituent selected from Ar1 to Ar4 has a different definition than the remaining substituents selected from Ar1 to Ar4, and that the two substituents Ar1 and Ar2 have a different definition than the two substituents Ar3 and Ar4.

[0068] Examples of suitable compounds of the formulae (1 ), (1 a), (1 b) and (1 c) are the structures shown below in Table 1.

[0069] Table 1:

[0070] Particularly suitable compounds of formula (1), (1a), (1b) and (1c) are compounds E1 to E27 of Table 2.

[0071] Table 2:

[0072] The preparation of compounds of formula (1), (1a), (1b), (1c), or of the preferred compounds of Table 1, and of compounds E1 to E27 is known to the person skilled in the art. Said compounds can be prepared by synthetic steps known to the person skilled in the art, such as halogenation reactions, preferably bromination reactions, and subsequent organometallic coupling reactions, such as Suzuki coupling, Heck coupling or Hiyama- Buchwald coupling. The preparation of compounds of formula (1), or of the preferred compounds of Table 1, and of compounds E1 to E27 can in particular be deduced from US 20160329502 A, WO 2017178311 A1 and WO 2021052921 A1. In particular in WO 2017178311 A1, reference is made to the synthetic examples on page 46 and pages 81 to 106. In particular in WO 2021052921 A1, reference is made to the synthetic examples on page 32 and pages 116 to 125.

[0073] Compounds of formula (1) can be prepared according to the following Scheme 1, wherein L1, L2, Z, Ar1, Ar2, Ar3and Ar4have one of the above given or preferably given definitions.

[0074] Scheme 1:

[0075] Detailed reaction conditions are known from the prior art or described in the examples section.

[0076] These methods, if necessary, can then be followed by purification, such as recrystallization or sublimation, to obtain the compound of formula (1) with high purity, preferably greater than 99% (using [methods]). 1 (H NMR and / or HPLC determination).

[0077] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for deuterium atoms is to treat the compound to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound containing one or more deuterium atoms that is capable of releasing them under suitable conditions.

[0078] The platinum catalyst is preferably carbon-supported dry platinum, more preferably 5% carbon-supported dry platinum. The palladium catalyst is preferably carbon-supported dry palladium, more preferably 5% carbon-supported dry palladium. Suitable deuterium sources are D₂O, benzene-d₆, chloroform-d, acetonitrile-d₃, acetone-d₆, acetic acid-d₄, methanol-d₄, or toluene-d₈. Preferred deuterium sources are D₂O or a combination of D₂O and a fully deuterated organic solvent. Particularly preferred deuterium sources are combinations of D₂O and fully deuterated organic solvents, with no limitation on the fully deuterated solvent. Particularly suitable fully deuterated solvents are benzene-d₆ and toluene-d₈. Particularly preferred deuterium sources are combinations of D₂O and toluene-d₈. The reaction is preferably carried out under heating, more preferably at a temperature between 100°C and 200°C. Furthermore, the reaction is preferably carried out under pressure.

[0079] The following describes the compound of formula (2) (body material 2) and its preferred embodiments in the device of the present invention. The preferred embodiments of body material 2 of formula (2) are also applicable to the mixtures and / or formulations of the present invention.

[0080] The preferred compounds of formula (2) are compounds of formulas (2a), (2b), (2c), (2d), and (2e). Equation (2a), Equation (2b), Equation (2c), Equation (2d), Equation (2e), Among them, Ar5, R 6 , s and u have the definitions given above or preferably given later, and at least one of them is present in the compounds of formula (2a), (2b), (2c), (2d) and (2e).

[0081] The compounds of formulas (2a), (2b), (2d), and (2e) are particularly preferred embodiments of the compounds of formula (2), wherein Ar5, R 6s and u have the definitions given above or preferably given later.

[0082] The compounds of the formula (2a) and (2e) are very particularly preferred embodiments of the compounds of the formula (2), wherein Ar5, R 6 s and u have the definitions given above or preferably given later.

[0083] The compounds of the formula (2a) are particularly preferred embodiments of the compounds of the formula (2), wherein Ar5, R 6 s and u have the definitions given above or preferably given later.

[0084] The application therefore also provides an organic electroluminescent device as described above or as preferably described, wherein the at least one compound of the formula (2) corresponds to a compound of the formula (2a), (2b), (2c), (2d) or (2e) and wherein at least one deuterium is present in the compounds of the formula (2a), (2b), (2c), (2d) and (2e).

[0085] In this embodiment of the compounds of the formula (2), (2a), (2b), (2c), (2d) and (2e), the compounds are partially or completely deuterated, wherein the degree of deuteration of the compounds of the formula (2), (2a), (2b), (2c), (2d) and (2e) is preferably at least 10% to 100%, more preferably 50% to 95%, most preferably 70% to 90%. The degree of deuteration is reported in units of mol%.

[0086] The application therefore also provides an organic electronic device as described above, wherein the at least one compound of the formula (2) has a degree of deuteration of 10 mol% to 100 mol%.

[0087] If the deuterated matrix material 1 or 2 is a deuterated compound, it is possible that the at least one matrix material 1 or 2 is a mixture of deuterated compounds of the same chemical base structure, which only differ in the position of the deuterium atoms in the chemical base structure.

[0088] As described above, the corresponding deuterated methods are known to the person skilled in the art or are described, for example, in KR 2016041014 A, WO 2017 / 122988 A1, KR 2020052820 A, KR 101978651 B1 and WO 2018 / 110887 A1, or in Bulletin of the Chemical Society of Japan, 2021, 94(2), 600-605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071.

[0089] In one embodiment of the application, for the device of the application, a compound of the formula (2), (2a), (2b), (2c), (2d) or (2e) as described above is selected and these are used in the organic layer, preferably in the light-emitting layer, together with a compound of the formula (1) as described above or as preferred or together with a compound from Table 1 or the compounds E1 to E27.

[0090] In the compounds of the formula (2), (2a), (2b), (2c), (2d) and (2e), R 6 is preferably D, CN or an aromatic ring system having 6 to 60 ring atoms which in each case is substituted by one or more R 7 groups, where R 7 has the definitions given above or preferably given below. In the compounds of the formula (2), (2a), (2b), (2c), (2d) and (2e), R 6 is preferably D, a partially or completely deuterated phenyl, naphthyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl or triphenylmethanediyl.

[0091] In one preferred embodiment of the compounds of the formula (2), (2a), (2b), (2c), (2d) and (2e), R 6 is preferably D and s is 4 and u is 2 in each case, i.e. the compound is a compound of the formula (2), (2a), (2b), (2c), (2d) and (2e) which is completely deuterated on the indolocarbazole base skeleton, where Ar5 has the definitions given above or preferably given below.

[0092] In the compounds of the formula (2), (2a), (2b), (2c), (2d) and (2e) or preferably of the formula (2), (2a), (2b), (2c), (2d) and (2e), Ar5is identical or different in each case and is preferably Ar-1 to Ar-28 as described above, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms of Ar-29 to Ar-36, , wherein Y 3 , Ar, m, R 3 have the definitions given above or preferably given above and V2is O or S.

[0093] V2is preferably O.

[0094] In the structures Ar-29 to Ar-36, the substituents R 3 are preferably identical or different in each case and are selected from H, D, F, CN or an aromatic ring system having 6 to 30 ring atoms and which can be deuterated. In the structures Ar-29 to Ar-36, the substituents R 3 are more preferably identical or different in each case and are selected from H, D, non-deuterated or partially or completely deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl. In the structures Ar-29 to Ar-36, the substituents R 3 are most preferably identical or different in each case and are selected from H and D.

[0095] In the compounds of the formula (2), (2a), (2b), (2c), (2d) and (2e) or preferably of the formula (2), (2a), (2b), (2c), (2d) and (2e), Ar5is identical or different in each case and is preferably selected from Ar-1, Ar-2 to Ar-7, Ar-12 to Ar-16, Ar-21, Ar-22 and Ar-29 to Ar-32 as described above, wherein Y 3 , Ar, m, R 3 have the definitions given above or preferably given above.

[0096] In the compounds of the formula (2), (2a), (2b), (2c), (2d) and (2e) or preferably of the formula (2), (2a), (2b), (2c), (2d) and (2e), Ar5is in each case identical or different and is more preferably selected from Ar-1, Ar-2, Ar-3, Ar-4, Ar-5, Ar-12, Ar-13, Ar-14, Ar-15, Ar-16, Ar-22, Ar-29, Ar-30, Ar-31 and Ar-32 as described above, wherein Y 3 , Ar, m, R 3 have the definitions given above or preferably given above.

[0097] Preferably, the substituents Ar5are also at least partially or completely deuterated as described above or as preferably described.

[0098] In one preferred embodiment of the compounds of the formula (2), (2a), (2b), (2c), (2d) and (2e), R 6 is preferably D or a phenyl, naphthyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl or triphenyl-2-yl group which is partially or completely deuterated, and s is in each case 4 and u is 2, i.e. however, wherein at least one substituent R 6 and preferably one substituent R 6 is not D.

[0099] Examples of suitable compounds of the formula (2), (2a), (2b), (2c), (2d) and (2e) for combination with a compound of the formula (1) or a preferred compound of the formula (1) as described above or as preferably described are the compounds described in WO 19066315 A2 on pages 28 to 47, which are correspondingly deuterated.

[0100] Examples of suitable compounds of the formula (2), (2a), (2b), (2c), (2d) and (2e) for combination with a compound of the formula (1) or a preferred compound of the formula (1) as described above or as preferably described are the indolocarbazole compounds described in WO 22038066 A1 on pages 34 to 62, which are correspondingly deuterated.

[0101] Examples of suitable host materials of the formula (2), (2a), (2b), (2c), (2d) and (2e) selected according to the application and preferably for use in combination with at least one compound of the formula (1) in an electronic device according to the application are the structures given in Table 3 below.

[0102] The designations D1-Dx, e.g. D1 to D20, of the compounds in Table 3 and Table 4 mean that from 1 to x deuterium atoms, e.g. from 1 to 20 deuterium atoms, are present in the respective designated compound. The symbol x in Dx indicates the maximum possible number of deuterium substitution positions given in the following molecules.

[0103] Table 3:

[0104] Particularly suitable compounds of formula (2), (2a), (2b), (2c), (2d) and (2e) for use in combination with at least one compound of formula (1) in the electronic device of the present application are the compounds H1 to H30 in Table 4.

[0105] Table 4:

[0106] The preparation of compounds of formula (2), or preferably of compounds of formula (2), (2a), (2b), (2c), (2d) and (2e), and the preparation of the compounds from Table 3 and Table 4, is known to the person skilled in the art. Some of the compounds of formula (2) are commercially available. A suitable synthesis results from the synthesis examples on pages 86 to 91 of WO 19066315 A2.

[0107] Suitable deuterium substitution methods have been described above and apply accordingly.

[0108] The above-mentioned compounds of formula (1) and their preferred embodiments as described or the compounds from Table 1 and compounds E1 to E27 can be combined in the device of the present application with the mentioned compounds of formula (2), (2a), (2b), (2c), (2d) and (2e) and their preferred embodiments as described or the compounds from Table 3 or compounds H1 to H36 as desired.

[0109] The above specified combination of host materials of formula (1) with host materials of formula (2) is preferably as described above. Preferred combinations of host materials are likewise described below.

[0110] The application likewise provides a mixture comprising at least one compound of formula (1) and the compounds described as preferred embodiments thereof or from Table 1 and compounds E1 to E27 and at least one compound of formulae (2), (2a), (2b), (2c), (2d) and (2e) and the compounds described as preferred embodiments thereof or from Table 3 or compounds H1 to H36.

[0111] Very particularly preferred mixtures of compounds of formula (1) with compounds of formula (2) for use in the inventive device are obtained by combinations of compounds E1 to E27 with compounds H1 to H36, as shown in Table 5 below. For example, a first mixture M1 is a combination of compounds E1 with H1.

[0112] Table 5:

[0113] In the mixtures of the application or in the organic or light-emitting layer of the inventive device, the concentration of the host material of formula (1) as described above or as preferred is typically in the range of from 5 to 90% by weight, preferably in the range of from 10 to 85% by weight, more preferably in the range of from 20 to 85% by weight, even more preferably in the range of from 30 to 80% by weight, very particularly preferably in the range of from 20 to 60% by weight, most preferably in the range of from 30 to 50% by weight, based on the overall mixture or on the overall composition of the organic / light-emitting layer.

[0114] The concentration of the host material of formula (2) as described above or as preferably described in the mixture of the present application or in the organic layer or light-emitting layer of the device of the present application is in the range of from 10 to 95 % by weight, preferably in the range of from 15 to 90 % by weight, more preferably in the range of from 15 to 80 % by weight, even more preferably in the range of from 20 to 70 % by weight, very particularly preferably in the range of from 40 to 80 % by weight, and most preferably in the range of from 50 to 70 % by weight, based on the overall mixture or based on the overall composition of the organic layer or light-emitting layer.

[0115] The present application also relates to a mixture, which contains, in addition to the above-mentioned host materials 1 and 2 of formula (1) and (2) as described above or as preferably described, in particular mixtures M1 to M972, at least one further compound and / or a solvent.

[0116] The present application also relates to a mixture, which contains, in addition to the above-mentioned host materials 1 and 2 of formula (1) and (2) as described above or as preferably described, in particular mixtures M1 to M972, at least one further compound, which is selected from matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters showing TADF (thermally activated delayed fluorescence).

[0117] For processing the mixtures of the present application from the liquid phase, for example by spin coating or by printing processes, formulations of the mixtures of the present application are required. These formulations can be, for example, solutions, dispersions or emulsions. The solvent used can preferably be a mixture of two or more solvents. Suitable and preferred solvents are, for example: toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetraline, o-dianisole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1 -methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decaline, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropyl naphthalene, amylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1 -bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1 -methylnaphthalene, 1 -ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate, or mixtures of these solvents.

[0118] If the mixtures of the present application using compounds of the formulae (1 ) and (2) as described above are used as matrix material or synonymously host material in the light-emitting layer, it is preferred to use them in combination with other compounds, for example in combination with other matrix materials, as a combination of a three-component host material.

[0119] In the light-emitting layer of the device of the present application, the concentration of the sum of all host materials is generally in the range from 10 to 95% by weight, preferably in the range from 15 to 90% by weight, more preferably in the range from 15 to 80% by weight, even more preferably in the range from 20 to 70% by weight, very particularly preferably in the range from 40 to 80% by weight, most preferably in the range from 50 to 70% by weight, based on the overall composition of the light-emitting layer.

[0120] Suitable matrix materials and emitters which can be used in the mixtures of the present application or in the organic layers of the present application are described below.

[0121] The person skilled in the art can easily consider the various materials known from the prior art and thus select materials suitable for use in the layers of an organic electroluminescent device. Here, the person skilled in the art will reflect the chemical and physical properties of the materials in the usual way, as he knows that the materials in an organic electroluminescent device interact with one another. This relates, for example, to the energy levels of the orbitals (HOMO, LUMO) or else triplet and singlet levels, and other material properties.

[0122] Suitable matrix materials which can be used in combination with the compounds according to the application are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triaryl amines, carbazole derivatives, biscarbazoles, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, ambipolar matrix materials, borazoles or borates, triazine derivatives, zinc complexes, sila- or germa- azacyclopentadiene derivatives, phosphacyclopentadiene derivatives, bridged carbazole derivatives, mu-tetraphenyl derivatives or dibenzofuran derivatives. It is likewise possible for other phosphorescent emitters with a shorter emission wavelength than the actual emitter to be present in the mixture as co-hosts, or for compounds which do not participate in the charge transport to an appreciable extent, for example wide-bandgap compounds.

[0123] Wide-bandgap materials in the present context are materials within the scope of the disclosure of US 7,294,849, which are characterized by a bandgap of at least 3.5 eV, the bandgap referring to the gap between the HOMO and LUMO levels of the material.

[0124] The application also relates to a mixture which, in addition to the host materials of the formulae (1) and (2) mentioned above, in particular the mixtures M1 to M972, as described above or as preferred, comprises at least one phosphorescent emitter.

[0125] The application also relates to an organic electroluminescent device as described above or as preferred, wherein the light-emitting layer comprises, in addition to the host materials of the formulae (1) and (2) mentioned above, in particular the material combinations M1 to M972, at least one phosphorescent emitter.

[0126] The term "phosphorescent emitter" generally encompasses compounds which emit light by spin-forbidden transitions from excited states with higher spin multiplicity, i.e. spin states > 1, for example by transitions from triplet states or states with higher spin quantum number, for example quintet states. This preferably means transitions from triplet states.

[0127] Suitable phosphorescent emitters (= triplet emitters) are, in particular, compounds which, when suitably excited, emit light, preferably in the visible region; and which also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially a metal having this atomic number. Preferred phosphorescent emitters to be used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or platinum. In the context of the present application, all luminescent compounds containing the above-mentioned metals are regarded as phosphorescent emitters.

[0128] Generally, all phosphorescent complexes known to the person skilled in the art for use in the field of phosphorescent OLEDs and organic electroluminescent devices are suitable.

[0129] Preferred phosphorescent emitters according to the application comply with formula (IX), formula (IX), wherein the symbols and indices of this formula (IX) are defined as follows: n + m is 3, n is 1 or 2, m is 2 or 1, X is in each case identical or different and is N or CR, R is in each case identical or different and is H, D, F, CN or a branched or unbranched alkyl group having 1 to 10 carbon atoms or a partially or completely deuterated branched or unbranched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 4 to 7 carbon atoms which can be partially or completely substituted by deuterium, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms which can be partially or completely substituted by deuterium.

[0130] The application therefore also provides an organic electroluminescent device as described above or as preferred, characterized in that the emission layer, in addition to comprising the host materials 1 and 2, also comprises at least one phosphorescent emitter complying with formula (IX) as described above.

[0131] In the emitter of formula (IX), n is preferably 1 and m is preferably 2.

[0132] In the emitter of formula (IX), preferably one X is selected from N and the other X is CR, or all X are in each case identical or different and are CR.

[0133] In the emitter of formula (IX), at least one R is preferably different from H. In the emitter of formula (IX), preferably two R are different from H and have one of the other definitions given above for the emitter of formula (IX).

[0134] Preferred phosphorescent emitters according to the present application comply with formula (I), (II), (III), (IV) or (V), Formula (I) , Formula (II) , Formula (III) , Formula (IV) , Formula (V) , wherein the symbols and indices of these formulae (I), (II), (III), (IV) and (V) are defined as follows: R1is H or D, R2is H, D, F, CN or a branched or linear alkyl group having 1 to 10 carbon atoms or a partially or completely deuterated branched or linear alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 4 to 10 carbon atoms and which can be partially or completely substituted by deuterium.

[0135] Preferred phosphorescent emitters according to the present application comply with formula (VI), (VII) or (VIII), Formula (VI) , Formula (VII) , Formula (VIII) , wherein the symbols and indices of these formulae (VI), (VII) and (VIII) are defined as follows: R1is H or D, R2is H, D, F, CN or a branched or linear alkyl group having 1 to 10 carbon atoms or a partially or completely deuterated branched or linear alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 4 to 10 carbon atoms and which can be partially or completely substituted by deuterium.

[0136] Preferred examples of phosphorescent emitters are described in Table 5 on pages 120 to 126 and Table 6 on pages 127 to 129 of WO 2019 / 007867. The emitters described in said reference are incorporated into the present specification.

[0137] Particularly preferred examples of phosphorescent emitters are listed in the following Table 6.

[0138] Table 6:

[0139] In the mixtures of the present application or in the light-emitting layer of the device of the present application, preferably any mixture selected from the sum of mixtures M1 to M972 is combined with a compound of formula (I) to (IX) or a compound from Table 6.

[0140] The light-emitting layer of the organic electroluminescent device of the present application comprising at least one phosphorescent emitter is preferably an infrared, or yellow, orange, red, green, blue, or ultraviolet light-emitting layer, more preferably a yellow or green light-emitting layer, most preferably a green light-emitting layer.

[0141] Herein, a yellow light-emitting layer means a layer with a photoluminescence peak in the range from 540 nm to 570 nm. An orange light-emitting layer means a layer with a photoluminescence peak in the range from 570 nm to 600 nm. A red light-emitting layer means a layer with a photoluminescence peak in the range from 600 nm to 750 nm. A green light-emitting layer means a layer with a photoluminescence peak in the range from 490 nm to 540 nm. A blue light-emitting layer means a layer with a photoluminescence peak in the range from 440 nm to 490 nm. Herein the photoluminescence peak of a layer is determined by measuring the photoluminescence spectrum of a layer with a layer thickness of 50 nm at room temperature, wherein the layer comprises the host material 1 of formula (1), (1a), (1b) or (1c) and the combination of the present application of a host material 2 consisting of at least one of formula (2), (2a), (2b), (2c), (2d) and (2e), and the respective emitter.

[0142] The photoluminescence spectrum of the layer is recorded, for example, with a commercial photoluminescence spectrometer.

[0143] Typically, the photoluminescence spectrum of the selected emitter is measured in a 10 -5 The photoluminescence spectrum of the selected emitter is measured in a 10

[0144] Thus, preferred phosphorescent emitters are yellow emitters, preferably phosphorescent emitters of formula (I) to (IX) or from Table 6, with a triplet energy T1 of preferably about 2.3 eV to about 2.1 eV.

[0145] Thus, preferred phosphorescent emitters are green emitters, preferably phosphorescent emitters of the formulae (I) to (IX) or from Table 6, whose triplet energy T1 is preferably from about 2.5 eV to about 2.3 eV.

[0146] Thus, particularly preferred phosphorescent emitters are green emitters, preferably phosphorescent emitters of the formulae (I) to (IX) or from Table 6 as described above, whose triplet energy T1 is preferably from about 2.5 eV to about 2.3 eV.

[0147] Very particularly preferred is the selection of phosphorescent emitters, preferably phosphorescent emitters of the formulae (I) to (IX) or from Table 6 as described above, whose triplet energy T1 is preferably from about 2.5 eV to about 2.3 eV, which satisfy the above-mentioned prescribed energy level conditions with the compound of the formula (2) selected as hTMM: emitter-HOMO(calc) - hTMM-HOMO(calc) < 0.35 eV, preferably < 0.23 eV, more preferably < 0.15 eV.

[0148] It is also possible for fluorescent emitters to be present in the light-emitting layer of the inventive device or in the inventive mixture.

[0149] Preferred fluorescent light-emitting compounds are selected from aryl amines, wherein preferably at least one of the aromatic or heteroaromatic ring systems of the aryl amine is a fused ring system, more preferably at least having 14 ring atoms. Preferred examples of these compounds are aromatic anthracene amines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic boryl amines or aromatic boryl diamines. Aromatic anthracene amines are compounds in which a diaryl amino group is bonded directly to an anthracene radical, preferably in the 9-position. Aromatic anthracene diamines are compounds in which two diaryl amino groups are bonded directly to an anthracene radical, preferably in the 9,10-position. Aromatic pyrene amines, pyrene diamines, boryl amines and boryl diamines are defined analogously, wherein the diaryl amino group is bonded to the pyrene preferably in the 1 -position or in the 1,6-position. Further preferred light-emitting compounds are indenofluorene amines or indenofluorene diamines, benzoindenofluorene amines or benzoindenofluorene diamines, and diphenzoindenofluorene amines or diphenzoindenofluorene diamines, and indenofluorene derivatives having fused aryl radicals. Also preferred are pyrene aryl amines. Also preferred are benzoindenofluorene amines, benzo fluorene amines, expanded benzoindenofluorenes, phenoxazine, and fluorene derivatives connected with furan units or with thiophene units. The light-emitting device or mixture of the invention can additionally comprise materials which exhibit TADF (thermally activated delayed fluorescence).

[0150] In another preferred embodiment of the present application, at least one light-emitting layer of the organic electroluminescent device can have three or four different matrix materials, preferably three different matrix materials. These respective hybrid matrix systems can consist of the matrix materials described for host material 1 and host material 2, but in addition to comprising host material 1 or host material 2, a third or fourth matrix material can be comprised, for example a wide band gap material, a bipolar host material, an electron transport material (ETM) or a hole transport material (HTM).

[0151] Preferably, the hybrid matrix system is optimized for an emitter of one of the formulae (I) to (IX) or for an emitter from Table 6.

[0152] In one embodiment of the present application, the mixture comprises no further components, i.e. functional materials, in addition to the constituents of host material 1 of formula (1) and host material 2 as described above or as preferred. These are the material mixtures as such for the production of the light-emitting layer. These mixtures, also referred to as pre-mix systems, are used as the sole source of material for the vapor deposition of the light-emitting layer host material and maintain a constant mixing ratio in the vapor deposition. In this way, the vapor deposition of layers with a uniform distribution of components can be achieved in a simple and fast manner without the need for precise control of multiple material sources.

[0153] In an alternative embodiment of the present application, the mixture comprises, in addition to the constituents of host material 1 of formula (1) and host material 2 of formula (2) as described above or as preferred, a phosphorescent emitter as described above. This mixture can also be used as the sole source of material in the vapor deposition, with the mixing ratio being appropriate.

[0154] Preferably, the pre-mix system consists of two matrix materials, namely one compound of formula (1), (1a), (1b) or (1c) and one compound of one of formulae (2), (2a), (2b), (2c), (2d) or (2e).

[0155] The components or constituents of the organic layers of the devices of the present application can thus be processed by vapor deposition or from solution. In the case of processing from solution, the combination of host materials 1 and 2 as described above or as preferred, optionally with a phosphorescent emitter as described above or as preferred, is provided in a formulation containing at least one solvent. Suitable formulations have been described above.

[0156] According to preferred embodiments and luminescent compounds, the luminescent layer in the device of the present invention preferably contains a matrix material with an overall composition of 99.9 vol% to 1 vol%, more preferably 99 vol% to 10 vol%, particularly preferably 98 vol% to 60 vol%, and very particularly preferably 97 vol% to 80 vol%, based on the total composition of the luminescent material and the matrix material. The matrix material is composed of at least one compound of formula (1), (1a), (1b), or (1c) and at least one compound of one of (2), (2a), (2b), (2c), (2d), or (2e) according to preferred embodiments. Accordingly, the luminescent layer in the device of the present invention preferably contains a luminescent material with an overall composition of 0.1 vol% to 99 vol%, more preferably 1 vol% to 90 vol%, more preferably 2 vol% to 40 vol%, and most preferably 3 vol% to 20 vol%. If the compound is processed by solution, it is preferable to use an amount in weight % rather than the amount in volume % as specified above.

[0157] The present invention also relates to an organic electroluminescent device as described above or as preferably described, wherein the organic layer comprises a hole injection layer (HIL) and / or a hole transport layer (HTL), wherein the hole injection material and the hole transport material belong to the arylamine class.

[0158] The preferred layer order in the organic electroluminescent device of the present invention is as follows: Anode / hole injection layer / hole transport layer / light emission layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0159] This layer order is the preferred order.

[0160] At the same time, it should be pointed out again that not all of the mentioned layers must exist, and / or other layers may exist.

[0161] The material used for the electron transport layer can be any material that serves as the electron transport material in the electron transport layer according to existing technology. Particularly suitable are aluminum complexes such as Alq3, zirconium complexes such as Zrq4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, diazole derivatives, aromatic ketones, lactams, boranes, phosphazacyclopentane derivatives, and phosphine oxide derivatives.

[0162] The present invention also relates to an organic electroluminescent device as described above or as preferably described, wherein the organic layer comprises an electron injection layer (EIL) and / or an electron transport layer (ETL) and / or a hole blocking layer, wherein the electron injection material and / or electron transport material is selected from compounds of formulas (1), (1a), (1b) and (1c) as described above or as preferably described.

[0163] Suitable cathodes for the devices according to the application are metals with low work function, metal alloys or multilayer systems composed of various metals, for example alkali earth metals, alkali metals, main group metals or lanthanides (for example Ca, Ba, Mg, Al, In, Yb, Sm, etc.). Also suitable are alloys composed of alkali or alkali earth metals and silver, for example alloys composed of magnesium and silver. In the case of multilayer systems, in addition to the metals mentioned, other metals with relatively high work function, for example Ag or Al, can also be used, in which case combinations of the said metals are generally used, for example Ca / Ag, Mg / Ag or Ba / Ag. It can also be preferred to introduce a thin intermediate layer of a material with high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials which are useful for this purpose are alkali or alkali earth metal fluorides, but also the corresponding oxides or carbonates (for example LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Lithium quinolate (LiQ) can also be used for this purpose. The layer thickness of this layer is preferably between 0.5 nm and 5 nm.

[0164] Preferred anodes are materials with high work function. Preferably, the anode has a work function of greater than 4.5 eV versus vacuum. Firstly, for this purpose metals with high redox potential are suitable, for example Ag, Pt or Au. Secondly, metal / metal oxide electrodes (for example Al / Ni / NiO x , Al / PtO x ) can also be preferred. For some applications at least one of the electrodes must be transparent or partially transparent, so that the organic material can be irradiated (organic solar cells) or light can be coupled out (OLEDs, O-lasers). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Conductively doped organic materials, in particular conductively doped polymers, are also preferred. Furthermore, the anode can also consist of two or more layers, for example an inner layer of ITO and an outer layer of a metal oxide, which is preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0165] Since the presence of water and / or air can shorten the lifetime of the devices according to the application, the organic electroluminescent devices according to the application are structured as appropriate, provided with contact connections and finally sealed during the manufacturing process (depending on the application).

[0166] The manufacture of the devices according to the application is not limited here. One or more organic layers, including the light-emitting layer, can be applied by sublimation. In this case the material is applied by vapour deposition in a vacuum sublimation system at an initial pressure of less than 10 -5 millibar, preferably less than 10 -6 millibar. However, in this case even lower, for example less than 10 -7Initial pressures in the range of 10"1mbar are also possible.

[0167] The organic electroluminescent device according to the application is preferably characterized in that one or more layers are applied by the OVPD (organic vapor phase deposition) method or by means of carrier gas sublimation. In this case, the materials are applied at a pressure of 10"1mbar to 1 bar. A special case of this method is the OVJP (organic vapor phase jet printing) method, in which the materials are applied directly through a nozzle, whereby structuring is achieved (for example M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301). -5

[0168] The organic electroluminescent device according to the application is also preferably characterized in that one or more organic layers comprising the composition according to the application are produced from solution, for example by spin coating, or by any printing method such as screen printing, flexographic printing, nozzle printing or offset printing, but more preferably by LITI (light induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble host materials 1 and 2 as well as the phosphorescent emitter are required. The advantage of processing from solution is that, for example, the emission layer can be applied in a very simple and cost-effective manner. This technology is particularly suitable for large-scale production of organic electroluminescent devices.

[0169] Furthermore, hybrid methods are possible, for example, in which one or more layers are applied from solution and one or more further layers are applied by vapor deposition.

[0170] These methods are generally known to the person skilled in the art and can be applied to organic electroluminescent devices.

[0171] The application therefore also provides a method for producing an organic electroluminescent device according to the application as described above or as preferred, characterized in that the organic layers, preferably the emission layer, are applied by vapor deposition, in particular by the sublimation method and / or by OVPD (organic vapor phase deposition), and / or by means of carrier gas sublimation, or from solution, in particular by spin coating or by a printing method.

[0172] In the case of production by means of vapor deposition, in principle there are two ways in which the organic layers, preferably the emission layer, according to the application can be applied or vapor-deposited onto any substrate or previous layer. Firstly, the materials used are initially each contained in a material source and can finally be evaporated from different material sources ("co-evaporation"). Secondly, the individual materials can be premixed (premix system), the mixture being initially contained in a single material source and can finally be evaporated therefrom ("premix evaporation"). In this way, vapor deposition of an emission layer with a uniform distribution of the components can be achieved in a simple and rapid manner without the need for precise driving of a plurality of material sources.

[0173] The following processes are possible: ​A process for the production of an organic electronic device according to the application as described above or as preferred, characterized in that the organic layers, preferably the emitting layer, are applied by vapor deposition, especially by sublimation and / or by OVPD (organic vapor phase deposition) and / or by means of a carrier gas sublimation, or from solution, especially by spin coating or by printing processes.

[0174] A process for the production of an organic electronic device according to the application as described above or as preferred, characterized in that the emitting layer of the organic layers is applied by vapor deposition, wherein at least one compound of the formulae (1), (1a), (1b) and (1c) and at least one compound of the formulae (2), (2a), (2b), (2c), (2d) and (2e) are vapor-deposited from at least two material sources, either sequentially or simultaneously, together with any further material forming the emitting layer.

[0175] A process for the production of a device according to the application, characterized in that the emitting layer of the organic layers is applied by vapor deposition, wherein at least one compound of the formulae (1), (1a), (1b) and (1c) and at least one compound of the formulae (2), (2a), (2b), (2c), (2d) and (2e) are vapor-deposited as a premix together with an emitting material selected from the group consisting of phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence), either sequentially or simultaneously.

[0176] The electronic devices, especially organic electroluminescent devices, according to the application have one or more of the following surprising advantages compared to the prior art: 1. Electronic devices, especially organic electroluminescent devices, comprising a mixture or preferred embodiments of the compounds of the formulae (1) and (2) described above and below, especially as matrix material, have a very good lifetime, especially at low emitter concentrations.

[0177] 2. Electronic devices, especially organic electroluminescent devices, comprising a mixture or preferred embodiments of the compounds of the formulae (1) and (2) described above and below as matrix material have an excellent efficiency. In this case, the compounds of the formulae (1) and (2) of the application or the inventive mixtures of preferred embodiments described above and below lead to a low operating voltage when used in electronic devices.

[0178] 3. The mixtures or preferred embodiments of the compounds of the formulae (1) and (2) described above and below have an excellent glass film formation.

[0179] These above-mentioned advantages are not accompanied by an exceptionally severe deterioration of other electronic properties.

[0180] It should be noted that variations of the embodiments described in this application are covered by the scope of the present application. Any feature disclosed in this application may be substituted for any other feature disclosed in this application, unless the features are mutually exclusive. Consequently, any feature disclosed in this application should be seen as an example of a generic series or as an equivalent or similar feature, unless stated otherwise.

[0181] Unless particular features and / or steps are mutually exclusive, all features of the present application can be combined with each other in any way. This is especially true for preferred features of the present application. Likewise, features of non-essential combinations can be used individually (and not in combination).

[0182] The technical teachings disclosed in this application can be distilled and combined with other examples.

[0183] The present application is illustrated in detail by the following examples, without intending to be limited thereby.

[0184] Examples

[0185] General methods: In all quantum chemistry calculations, the Gaussian16 (version B.01) software package was used. Neutral singlet ground states were optimized at the B3LYP / 6-31G(d) level. HOMO and LUMO values were determined at the B3LYP / 6-31G(d) level against the ground state energy optimized at the B3LYP / 6-31G(d) level. Then, TD-DFT singlet and triplet excitations (vertical excitations) were calculated by the same method (B3LYP / 6-31G(d)) and optimized ground state geometries. Standard SCF and gradient convergence settings were used.

[0186] From the energy calculation, the HOMO(calc) as the last orbital occupied by two electrons (alpha occ. eigenvalue) and the LUMO(calc) as the first unoccupied orbital (alpha virt. eigenvalue) in Hartree units were obtained, where HEhand LEhdenote the HOMO energy in Hartree units and the LUMO energy in Hartree units, respectively. This was used to determine the HOMO and LUMO values in electron volts, calibrated by cyclic voltammetry, as follows: HOMO(calc) = 0.90603 x HEh x 27.211385 - 0.84836 LUMO(calc) = 0.99687 x LEh x 27.211385 - 0.72445 The triplet energy level T1 of a material is defined as the excitation energy (in eV) of the lowest excited state of multiplicity 3, i.e. (triplet), obtained from quantum chemical TD-DFT calculations.

[0187] The singlet energy level S1 of a material is defined as the excitation energy (in eV) of the lowest excited state of multiplicity 1, i.e. (singlet), obtained from quantum chemical TD-DFT calculations.

[0188] The lowest energy singlet state is referred to as S0.

[0189] The methods described herein are independent of the software package used and always give the same results. Examples of software commonly used for this purpose are “Gaussian09” (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.). In the present case, the energies were calculated using the software package “Gaussian16 (version B.01)”.

[0190] Synthesis Example

[0191] The following syntheses were all carried out in dry solvents under an atmosphere of protective gas, unless otherwise stated. The compounds can be prepared by synthetic methods known to the person skilled in the art.

[0192] 1) 2-dibenzofuran-1-yl-4,6-diphenyl[1,3,5]triazine

[0193] Dibenzofuran-1-boronic acid, 2-chloro-4,6-diphenyl-1,3,5-triazine and sodium carbonate were suspended in ethyleneglycol dimethyl ether and water. To this suspension, tri-o-tolylphosphine was added, followed by palladium(II) acetate, and the reaction mixture was heated under reflux for 16 hours. After cooling, the organic phase was separated, filtered through silica gel, washed three times with 200 ml of water and concentrated to dryness. The residue was recrystallized from toluene and dichloromethane / heptane. Yield 37 g (94 mmol), corresponding to 87% of the theoretical value.

[0194] 2) 2-(8-bromodibenzofuran-1-yl)-4,6-diphenyl[1,3,5]triazine

[0195] 70 g (190.0 mmol) of 2-dibenzofuran-1-yl-4,6-diphenyl[1,3,5]triazine was suspended in 2000 ml of acetic acid (100%) and 2000 ml of sulfuric acid (95%–98%). 34 g (190 mmol) of NBS was added in portions to the suspension, and the mixture was stirred in the dark for 2 hours. Subsequently, water / ice was added, and the solids were removed and washed with ethanol. The residue was recrystallized in toluene. The yield was 80 g (167 mmol), equivalent to 87% of the theoretical yield.

[0196] 3) 2,4-Diphenyl-6-[8-(4,4,5,5-tetramethyl[1,3,2]dioxaborphane-2-yl)-dibenzofuran-1-yl][1,3,5]triazine

[0197] In a 500 mL flask under a protective atmosphere, 60 g (125 mmol) of 2-(8-bromodibenzofuran-1-yl)-4,6-diphenyl-[1,3,5]triazine and 39 g (1051 mmol) of pinacol diborate (CAS 73183-34-3) were dissolved in 900 mL of dry DMF, and the mixture was degassed for 30 min. Subsequently, 37 g (376 mmol) of potassium acetate and 1.9 g (8.7 mmol) of palladium acetate were added, and the mixture was heated to 80 °C overnight. After the reaction was complete, the mixture was diluted with 300 mL of toluene and extracted with water. The solvent was removed by rotary evaporation, and the mixture was recrystallized from heptane. Yield: 61 g (117 mmol), 94% of theoretical value.

[0198] The following compounds were prepared in a similar manner:

[0199] 4) 2,4-Diphenyl-6-[8-(2,4-diphenyl-[1,3,5]triazine-2-yl)dibenzofuran-1-yl]-[1,3,5]triazine

[0200] 68.7 g (110.0 mmol) of 2,4-diphenyl-6-[8-(4,4,5,5-tetramethyl-[1,3,2]dioxaborphane-2-yl)-dibenzofuran-1-yl]-[1,3,5]triazine, 29.3 g (110.0 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine, and 21 g (210.0 mmol) of sodium carbonate were suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine was added to the suspension, followed by 112 mg (0.5 mmol) of palladium(II) acetate, and the reaction mixture was heated under reflux for 16 hours. After cooling, the organic phase was separated, filtered through silica gel, washed three times with 200 ml of water, and then concentrated to dryness. The product was purified by silica gel column chromatography using toluene / CHCl3 (1:1), and finally purified under high vacuum (p=5×10⁻⁶). -7 Sublimation at 1 mbar (purity 99.9%). Yield 51 g (81 mmol), equivalent to 74% of the theoretical value.

[0201] The following compounds were prepared in a similar manner:

[0202] 5) 5,8-Dihydro-5-phenyl-8-(2-triphenylidene)indolo[2,3- c ] carbazole-d 26

[0203] 21.3 g (38.4 mmol; 1.00 equivalent) of 5,8-dihydro-5-phenyl-8-(2-triphenylidene)indolo[2,3- c Carbazole was suspended in 520 ml (120 equivalents) of toluene-d8 [CAS 2037-26-5]. 12.28 ml (6.00 equivalents) of trifluoromethanesulfonic acid was added to the mixture while cooling. The reaction mixture was stirred at room temperature for 6 hours. Subsequently, 96 ml (130 equivalents) of deuterated water [CAS 7789-20-0] was added dropwise at 0°C. The mixture was neutralized with potassium sulfate solution, followed by extraction with toluene, and the combined organic phases were washed with physiological saline and dried over sodium sulfate. After filtration, the solvent was removed under reduced pressure. Following chromatographic purification, 17 g (29 mmol, 76% of the theoretical value) of the mixture of H / D isotope isomers and H / D isotopes as described above was obtained, and finally purified under high vacuum (p=5×10⁻⁶).-7 sublimation (purity 99.9%) at 10"5mbar.

[0204] The following products can likewise be obtained:

[0205] Manufacture of OLEDs

[0206] In the following examples V1 to V8 and Ex1-1 to Ex8-1 (see Tables 7 and 8), data for the respective OLEDs are presented. Examples Ex1-1 to Ex8-1 show data for inventive OLEDs; examples V1 to V8 show corresponding comparative examples according to the prior art.

[0207] The substrates used in the OLEDs in Table 7 were glass plates coated with structured ITO (indium tin oxide) having a thickness of 50 nm. The exact structure of the OLEDs can be found in Table 7. Materials required for the manufacture of the OLEDs, which are not described above, are indicated in Table 9.

[0208] All materials were applied in vacuum chamber by thermal vapour deposition. In this case, the light-emitting layer always consisted of at least one matrix material (also host material) and a light-emitting dopant (emitter), which was added to the matrix material in a certain volume ratio by co-evaporation. The detailed information reported in the form E13:H2:TEG3 (24%:70%:6%) 40 nm means that the material E13 as host material 1 was present in a volume fraction of 24%, the compound H2 as host material 2 in a fraction of 70% and TEG3 in a fraction of 6% in a layer having a thickness of 40 nm. In an analogous manner, the hole injection layer (HIL) and the electron transport layer (ETL) can also consist of a mixture of two materials.

[0209] The OLEDs were characterised in the standard manner. To this end, electroluminescence spectra and current-voltage-luminance characteristics (IUL characteristics) were measured; these were used to calculate the EQE. The calculation was carried out under the assumption of a Lambertian emission characteristic. The voltage required for a current density of 10 mA / cm 2 is called U10. EQE10 denotes the external quantum efficiency at a working luminance of 10 mA / cm 2 .

[0210] For each example, the relative EQE and the relative voltage are calculated in comparison with the respective comparative example: Relative U (Ex) = 100 x (U10(Ex) / U10(V)) Relative EQE (Ex) = 100 x (EQE10(Ex) / EQE10(V)).

[0211] Lifetime LT90 is defined as the time after which the luminance has dropped to 90% of the initial luminance L0 (in cd / m2) during operation at a constant current density j0 in mA / cm2. In the examples shown here, a current density of 60 mA / cm2was used. 2 2 2

[0212] For each example, the relative LT is calculated compared to the corresponding comparative example: Relative LT (Ex) = 100 x (LT90(Ex) / LT90(V)).

[0213] Use of the mixtures of the present application in OLEDs

[0214] The combination of compounds or materials of the present application can be used in the light-emitting layer in a phosphorescent green OLED.

[0215] The data of each OLED are summarized in Table 8. Examples V1 to V8 are comparative examples according to the prior art; examples Ex1-1 to Ex8-1 show the data of the OLEDs of the present application. The examples of the present application show a clear advantage, in particular in terms of lifetime of the device.

[0216] Table 7: Structure of the OLED

[0217] Table 8:

[0218] Table 9: Materials used which are not described above ​​​

Claims

1. An organic electronic device comprising an anode, a cathode, and at least one organic layer containing at least one compound of formula (1) and at least one compound of formula (2), Equation (1), Equation (2), The symbols and markings used are as follows: X is either N or CR. 8 Where at least one X is N; Z is selected from divalent groups Z-1 to Z-23. The groups Z-1 to Z-23 may be replaced by one or more substituents R. 7 Replace and wherein the dashed bonds are each bonded to L1 or L2; W represents O or S; Ar1, Ar2, Ar3, and Ar4 are the same or different and are independently composed of 5 to 40 ring atoms and can be denoted by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; Ar5 is the same or different in each case and independently has 5 to 40 ring atoms and can be generated by one or more R atoms. 7 Aromatic or electron-rich heteroaromatic ring systems with substituent groups, excluding indo-carbazolyl as an electron-rich heteroaromatic ring system; R 6 In each case, the same or different and being D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 7 The group is substituted and one or more of the non-adjacent CH2 groups can be replaced by Si(R) 7 2. C=O, NR 7 O, S or CONR 7 Instead, or having 6 to 60 ring atoms and in each case being able to be one or more R 7 Aromatic ring systems with substituted groups; R 1 R 7 The same or different in each case and for D, F, Cl, Br, I, N(R) 8 )2, CN, NO2, OR 8 SR 8 ,Si(R 8 )3, B(OR 8 )2,C(=O)R 8 , P(=O)(R 8 )2,S(=O)R 8 S(=O)2R 8 OSO2R 8 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 8 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Instead, or having 5 to 40 ring atoms and in each case being one or more R 8 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 7 The groups together can form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; preferably, R 7 The group does not form any such ring system; R 8 In each case, they may be the same or different and are H, D, F or aliphatic, aromatic or heteroaromatic organic groups having 1 to 20 carbon atoms, especially hydrocarbon groups, in which one or more hydrogen atoms may be replaced by F; s is the same or different in each case and is 0, 1, 2, 3 or 4; u is the same or different in each case and is 0, 1, or 2. The compound of formula (2) contains at least one deuterium.

2. The organic electronic device according to claim 1, wherein the compound of formula (2) conforms to one of formulas (2a) to (2e). Equation (2a), Equation (2b), Equation (2c), Equation (2d), Equation (2e), The symbols and markings used include Ar5 and R. 6 , s, and u are the same as those defined in claim 1.

3. The organic electronic device according to claim 1 or 2, wherein at least one compound of formula (2) has a deuteration level of 10 mol% to 100 mol%.

4. The organic electronic device according to one or more of claims 1 to 3, wherein at least one compound of formula (1) is partially or fully deuterated.

5. The organic electronic device according to one or more of claims 1 to 4, wherein the electronic device is selected from organic integrated circuits (OIC), organic field-effect transistors (OFET), organic thin-film transistors (OTFT), organic electroluminescent devices, organic solar cells (OSC), organic optical detectors, and organic photosensors.

6. The organic electronic device according to one or more of claims 1 to 5, wherein the electronic device is an electroluminescent device.

7. The organic electronic device according to claim 6, wherein the organic electronic device is selected from organic light-emitting transistors (OLET), organic field quenching devices (OFQD), organic light-emitting electrochemical cells (OLEC), organic laser diodes (O-lasers), and organic light-emitting diodes (OLEDs).

8. The organic electronic device according to one or more of claims 1 to 7, wherein the organic layer comprises at least one light-emitting layer comprising at least one compound of formula (1) and a compound of formula (2).

9. The organic electronic device according to claim 8, wherein the light-emitting layer contains at least one other compound selected from matrix materials, phosphors, fluorescent emitters, and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

10. The organic electronic device according to claim 8 or 9, wherein the light-emitting layer comprises a phosphorescent material.

11. The organic electronic device according to one or more of claims 1 to 10, wherein the organic layer comprises, in addition to the light-emitting layer (EML), a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), an exciton blocking layer, an electron blocking layer, and / or a charge generation layer.

12. A method for manufacturing an organic electronic device according to one or more of claims 1 to 11, characterized in that... The organic layer is applied by vapor deposition or from a solution.

13. A mixture comprising at least one compound of formula (1) and at least one compound of formula (2), Equation (1), Equation (2), The symbols and markings used are as follows: X is either N or CR. 8 Where at least one X is N; Z is selected from divalent groups Z-1 to Z-23. The groups Z-1 to Z-23 may be replaced by one or more substituents R. 7 Replace and wherein the dashed bonds are each bonded to L1 or L2; W represents O or S; L1 consists of 5 to 40 ring atoms and can be generated by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups; L2 is a single bond or has 5 to 40 ring atoms and can be bonded by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups; Ar1, Ar2, Ar3, and Ar4 are the same or different and are independently composed of 5 to 40 ring atoms and can be denoted by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; Ar5 is the same or different in each case and independently has 5 to 40 ring atoms and can be generated by one or more R atoms. 7 Aromatic or electron-rich heteroaromatic ring systems with substituent groups, excluding indo-carbazolyl as an electron-rich heteroaromatic ring system; R 6 In each case, the same or different and being D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 7 The group is substituted and one or more of the non-adjacent CH2 groups can be replaced by Si(R) 7 2. C=O, NR 7 O, S or CONR 7 Instead, or having 6 to 60 ring atoms and in each case being able to be one or more R 7 Aromatic ring systems with substituted groups; R 1 R 7 The same or different in each case and for D, F, Cl, Br, I, N(R) 8 )2, CN, NO2, OR 8 SR 8 ,Si(R 8 )3, B(OR 8 )2,C(=O)R 8 , P(=O)(R 8 )2,S(=O)R 8 S(=O)2R 8 OSO2R 8 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 8 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Instead, or having 5 to 40 ring atoms and in each case being one or more R 8 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 7 The groups together can form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; preferably, R 7 The group does not form any such ring system; R 8 In each case, they may be the same or different and are H, D, F or aliphatic, aromatic or heteroaromatic organic groups having 1 to 20 carbon atoms, especially hydrocarbon groups, in which one or more hydrogen atoms may be replaced by F; s is the same or different in each case and is 0, 1, 2, 3 or 4; u is the same or different in each case and is 0, 1, or 2. The compound of formula (2) contains at least one deuterium.

14. The mixture according to claim 13, wherein the mixture contains other compounds and / or solvents.

15. The mixture according to claim 14, wherein the other compound is selected from matrix materials, phosphorescent emitters, fluorescent emitters, and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

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