Organic electronic device

Abstract

The invention relates to an organic electronic device, in particular an organic light-emitting device, containing an organic layer, which contains a compound of the formula (1) as an OLED material and a second compound of the formula (2) as an OLED material, and a mixture or formulation containing the 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.

Description

[0001] Organic electronic device

[0002] Technical area

[0003] The present invention relates to an organic electronic device, in particular an organic light-emitting device, comprising an organic layer comprising a first compound of formula (1) and a second compound of formula (2), as well as a mixture or formulation comprising the compounds of formulas (1) and (2), wherein the compound of formula (1) is selected from the class of compounds comprising two pyrimidine or triazine units and the compound of (2) is selected from the class of indolocarbazoles.

[0004] State of the art

[0005] The construction of organic electronic devices, including electroluminescent devices (e.g. OLEDs - organic light emitting diodes or OLECs - organic light emitting electrochemical cells), in which organic semiconductors are used as functional materials, has long been known. In addition to fluorescent emitters, organometallic complexes that exhibit phosphorescence instead of fluorescence are increasingly being used as emitting materials. For quantum mechanical reasons, the use of organometallic compounds as phosphorescence emitters can result in up to a fourfold increase in energy and power efficiency. In general, however, there is still room for improvement with OLEDs, and particularly with OLEDs that exhibit triplet emission (phosphorescence), for example with regard to efficiency, operating voltage and lifetime. The properties of the device are not only determined by the triplet emitters used.The other materials used, such as matrix materials, are also particularly important here. Improvements to these materials can therefore also lead to significant improvements in OLED properties.

[0006] Host materials for use in organic electronic devices are well known to those skilled in the art. In the prior art, the term "matrix material" is often used to refer to a host material for phosphorescent emitters. This use of the term also applies to the present invention. A variety of host materials have now been developed for both fluorescent and phosphorescent electronic devices.

[0007] Another possibility to improve the performance of electronic devices, in particular organic electroluminescent devices, is to use combinations of two or more materials, in particular host materials or substrates.

[0008] matrix materials.

[0009] From KR20100131745 A, WO2012048779 A1, JP2015106658 A, WO2015169412 A1, WO 2015014434 A1, US2016329502 A, WO17178311 A1, CN 108250189 A, WO19132545 A1, WO19066315 A2, WO19231210 A1, US2019312215 A, US2019198780 A1, WO20235976 A1, WO2021052921 A1, WO20032428 A1, KR20200141385 A, KR20200145270 A, KR20200145198 A, US2023172055 A1, bistriazine compounds are known as host materials, which can also be used in combination with another host material.

[0010] Bistriazine compounds are known from US6229012 and US20140299192 as electron transport material or host material.

[0011] In general, there is still room for improvement with these materials, particularly for use as matrix materials. The object of the present invention is therefore to provide a matrix material which is suitable for use in an organic electronic device, in particular in a fluorescent or phosphorescent OLED, and which leads to good device properties, particularly with regard to an improved lifetime, and to provide the corresponding electronic device. This applies in particular to use in combination with a low to medium emitter concentration, ie emitter concentrations in the order of 3 to 20%, in particular 3 to 15%, particularly preferably 4 to 10%, and very particularly preferably 4 to 8%, since the device lifetime is limited in particular here.

[0012] It has now been found that electronic devices containing compounds according to the following formulas (1) and (2) exhibit improvements over the prior art, in particular when using the compounds as matrix material for phosphorescent dopants.

[0013] It has further been found that the combination of at least one compound of formula (1) as the first host material and at least one compound of formula (2) as the second host material in a light-emitting layer of an organic electronic device, in particular an organic electroluminescent device, achieves this object and eliminates the disadvantages of the prior art. The use of such a material combination for producing the light-emitting layer in an organic electronic device leads to very good properties of these devices, in particular with regard to lifetime, especially with the same or improved operating voltage and comparable efficiency.

[0014] Summary of the invention

[0015] A first object of the present invention is an organic electronic

[0016] Device comprising an anode, a cathode and at least one organic

[0017] Layer containing at least one compound of formula (1) and at least one

[0018] Compound of formula (2), where the symbols and indices used are:

[0019] Q

[0020] X independently represents N or CR, where at least one X represents N;

[0021] Z is selected from a bivalent group Z-1 to Z-23,

[0022] where the

[0023] Groups Z-1 to Z-23 with one or more substituents R 7 may be substituted and where the dashed bonds each bind to Li or l_2;

[0024] W is O or S;

[0025] An, Ar2, Ars, AR are the same or different, independently of one another, an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which is substituted with one or more radicals R 7 can be substituted;

[0026] Ars is, the same or different at each occurrence, independently of one another, an aromatic or an electron-rich heteroaromatic ring system with 5 to 40 ring atoms, which is substituted with one or more radicals R 7 can be substituted, excluding indolocarbazolyl as an electron-rich heteroaromatic ring system;

[0027] R 6 is, identically or differently at each occurrence, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7 or an aromatic ring system with 6 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted;

[0028] R 7 are the same or different at each occurrence D, F, CI, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 8may be substituted, with one or more non-adjacent CFh groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted; two or more radicals R 7 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R 7 no such ring system;

[0029] R 8is, on each occurrence, the same or different, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may also be replaced by F; s is, on each occurrence, the same or different, 0, 1, 2, 3 or 4; u is, on each occurrence, the same or different, 0, 1 or 2; where the compounds of the formula (2) contain at least one deuterium.

[0030] A further subject of the invention is a process for producing an organic electronic, preferably electroluminescent, device, as described above or preferably described below, wherein the organic layer is applied by vapor deposition or from solution.

[0031] The invention further provides a mixture comprising at least one compound of the formula (1), as described above or preferably described later, and at least one compound of the formula (2), as described above or preferably described later, optionally with a further compound selected from the group of phosphorescent emitters, fluorescent emitters and / or emitters which exhibit TADF (thermally activated delayed fluorescence), and / or a solvent. The corresponding preferred embodiments, as described below, are also subject of the present invention. The surprising and advantageous effects are achieved by specific selection of the compounds of the formula (1) and the compounds of the formula (2).

[0032] Description of the invention

[0033] In this patent application, “D” or “D atom” refers to deuterium.

[0034] The organic electronic device according to the invention is preferably selected from organic integrated circuits (OLCs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors or organic photoreceptors.

[0035] The organic electronic device according to the invention is particularly preferably an organic electroluminescent device.

[0036] The organic electroluminescent device according to the invention, 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 according to the invention is, in particular, an organic light-emitting diode or an organic light-emitting electrochemical cell. The device according to the invention is particularly preferably an OLED.

[0037] In one embodiment of the invention, the organic layer of the organic electronic device according to the invention contains a light-emitting layer which contains the at least one compound of formula (1) and formula (2) as described above or preferably described below.

[0038] The organic layer of the device according to the invention, which contains the light-emitting layer comprising the material combination of at least one compound of formula (1) and at least one compound of formula (2), as described above or below, preferably contains, in addition to a 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 charge-generation layers. The device according to the invention can also contain several layers from this group, preferably selected from EML, HIL, HTL, ETL, EIL, and HBL. Interlayers, which, for example, have an exciton-blocking function, can also be introduced between two emitting layers.

[0039] If a plurality of emission layers are present, these preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, resulting in an overall white emission, i.e. different emitting compounds which can fluoresce or phosphoresce are used in the emitting layers. A plurality of fluorescent and / or phosphorescent compounds can also be present in one emitting layer. Systems with three emitting layers are particularly preferred, wherein the three layers exhibit blue, green and orange or red emission. As an alternative to the combination as described above, an emitting layer can also exhibit yellow emission. Such combinations are known to the person skilled in the art. The organic electroluminescent device according to the invention can also be a tandem electroluminescent device, in particular for white-emitting OLEDs.

[0040] The device may also contain inorganic materials or layers made entirely of inorganic materials.

[0041] It is preferred that the light-emitting layer comprising at least one compound of formula (1) and at least one compound of formula (2) contains at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0042] It is particularly preferred that the light-emitting layer comprising at least one compound of formula (1) and at least one compound of formula (2) is a phosphorescent layer characterized in that, in addition to the host material combination of the compounds of formula (1) and formula (2), as described above, it contains at least one phosphorescent emitter. A suitable selection of emitters and preferred emitters are described below.

[0043] An aryl group within the meaning of this invention contains 6 to 40 ring atoms, preferably C atoms. A heteroaryl group within the meaning of this invention contains 5 to 40 ring atoms, where the ring atoms comprise C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e. phenyl, derived from benzene, or a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene, or a condensed aryl or heteroaryl group, for example derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline. An aryl group with 6 to 18 C atoms is therefore preferably phenyl, naphthyl, phenanthryl or triphenylenyl, whereby the attachment of the aryl group as a substituent is not restricted.The aryl or heteroaryl group within the meaning of this invention may carry one or more radicals, with the suitable radical being described below. If no such radical is described, the aryl or heteroaryl group is unsubstituted.

[0044] An aromatic ring system within the meaning of this invention contains 6 to 60 or 6 to 40 ring atoms, preferably carbon atoms, in the ring system. The aromatic ring system also includes aryl groups, as described above.

[0045] An aromatic ring system with 6 to 18 C atoms is preferably selected from phenyl, biphenyl, naphthyl, phenanthryl and triphenylenyl.

[0046] A heteroaromatic ring system within the meaning of this invention contains 5 to 40 ring atoms and at least one heteroatom. A preferred heteroaromatic ring system has 9 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system also includes heteroaryl groups, as described above. The heteroatoms in the heteroaromatic ring system are preferably selected from N, O, and / or S.

[0047] An aromatic or heteroaromatic ring system within the meaning of this invention is understood to mean a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be interrupted by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as a C or O atom or a carbonyl group. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diaryl ethers, stilbene, etc. are also to be understood as aromatic or heteroaromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group. Furthermore, systems in which two or more aryl or heteroaryl groups are directly bonded to one another, such asBiphenyl, terphenyl, quaterphenyl or bipyridine, are also included in the definition of the aromatic or heteroaromatic ring system.

[0048] An aromatic or heteroaromatic ring system with 5 to 40 or 6 to 60 ring atoms, which can be linked to the aromatic or heteroaromatic ring via any position, is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, Benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline,Phenothiazin, Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenan- thrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1 ,2-Thiazol, 1 ,3-Thiazol, Benzo- thiazol, Pyridazin, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1 ,5-Diaza- anthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1 ,6-Diazapyren, 1 ,8-Diazapyren, 4,5-Diaza- pyren, 4,5,9, 10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1 ,2,3-Triazol, 1 ,2,4- Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1 ,2,4-Oxadiazol, 1 ,2,5-Oxadiazol, 1 ,3,4-Oxadiazol, 1 ,2,3-Thiadiazol, 1 ,2,4-Thiadiazol, 1 ,2,5-Thiadiazol, 1 ,3,4-Thiadiazol, 1 ,3,5-Triazin, 1 ,2,4- Triazin, 1 ,2,3-Triazin, Tetrazol, 1 ,2,4,5-Tetrazin, 1 ,2,3,4-Tetrazin, 1 ,2,3,5-Tetrazin, Purin, Pteridin, Indolizin und Benzothiadiazol.,

[0049] An electron-rich heteroaromatic ring system is characterized in that it contains at least one electron-rich heteroaryl group, and particularly preferably does not contain an electron-poor heteroaryl group.

[0050] An electron-poor heteroaryl group is a six-membered ring heteroaryl group with at least one nitrogen atom or a five-membered ring heteroaryl group with at least two heteroatoms, one of which is a nitrogen atom and the other oxygen, sulfur, or a substituted nitrogen atom, to which further aryl or heteroaryl groups may be fused. In contrast, electron-rich heteroaryl groups are five-membered ring heteroaryl groups with exactly one heteroatom selected from oxygen, sulfur, or substituted nitrogen, to which further aryl groups and / or further electron-rich five-membered ring heteroaryl groups may be fused. Examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, or indenocarbazole. An electron-rich heteroaryl group is also referred to as an electron-rich heteroaromatic radical.

[0051] The abbreviations An, Ar2, Ars and AR mean, identically or differently, at each occurrence, an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which is substituted by one or more radicals R 7 may be substituted, where the radical R 7 or the substituents R 7 has / have a meaning as described above or below. A preferred meaning of An and Ar2 and Ars and AR is described below.

[0052] The abbreviation Ars stands, the same or different at each occurrence, for an aromatic or an electron-rich heteroaromatic ring system with 5 to 40 ring atoms, which is substituted by one or more radicals R 7 may be substituted, whereby indolocarbazolyl is excluded as an electron-rich heteroaromatic ring system and wherein the radical R 7 or the substituents R 7has / have a meaning as described above or below. A preferred meaning of Ars is described below.

[0053] For the purposes of this description, the phrase "two or more residues can form an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system" is understood to mean, among other things, that the two residues are linked by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0054] Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring.

[0055] This should be illustrated by the following diagram:

[0056] A cyclic alkyl group in the sense of this invention is understood to mean a monocyclic, a bicyclic or a polycyclic group.

[0057] In the context of the present invention, a straight-chain, branched or cyclic Ci- to C2o-alkyl group is understood to mean, for example, the radicals methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, 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-,

[0058] 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-,

[0059] 1.1-Diethyl-n-dec-1-yl-, 1,1-Diethyl-n-dodec-1-yl-, 1,1-Diethyl-n-tetradec-1-yl-, 1,1-Diethyln-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- understood.

[0060] Alkenyl groups are alkyl groups, as previously described, containing at least one double bond.

[0061] Alkynyl groups are alkyl groups, as previously described, containing at least one triple bond.

[0062] A phosphorescent emitter within the meaning of the present invention is a compound that exhibits luminescence from an excited state with higher spin multiplicity, i.e., a spin state > 1, in particular from an excited triplet state. For the purposes of this application, all luminescent complexes with transition metals or lanthanides are to be regarded as phosphorescent emitters. A more precise definition is given below. If the host materials of the light-emitting layer comprising at least one compound of formula (1), as described above or preferably described below, and at least one compound of formula (2), as described above or described below, are used for a phosphorescent emitter, it is preferred if their triplet energy is not significantly lower than the triplet energy of the phosphorescent emitter. The triplet level T1(emitter) - T1(matrix) ≤ 0 preferably applies here.2 eV, particularly preferably ≤ 0.15 eV, most preferably ≤ 0.1 eV. Here, T1(matrix) is the triplet level of the matrix material in the emission layer, whereby this condition applies to each of the two matrix materials, and T1(emitter) is the triplet level of the phosphorescent emitter. If the emission layer contains more than two matrix materials, the above relationship preferably also applies to each additional matrix material.When the host materials of the light-emitting layer comprising at least one compound of formula (1), as described above or preferably described below, and at least one compound of formula (2), as described above or preferably described below, are used for a phosphorescent emitter, it is preferred if the energy of the HOMO (highest occupied molecular orbital) of the hole transport material of formula (2), as described above or preferably described below, and calculated according to the method described in the experimental part, hereinafter abbreviated as hTMM-HOMO(calc), satisfies the following condition: hTMM-HOMO(calc) is ≥ -5.50 eV, preferably ≥ -5.37 eV and particularly preferably ≥ -5.27 eV.If the host materials of the light-emitting layer comprising at least one compound of formula (1), as described above or preferably described below, and at least one compound of formula (2), as described above or preferably described below, are used for a phosphorescent emitter, it is preferred if the energy of the HOMO (highest occupied molecular orbital) of the hole transport material of formula (2), as described above or preferably described below, hTMM-HOMO(calc), with the energy of the HOMO of the phosphorescent emitter, as preferably described below and calculated according to the method described in the experimental part, hereinafter abbreviated as emitter-HOMO(calc), satisfies the following condition: emitter-HOMO(calc) - hTMM-HOMO(calc) is ≤ 0.35 eV, preferably ≤ 0.23 eV and particularly preferably ≤ 0.15 eV.The compounds of formula (1) and their preferred embodiments, which are contained in the device according to the invention, are described below. The preferred embodiments also apply to the mixture or formulation according to the invention. Preferred compounds of formula (1) are compounds of formulas (1a), (1b) or (1c). where R 8 , Z, Ar1, Ar2, Ar3 and Ar4 have a meaning mentioned above or mentioned below with preference. The radical R 8 In the pyrimidine radicals of the compounds of formulas (1b) and (1c), at each occurrence, identically or differently, preferably H, D, F, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, each of which may be substituted by F or D, an aromatic ring system having 6 to 20 C atoms, each of which may be substituted by F or D. The radical R 8In the pyrimidine residues of the compounds of formulas (1b) and (1c), D, which may be identical or different at each occurrence, is particularly preferably a deuterated straight-chain alkyl group having 1 to 20 C atoms or a deuterated branched or cyclic alkyl group having 3 to 20 C atoms or a deuterated aromatic ring system having 6 to 20 C atoms. The residue R 8 in the pyrimidine residues of the compounds of formulas (1b) and (1c), at each occurrence, the same or different, is particularly preferably D, CD3, C6D6 or C 12 D 12Compounds of formula (1a) are particularly preferred embodiments of compounds of formula (1), wherein Z, Ar1, Ar2, Ar3 and Ar4 have a meaning mentioned above or mentioned with preference below. In a preferred embodiment of compounds of formulas (1), (1a), (1b) and (1c), the compounds are partially or fully deuterated, wherein the degree of deuteration of the compounds of formulas (1), (1a), (1b) and (1c) is preferably at least 10% to 100%, particularly preferably 20% to 80% and very particularly preferably 30% to 70%. The degree of deuteration is given in mol%. In one embodiment of compounds of formulas (1), (1a), (1b) and (1c), the bivalent group Z preferably represents a bivalent group Z-1 to Z-15, wherein W and R 7have a meaning mentioned above or mentioned below with preference, preferably for Z-1, Z-4, Z-5, Z-7, Z-9, Z-10 and Z-11. In one embodiment, the bivalent group Z is preferably selected from Z-1 to Z-10, where W and R 7 have a meaning mentioned above or mentioned below with preference. In one embodiment, the bivalent group Z is alternatively preferably selected from Z-1, Z-4, Z-5, Z-7, Z-9 and Z-10, where W and R 7 have a meaning mentioned above or mentioned below with preference. In this embodiment, the bivalent group Z is alternatively particularly preferably selected from Z-1, Z-4, Z-7 or Z-9, where W and R 7have a meaning mentioned above or mentioned with preference below. Z-1 is very particularly preferred. Z-9 is very particularly preferred. In compounds of the formulas (1), (1a), (1b) or (1c), as described above or preferably described, W preferably represents O. In one embodiment of compounds of the formulas (1), (1a), (1b) and (1c), the bivalent group Z preferably represents a bivalent group Z-16 to Z-23, where R 7 has a meaning mentioned above or mentioned below as preferred. In this embodiment, the bivalent group Z is alternatively preferably selected from Z-16, Z-18 or Z-23, where R 7 has a meaning mentioned above or preferred below. The radical R 7 in the bivalent groups Z-1 to Z-23, at each occurrence, identically or differently, preferably D, F, CN or an aromatic ring system having 6 to 20 C atoms, which may each be substituted by D or F. The radical R 7In the bivalent groups Z-1 to Z-23 of the compounds of the formulas (1), (1a), (1b) and (1c), D or a deuterated aromatic ring system having 6 to 20 C atoms is particularly preferably used at each occurrence, identically or differently. The radical R 7 in the bivalent groups Z-1 to Z-23 of the compounds of the formulas (1), (1a), (1b) and (1c), at each occurrence, the same or different, is particularly preferably D, C6D6 or C12D12, very particularly preferably D. R 8 in Si(R 8 )3 is preferably the same and is an aromatic ring system having 6 to 20 ring atoms, which may be substituted by one or more radicals D or F, particularly preferably D. In Si(R 8 )3is R 8particularly preferably selected from non-deuterated, partially deuterated or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl. In compounds of the formulas (1), (1a), (1b) and (1c) or preferred compounds of the formulas (1), (1a), (1b) and (1c), Ar1, Ar2, Ar3 and Ar4, identical or different, preferably represent an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is substituted by one or more radicals R 7 may be substituted; where R 7 has a meaning previously mentioned or preferred. In compounds of formulas (1), (1a), (1b) and (1c) or preferred compounds of formulas (1), (1a), (1b) and (1c), Ar1, Ar2, Ar3 and Ar4, identical or different, preferably represent an aromatic or heteroaromatic ring system having 5 to 40 ring atoms from the group Ar-1 to Ar-28,

[0063] where o

[0064] Y at each occurrence, identically or differently, represents O, S, NAr or C(R)2,

[0065] R is methyl or phenyl,

[0066] R 3 H or R 7 means; the dashed bond represents the bond to the remainder of formulas (1), (1a), (1b) and (1c); and Ar, when present, is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by D; m is 0 or 1, where m=0 means that the group Ar is not present and R 7 has a meaning previously mentioned. oo

[0067] Y is preferably O, S, NAr or C(CH3)2. Y is particularly preferably O or S, most preferably O.

[0068] Ar is preferably bivalent phenyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl, triphenylenyl, dibenzofuranyl, or dibenzothiophenyl, which may be partially or fully deuterated. Ar is particularly preferably phenyl, 1,2-biphenyl, 1,3-biphenyl, or 1,4-biphenyl, which may be partially or fully deuterated. o

[0069] In the structures Ar-1 to Ar-28, the substituent R is preferably selected, identically or differently, at each occurrence from the group consisting of H, D, F, CN or an aromatic ring system having 6 to 30 ring atoms, which may be deuterated. In the structures Ar-1 to Ar-28, the substituent R is particularly preferably selected at each occurrence

[0070] Occurrences are identical or different and are selected from the group consisting of H, D, non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl, or 1,2-biphenyl. In the structures Ar-1 to Ar-28, the substituent R is most preferably selected, identically or differently, at each occurrence from the group consisting of H or D.

[0071] In compounds of formulas (1), (1a), (1b) and (1c) or preferred compounds of formulas (1), (1a), (1b) and (1c), An, Ar2, Ars and AR are, identically or differently, on each occurrence preferably a group selected from Ar-1 to Ar-4 oo and Ar-12 to Ar-16, as described above, where Y, Ar, m, R have a meaning given above or given preferably.

[0072] In one embodiment of the invention, it is preferred if An in compounds of the formulas (1), (1a), (1b) or (1c) represents a group Ar-1 to Ar-3 or Ar-12 to Ar-16, o as described above, where Y is Y or S, Ar when occurring represents phenyl, 1,2-

[0073] Biphenyl, 1,3-biphenyl, or 1,4-biphenyl, which may be partially or completely deuterated, and m and R have a meaning previously indicated or preferably indicated. Particularly preferred is Ar, when it occurs, phenylene, which may be partially or completely deuterated.

[0074] In one embodiment of the invention, it is preferred if Ar2 in compounds of formulas (1), (1a), (1b) or (1c) represents a group Ar-1 to Ar-34 or Ar-12 to Ar-16, o as described above, where Y is YO or S, Ar when occurring represents phenyl, 1,2-

[0075] biphenyl, 1,3-biphenyl or 1,4-biphenyl, which may be partially deuterated or fully deuterated and m and R have a meaning given above or preferred.

[0076] In one embodiment of the invention, it is preferred if Ars in compounds of formulas (1), (1a), (1b) or (1c) represents a group Ar-1 to Ar-3 or Ar-12 to Ar-16, o as described above, where Y is Y or S, Ar when occurring represents phenyl, 1,2-

[0077] biphenyl, 1,3-biphenyl or 1,4-biphenyl, which may be partially deuterated or fully deuterated and m and R have a meaning given above or preferred.

[0078] In one embodiment of the invention, it is preferred if AM in compounds of the formulas (1), (1a), (1b) or (1c) represents a group Ar-1 to Ar-3 or Ar-12 to Ar-16, o as described above, where Y is Y or S, Ar when occurring represents divalent

[0079] Phenyl, 1,2-biphenyl, 1,3-biphenyl or 1,4-biphenyl, which may be partially deuterated or completely deuterated and m and R have a meaning given previously or preferably.

[0080] In one embodiment of the invention, it is preferred if at least An or at least Ars in one of the formulas (1), (1a), (1b) or (1c) represents the group Ar-2 or Ar- o

[0081] 13, where R has a meaning previously given or preferred.

[0082] In one embodiment of the invention, it is particularly preferred if at least one substituent selected from An to AM has a different meaning than the remaining substituents selected from An to AM. In one embodiment of the invention, it is particularly preferred if at least two substituents selected from An to An have a different meaning than the remaining substituents selected from An to AR.

[0083] In one embodiment of the invention, it is very particularly preferred if at least one substituent selected from An to An has a different meaning than the remaining substituents selected from An to An and that the two substituents An and Ar2 have a different meaning compared to the two substituents Ars and AR.

[0084] Examples of suitable compounds of formulas (1), (1a), (1b) and (1c) are the structures shown below in Table 1.

[0085] Table 1 :

[0086] 

[0087] oo C\lo co

[0088]

[0089]

[0090] Particularly suitable compounds of formulas (1), (1a), (1b) and (1c) are compounds E1 to E27 of Table 2.

[0091] Table 2:

[0092]

[0093]

[0094] The preparation of the compounds of formulas (1), (1a), (1b), (1c) or the preferred compounds of Table 1 as well as the compounds E1 to E27 is known to the person skilled in the art. The compounds can be prepared by synthesis steps known to the person skilled in the art, such as halogenation, preferably bromination, and a subsequent organometallic coupling reaction, e.g. Suzuki coupling, Heck coupling or Hartwig-Buchwald coupling. The preparation of the compounds of formula (1) or the preferred compounds of Table 1 as well as the compounds E1 to E27 is known in particular from US20160329502 A, WO2017178311 A1 and

[0095] WO2021052921 A1. In WO2017178311 A1, particular reference should be made to the description on page 46 and the synthesis examples on pages 81 to 106. In WO2021052921 A1, particular reference should be made to the description on page 32 and the synthesis examples on pages 116 to 125. The compounds of formula (1) can be prepared according to Scheme 1 below, where Li, l_2, Z, An, Ar2, Ars, and AR have one of the meanings given above or preferred.

[0096] Scheme 1 :

[0097] Detailed reaction conditions are known from the state of the art or are described in the examples section.

[0098] By these processes, optionally followed by purification, such as recrystallization or sublimation, the compounds of formula (1) can be obtained in high purity, preferably more than 99% (determined by 1 H-NMR and / or HPLC).

[0099] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for diatoms 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 diatoms and capable of releasing them under suitable conditions.

[0100] The platinum catalyst is preferably dry platinum on carbon, preferably 5% dry platinum on carbon. The palladium catalyst is preferably dry palladium on carbon, preferably 5% dry palladium on carbon. A suitable deuterium source is D2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4, or toluene-d8. A preferred deuterium source is D2O or a combination of D2O and a fully deuterated organic solvent. A particularly preferred deuterium source is the combination of D2O with a fully deuterated organic solvent, whereby the fully deuterated solvent is not limited here. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. A particularly preferred deuterium source is a combination of D2O and toluene-d8.The reaction is preferably carried out with heating, more preferably with heating to temperatures between 100 °C and 200 °C. Furthermore, the reaction is preferably carried out under pressure.

[0101] The following describes compounds of formula (2) (host material 2) and their preferred embodiments, which are contained in the device according to the invention. The preferred embodiments of host material 2 of formula (2) also apply to the mixture and / or formulation according to the invention.

[0102] Preferred compounds of formula (2) are compounds of formulas (2a), (2b), (2c),

[0103] (2d) and (2e), where Ars, R 6 , s and u a previously specified or later preferred

[0104] meaning and wherein compounds of formulas (2a), (2b), (2c), (2d) and (2e) contain at least one deuterium.

[0105] Compounds of formulas (2a), (2b), (2d) and (2e) are particularly preferred embodiments of compounds of formula (2), wherein Ars, R 6 , s and u have a meaning previously specified or later preferred.

[0106] Compounds of formulas (2a) and (2e) are very particularly preferred embodiments of compounds of formula (2), where Ars, R 6 , s and u have a meaning given above or given later with preference. Compounds of the formula (2a) are particularly preferred embodiments of compounds of the formula (2), where Ars, R 6 , s and u have a meaning previously specified or later preferred.

[0107] A further subject matter of the invention is accordingly an organic electroluminescent device as described above or preferably described, wherein the at least one compound of formula (2) corresponds to a compound of formulas (2a), (2b), (2c), (2d) or (2e) and wherein at least one deuterium is contained in compounds of formulas (2a), (2b), (2c), (2d) and (2e).

[0108] In this embodiment of compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), the compounds are partially or fully deuterated, with the degree of deuteration of the compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e) preferably being at least 10% to 100%, particularly preferably 50% to 95%, and most particularly preferably 70% to 90%. The degree of deuteration is given in mol%.

[0109] A further subject of the invention is therefore an organic electronic device as described above, wherein the at least one compound of formula (2) has a degree of deuteration of 10 to 100 mol%.

[0110] If the deuterated matrix material 1 or 2 is a deuterated compound, it is possible that this at least one matrix material 1 or 2 is a mixture of deuterated compounds of the same basic chemical structure, which differ only in the position of the D atoms in the basic chemical structure. Corresponding deuteration methods are known to the person skilled in the art, as described above, or are described, for example, in KR2016041014 A, WO2017 / 122988 A1, KR2020052820 A, KR101978651 B1 and WO2018 / 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.

[0111] In one embodiment of the invention, compounds of formula (2), (2a), (2b), (2c), (2d) or (2e) are selected for the device according to the invention, as described above, which are used with compounds of formula (1), as described above or preferably described, or with the compounds of Table 1 or compounds E1 to E27, in the organic layer, preferably the light-emitting layer. In compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e), R 6 preferably D, CN or an aromatic ring system with 6 to 60 ring atoms, each of which is substituted by one or more radicals R 7 may be substituted, where R 7 has a meaning previously indicated or preferred. In compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e), R 6 at each occurrence preferably represents D, partially or fully deuterated phenyl, naphthyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl or triphenylenyl.

[0112] In a preferred embodiment of the compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e), R 6 preferably for D and s means 4 at each occurrence and u means 2, ie these are compounds of the formulas (2), (2a), (2b), (2c), (2d) and (2e) which are completely deuterated on the indolocarbazole basic structure, where Ars has a meaning given previously or given below with preference.

[0113] In compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e) or preferably mentioned

[0114] In compounds of the formulas (2), (2a), (2b), (2c), (2d) and (2e), Ars at each occurrence, identically or differently, preferably represents an aromatic or heteroaromatic

[0115] Ring system with 5 to 40 ring atoms of the groups Ar-1 to Ar-28, as previously described, or Ar-29 to Ar-36,

[0116] Ar-31 Ar-32

[0117] oo where Y, Ar, m, R have a meaning given above or preferred and V2 is O or S.

[0118] V? is preferred O. o

[0119] In the structures Ar-29 to Ar-36, the substituent R is preferably selected, identically or differently on each occurrence, from the group consisting of H, D, F, CN or an aromatic ring system having 6 to 30 ring atoms, which may be deuterated. In the structures Ar-29 to Ar-36, the substituent R is particularly preferably selected, identically or differently on each occurrence, from the group consisting of H, D, non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl. In the structures Ar-29 to Ar-36, the substituent R is very particularly preferably selected, identically or differently on each occurrence, from the group consisting of H or D.

[0120] In compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e) or preferred compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e), Ars on each occurrence, identically or differently, preferably represents a group selected from Ar-1, Ar-2 to Ar-7, Ar-12 to Ar-16, Ar-21, Ar-22, Ar-29 to Ar-32, as described above, where Y 3 , Ar, m, R 3 have a previously specified or preferred meaning.

[0121] In compounds of the formulas (2), (2a), (2b), (2c), (2d) and (2e) or preferred compounds of the formulas (2), (2a), (2b), (2c), (2d) and (2e), Ars on each occurrence, identically or differently, particularly preferably represents a group 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, oo as described above, where Y, Ar, m, R have a meaning given above or given with preference.

[0122] Preferably, the substituents Ars are also at least partially or completely deuterated, as previously described or preferably described.

[0123] In a preferred embodiment of the compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e), R 6 preferably represents D or partially or fully deuterated phenyl, naphthyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl or triphenylenyl and s is 4 at each occurrence and u is 2, ie where, however, at least one substituent R 6 or preferably a substituent R 6 is not equal to D.

[0124] Examples of suitable compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e) for combination with compounds of formula (1) or preferred compounds of formula (1) as previously described or preferably described are the compounds described in WO19066315 A2, on pages 28 to 47, which are appropriately deuterated.

[0125] Examples of suitable compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e) for combination with compounds of formula (1) or preferred compounds of formula (1) as previously described or preferably described are the indolocarbazole compounds described in WO22038066 A1, on pages 34 to 62, which are appropriately deuterated.

[0126] Examples of suitable host materials of formulas (2), (2a), (2b), (2c), (2d), and (2e), which are selected according to the invention and are preferably used in combination with at least one compound of formula (1) in the electronic device according to the invention, are the structures listed below in Table 3. The designation D1-Dx, for example D1 to D20, in compounds of Tables 3 and 4 means that 1 to x D atoms, for example 1 to 20 D atoms, are present in the correspondingly labeled compound. The symbol x in Dx represents the maximum possible deuterated positions in the molecule listed below.

[0127] Table 3:

[0128]

[0129] Particularly suitable compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e), which are preferably used in combination with at least one compound of formula (1) in the electronic device according to the invention, are the compounds H1 to H30 of Table 4.

[0130] Table 4:

[0131]

[0132] The preparation of the compounds of formula (2) or the preferred compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), as well as the compounds of Tables 3 and 4, is known to the person skilled in the art. Some of the compounds of formula (2) are commercially available. Suitable syntheses are derived from the synthesis examples in WO1 9066315 A2, pages 86 to 91.

[0133] Suitable deuteration methods have been described previously and apply accordingly. The above-mentioned compounds of formula (1) and their preferred embodiments, or the compounds of Table 1 and compounds E1 to E27, can be combined in any desired manner in the device according to the invention with the above-mentioned compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), and their preferred embodiments, or the compounds of Table 3 or compounds H1 to H36.

[0134] The aforementioned specific combinations of host materials of formula (1) with host materials of formula (2) are preferred, as described above. Preferred combinations of host materials are also described below.

[0135] The invention furthermore also relates to mixtures comprising at least one compound of the formula (1) and the preferred embodiments thereof or the compounds of Table 1 and the compounds E1 to E27 and at least one compound of the formulas (2), (2a), (2b), (2c), (2d) and (2e) and the preferred embodiments thereof or the compounds of Table 3 or the compounds H1 to H36.

[0136] Very particularly preferred mixtures of the compounds of formula (1) with the compounds of formula (2) for the device according to the invention are obtained by combining the compounds E1 to E27 with the compounds H1 to H36 as shown below in Table 5. The first mixture M1, for example, is a combination of the compound E1 with H1.

[0137] Table 5:

[0138] The concentration of the host material of formula (1), as described above or preferably described, in the mixture according to the invention or in the organic or light-emitting layer of the device according to the invention is usually in the range from 5 wt.% to 90 wt.%, preferably in the range from 10 wt.% to 85 wt.%, more preferably in the range from 20 wt.% to 85 wt.%, even more preferably in the range from 30 wt.% to 80 wt.%, very particularly preferably in the range from 20 wt.% to 60 wt.% and most preferably in the range from 30 wt.% to 50 wt.%, based on the total mixture or based on the total composition of the organic layer / light-emitting layer.

[0139] The concentration of the host material of formula (2), as described above or described as preferred, in the mixture according to the invention or in the organic or light-emitting layer of the device according to the invention is in the range from 10 wt.% to 95 wt.%, preferably in the range from 15 wt.% to 90 wt.%, more preferably in the range from 15 wt.% to 80 wt.%, even more preferably in the range from 20 wt.% to 70 wt.%, very particularly preferably in the range from 40 wt.% to 80 wt.% and most preferably in the range from 50 wt.% to 70 wt.%, based on the total mixture or based on the total composition of the organic layer or light-emitting layer.

[0140] The present invention also relates to a mixture which, in addition to the above-mentioned host materials 1 and 2 of the formulas (1) and (2), as described above or preferably described, in particular mixtures M1 to M972, contains at least one further compound and / or a solvent.

[0141] The present invention also relates to a mixture which, in addition to the above-mentioned host materials 1 and 2 of the formulas (1) and (2), as described above or preferably described, in particular mixtures M1 to M972, contains at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters which exhibit TADF (thermally activated delayed fluorescence).

[0142] For processing the mixture according to the invention from the liquid phase, for example by spin coating or printing processes, formulations of mixtures according to the invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferred to use mixtures of two or more solvents as solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, Cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene,Phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butylmethyl ether, triethylene glycol butylmethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, 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, cyclohexylhexanoate or mixtures of these solvents.

[0143] When the mixture according to the invention of the compounds of formulas (1) and (2), as described above, is used as matrix material or synonymously host material in an emitting layer, it is preferably used in combination with another compound, for example with another matrix material as a triple combination of host materials.

[0144] The concentration of the sum of all host materials in the light-emitting layer of the device according to the invention is typically in the range from 10 wt.% to 95 wt.%, preferably in the range from 15 wt.% to 90 wt.%, more preferably in the range from 15 wt.% to 80 wt.%, even more preferably in the range from 20 wt.% to 70 wt.%, very particularly preferably in the range from 40 wt.% to 80 wt.%, and most preferably in the range from 50 wt.% to 70 wt.%, based on the total composition of the light-emitting layer. Suitable matrix materials and emitters that can be used in this mixture according to the invention or in the organic layer according to the invention are described below.

[0145] It is not difficult for a person skilled in the art to draw on a multitude of materials known in the prior art to select suitable materials for use in the layers of the organic electroluminescent device described above. In doing so, the person skilled in the art will consider common considerations regarding the chemical and physical properties of the materials, as they are aware that the materials in an organic electroluminescent device are interrelated. This applies, for example, to the energy positions of the orbitals (HOMO, LIIMO) or the position of triplet and singlet energies, as well as other material properties.

[0146] Suitable matrix materials that can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, biscarbazoles, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasilole or tetraazasilole derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or dibenzofuran derivatives. Likewise, another phosphorescent emitter that emits at a shorter wavelength than the actual emitter can be present in the mixture as a cohost, or a compound that does not participate, or does not participate to a significant extent, in charge transport, such as a wide-band-gap compound.

[0147] A wide-band-gap material is understood herein to mean a material within the meaning of the disclosure of US 7,294,849, which is characterized by a band gap of at least 3.5 eV, where the band gap is understood to be the distance between the HOMO and LUMO energy of a material.

[0148] The present invention also relates to a mixture which, in addition to the aforementioned host materials of formulas (1) and (2), as described above or preferably described, in particular the mixtures M1 to M972, also contains at least one phosphorescent emitter. The present invention also relates to an organic electroluminescent device, as described above or preferably described, wherein the light-emitting layer, in addition to the aforementioned host materials of formulas (1) and (2), in particular the material combinations M1 to M972, also contains at least one phosphorescent emitter.

[0149] The term "phosphorescent emitters" typically encompasses compounds in which light emission occurs through a spin-forbidden transition from an excited state with higher spin multiplicity, i.e., a spin state > 1, for example, through a transition from a triplet state or a state with an even higher spin quantum number, such as a quintet state. Preferably, this refers to a transition from a triplet state.

[0150] Particularly suitable phosphorescent emitters (= triplet emitters) are compounds that emit light upon suitable excitation, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are used as phosphorescent emitters, in particular compounds containing iridium or platinum. For the purposes of the present invention, all luminescent compounds containing the above-mentioned metals are considered phosphorescent emitters.

[0151] In general, all phosphorescent complexes as used in the prior art for phosphorescent OLEDs and as known to the person skilled in the art in the field of organic electroluminescent devices are suitable.

[0152] Preferred phosphorescent emitters according to the present invention correspond to the formula (IX), Formula (IX), where the symbols and indices for this formula (IX) have the meaning: n+m is 3, n is 1 or 2, m is 2 or 1 ,

[0153] X is the same or different at each occurrence, N or CR,

[0154] R is, on each occurrence, identically or differently, H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 7 C atoms which may be partially or fully substituted with deuterium or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms which may be partially or fully substituted with deuterium.

[0155] A further subject matter of the invention is accordingly an organic electroluminescent device as described above or preferably described, characterized in that the light-emitting layer contains, in addition to the host materials 1 and 2, at least one phosphorescent emitter which corresponds to the formula (IX), as described above.

[0156] In emitters of formula (IX), n is preferably 1 and m is preferably 2.

[0157] In emitters of formula (IX), one X is preferably selected from N and the other Xs are CR or all Xs, identically or differently on each occurrence, are CR. In emitters of formula (IX), at least one R is preferably different from H. In emitters of formula (IX), two Rs are preferably different from H and have one of the meanings otherwise previously given for the emitters of formula (IX).

[0158] Preferred phosphorescent emitters according to the present invention correspond to the formulas (I), (II), (III), (IV) or (V),

[0159] formula

[0160] where the symbols and indices for these formulas (I), (II), (III), (IV) and (V) have the meaning:

[0161] Ri is H or D, R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium.

[0162] Preferred phosphorescent emitters according to the present invention correspond to the formulas (VI), (VII) or (VIII), where the symbols and indices for these formulas (VI), (VII) and (VIII) have the meaning: Ri is H or D, R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium.

[0163] Preferred examples of phosphorescent emitters are described in WO2019 / 007867 on pages 120 to 126 in Table 5 and on pages 127 to 129 in Table 6. The emitters are incorporated into the description by this reference.

[0164] Particularly preferred examples of phosphorescent emitters are listed in Table 6 below.

[0165] Table 6:

[0166]

[0167] In the mixtures according to the invention or in the light-emitting layer of the device according to the invention, each mixture selected from the sum of the mixtures M1 to M972 is preferably combined with a compound of the formulas (I) to (IX) or a compound from Table 6.

[0168] The light-emitting layer in the organic electroluminescent device according to the invention containing at least one phosphorescent emitter is preferably an infrared-emitting, yellow, orange, red, green, blue or ultraviolet-emitting layer, particularly preferably a yellow or green-emitting layer and very particularly preferably a green-emitting layer.

[0169] A yellow-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 540 to 570 nm. An orange-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 570 to 600 nm. A red-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 600 to 750 nm.

[0170] A green-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 490 to 540 nm. A blue-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 440 to 490 nm. The photoluminescence maximum of the layer is determined by measuring the photoluminescence spectrum of the layer with a layer thickness of 50 nm at room temperature, wherein the layer contains the inventive combination of the host material 1 of the formulas (1), (1a), (1b) or (1c) and the host material 2, consisting of at least one of the formulas (2), (2a), (2b), (2c), (2d) and (2e), and the corresponding emitter.

[0171] The photoluminescence spectrum of the layer is recorded, for example, using a commercially available photoluminescence spectrometer.

[0172] The photoluminescence spectrum of the selected emitter is usually measured in an oxygen-free, 10 molar solution. The measurement is performed at room temperature. Any solvent in which the selected emitter dissolves at the specified concentration is suitable. Particularly suitable solvents are usually toluene or 2-methyl-THF, but also dichloromethane. The measurement is performed using a commercially available photoluminescence spectrometer. The triplet energy T1 in eV is determined from the photoluminescence spectra of the emitters. First, the peak maximum Plmax. (in nm) of the photoluminescence spectrum is determined. The peak maximum Plmax. (in nm) is then converted to eV according to: E(T1 in eV) = 1240 / E(T1 in nm) = 1240 / PLmax. (in nm).

[0173] Preferred phosphorescent emitters are therefore yellow emitters, preferably of the formulas (I) to (IX) or from Table 6, whose triplet energy T is preferably between ~2.3 eV and ~2.1 eV.

[0174] Preferred phosphorescent emitters are therefore green emitters, preferably of the formulas (I) to (IX) or from Table 6, whose triplet energy T-| is preferably between ~2.5 eV and ~2.3 eV.

[0175] Particularly preferred phosphorescent emitters are accordingly green emitters, preferably of the formulas (I) to (IX) or from Table 6, as described above, whose triplet energy T 1 is preferably between ~2.5 eV and ~2.3 eV.

[0176] Very particularly preferred phosphorescent emitters, preferably of formulas (I) to (IX) or from Table 6 as previously described, are selected which satisfy the previously stated condition of the energy levels with the selected compounds of formula (2) as hTMM:

[0177] Emitter HOMO(calc) - hTMM HOMO(calc) is < 0.35 eV, preferably < 0.23 eV and most preferably < 0.15 eV.

[0178] Fluorescent emitters can also be present in the light-emitting layer of the device according to the invention or in the mixture according to the invention. Preferred fluorescent emitting compounds are selected from the class of arylamines, wherein preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, particularly preferably with at least 14 ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to be a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position.An aromatic anthracenediamine is understood to be a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably in the 9,10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, with the diarylamino groups on the pyrene preferably being bonded in the 1-position or 1,6-position, respectively. Further preferred emitting compounds are indenofluorenamines and diamines, benzoindenofluorenamines and diamines, and dibenzoindenofluorenamines and diamines, as well as indenofluorene derivatives with fused aryl groups. Pyrene-arylamines are also preferred. Also preferred are benzoindenofluoreneamines, benzofluoreneamines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives bonded to furan units or thiophene units. In addition, the light-emitting device orthe mixture according to the invention may also contain materials that exhibit TADF (thermally activated delayed fluorescence).

[0179] In a further preferred embodiment of the invention, the 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 corresponding mixed-matrix systems can consist of the matrix materials described for host material 1 and host material 2, but they can also contain, as a third or fourth matrix material, for example, in addition to host material 1 or host material 2, w / de-öand-gap materials, bipolar host materials, electron-transport materials (ETM), or hole-transport materials (HTM). The mixed-matrix system is preferably optimized for an emitter of one of the formulas (I) to (IX) or for an emitter from Table 6.

[0180] According to one embodiment of the present invention, the mixture contains no further components, i.e., functional materials, apart from the constituents of the host material of formula (1) and the host material 2, as previously described or preferably described. These are material mixtures that are used as such to produce the light-emitting layer. These mixtures are also referred to as premix systems, which are used as the sole material source during the vapor deposition of the host materials for the light-emitting layer and which have a constant mixing ratio during vapor deposition. This enables the vapor deposition of a layer with a uniform distribution of the components to be achieved in a simple and rapid manner, without the need for precise control of a large number of material sources.

[0181] According to an alternative embodiment of the present invention, the mixture contains, in addition to the components of the host material of formula (1) and the host material 2 of formula (2), as described above or preferably described, a phosphorescent emitter as described above. With a suitable mixing ratio during vapor deposition, this mixture can also be used as the sole material source.

[0182] Preferred are premix systems consisting of two matrix materials, namely a compound of formulas (1), (1a), (1b) or (1c) and a compound of one of formulas (2), (2a), (2b), (2c), (2d) or (2e).

[0183] The components or constituents of the organic layer of the device according to the invention can thus be processed by vapor deposition or from solution. When processed from solution, the material combination of host materials 1 and 2, as described above or preferably described, optionally with the phosphorescent emitter, as described above or preferably described, is provided in a formulation containing at least one solvent. Suitable formulations have been described previously.

[0184] The light-emitting layer in the device according to the invention according to the preferred embodiments and the emitting compound preferably contains between 99.9 and 1 vol.%, more preferably between 99 and 10 vol.%, particularly preferably between 98 and 60 vol.%, very particularly preferably between 97 and 80 vol.% of matrix material made of at least one compound of the formulas (1), (1a), (1b) or (1c) and at least one compound of one of (2), (2a), (2b), (2c), (2d) or (2e) according to the preferred embodiments, based on the total composition of emitter and matrix material. Accordingly, the light-emitting layer in the device according to the invention preferably contains between 0.1 and 99 vol.%, more preferably between 1 and 90 vol.%, particularly preferably between 2 and 40 vol.%, very particularly preferably between 3 and 20 vol.-% of the emitter based on the total composition of the light-emitting layer consisting of emitter and matrix material. If the compounds are processed from solution, the corresponding amounts in wt.% are preferably used instead of the above-mentioned amounts in vol.%.

[0185] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the organic layer contains a hole injection layer (HIL) and / or a hole transport layer (HTL), whose hole injecting material and hole transporting material belong to the class of arylamines.

[0186] The sequence of layers in the organic electroluminescent device according to the invention is preferably as follows:

[0187] Anode / hole injection layer / hole transport layer / emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0188] This sequence of layers is a preferred sequence.

[0189] It should be noted again that not all of the layers mentioned need to be present and / or that additional layers may be present.

[0190] All materials used in the prior art as electron-transport materials in the electron-transport layer can be used as materials for the electron-transport layer. Particularly suitable are aluminum complexes, for example Alqβ, zirconium complexes, for example Zrq4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives.The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the organic layer contains an electron injection layer (EIL) and / or an electron transport layer (ETL) and / or a hole blocking layer, whose electron injecting material and / or electron transporting material is selected from the compounds of formulas (1), (1a), (1b) or (1c), as described above or preferably described.

[0191] Suitable cathodes for the device according to the invention include metals with low work functions, metal alloys, or multilayer structures made of different metals, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys made of an alkali or alkaline earth metal and silver, for example, an alloy of magnesium and silver, are also suitable. In multilayer structures, in addition to the metals mentioned, other metals with a relatively high work function, such as Ag or Al, can also be used. Combinations of the metals, such as Ca / Ag, Mg / Ag, or Ba / Ag, are then generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor.Suitable materials for this purpose include alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Ü2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). Lithium quinolinate (LiQ) can also be used. The thickness of this layer is preferably between 0.5 and 5 nm.

[0192] Materials with a high work function are preferred as anodes. The anode preferably has a work function greater than 4.5 eV vs. vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Metal / metal oxide electrodes (e.g., Al / Ni / NiO) can also be used. x , AI / PtO x) may be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to enable either the irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive, doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of several layers, for example an inner layer made of ITO and an outer layer made of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.The organic electroluminescent device according to the invention is structured, contacted and finally sealed accordingly (depending on the application) during production, since the lifetime of the devices according to the invention is shortened in the presence of water and / or air.

[0193] The production of the device according to the invention is not restricted in this respect. It is possible for one or more organic layers, including the light-emitting layer, to be coated using a sublimation process. The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10'5 mbar, preferably less than 10'0 mbar. However, it is also possible for the initial pressure to be even lower, for example, less than 10'7 mbar.

[0194] The organic electroluminescent device according to the invention is preferably characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are applied at a pressure between 10'5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (e.g., BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0195] Furthermore, the organic electroluminescent device according to the invention is preferably characterized in that one or more organic layers comprising the composition according to the invention are produced from solution, for example by spin coating, or by any printing process, such as screen printing, flexographic printing, nozzle printing, or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or inkjet printing. Soluble host materials 1 and 2 and phosphorescent emitters are required for this purpose. Processing from solution has the advantage that, for example, the light-emitting layer can be applied very easily and cost-effectively. This technique is particularly suitable for the mass production of organic electroluminescent devices.

[0196] Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more additional layers are deposited by vapor deposition. These processes are generally known to those skilled in the art and can be applied to organic electroluminescent devices.

[0197] A further subject of the invention is therefore a process for producing the organic electroluminescent device according to the invention, as described above or preferably described, characterized in that the organic layer, preferably the light-emitting layer, is applied by vapor phase deposition, in particular with a sublimation process and / or with an OVPD (Organic Vapor Phase Deposition) process and / or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing process.

[0198] When manufactured by vapor deposition, there are basically two ways in which the organic layer according to the invention, preferably the light-emitting layer, can be applied or vapor-deposited onto any substrate or the previous layer. Firstly, the materials used can each be placed in a material source and then evaporated from the various material sources ("co-evaporation"). Secondly, the various materials can be premixed ("premixed" systems) and the mixture placed in a single material source, from which it is then vaporized ("premix evaporation"). This allows for the vapor deposition of the light-emitting layer with a uniform distribution of the components in a simple and rapid manner, without the need for precise control of a large number of material sources.

[0199] The following procedures are possible:

[0200] A method for producing the organic electronic device according to the invention, as described above or preferably described, characterized in that the organic layer, preferably the light-emitting layer, is applied by vapor phase deposition, in particular with a sublimation process and / or with an OVPD (Organic Vapor Phase Deposition) process and / or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing process.

[0201] A method for producing the organic electronic device according to the invention, as described above or preferably described, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of the formulas (1), (1a), (1b) or (1c) and the at least one compound of the formulas (2), (2a), (2b), (2c), (2d) or (2e) together with the optionally further materials which form the light-emitting layer are deposited successively or simultaneously from at least two material sources from the gas phase.

[0202] A method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein the at least one compound of the formulas (1), (1a), (1b) or (1c) together with the at least one compound of the formulas (2), (2a), (2b), (2c), (2d) or (2e) is deposited from the vapor phase as a premix, one after the other or simultaneously with the light-emitting materials selected from the group of phosphorescent emitters, fluorescent emitters and / or emitters which exhibit TADF (thermally activated delayed fluorescence).

[0203] The electronic devices according to the invention, in particular organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art:

[0204] 1. Electronic devices, in particular organic electroluminescent devices containing mixtures of compounds according to formulas (1) and (2) or the preferred embodiments set out above and below, in particular as matrix material, have a very good lifetime, in particular at low emitter concentrations.

[0205] 2. Electronic devices, in particular organic electroluminescent devices containing mixtures of compounds according to formulas (1) and (2) or the preferred embodiments set out above and below as matrix materials have excellent efficiency. Mixtures of compounds according to the invention according to formulas (1) and (2) or the preferred embodiments set out above and below result in a low operating voltage when used in electronic devices.

[0206] 3. Mixtures of compounds according to formulas (1) and (2) or the preferred embodiments described above and below exhibit excellent glass film formation. These aforementioned advantages are not accompanied by an excessive deterioration of other electronic properties.

[0207] It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Any feature disclosed in the present invention may, unless explicitly excluded, be replaced by alternative features serving the same, equivalent, or similar purpose. Thus, unless otherwise stated, any feature disclosed in the present invention is to be considered an example of a generic series or an equivalent or similar feature.

[0208] All features of the present invention may be combined with each other in any way, unless certain features and / or steps are mutually exclusive. This applies in particular to preferred features of the present invention. Likewise, features of non-essential combinations may be used separately (and not in combination).

[0209] The teaching of technical action disclosed in the present invention can be abstracted and combined with other examples.

[0210] The invention is explained in more detail by the following examples, without intending to limit it thereby.

[0211] Examples

[0212] General methods:

[0213] The Gaussian16 program package (Rev. B.01) is used for all quantum chemical calculations. The neutral singlet ground state is optimized at the B3LYP / 6-31G(d) level. HOMO and LUMO values ​​are determined at the B3LYP / 6-31G(d) level for the ground-state energy optimized with B3LYP / 6-31G(d). TD-DFT singlet and triplet excitations (vertical excitations) are then calculated using the same method (B3LYP / 6-31G(d)) and the optimized ground-state geometry. The default settings for SCF and gradient convergence are used.

[0214] From the energy calculation, the HOMO(calc) is obtained as the last orbital occupied by two electrons (alpha occupancy eigenvalues) and the LUMO(calc) as the first unoccupied orbital (alpha virtual eigenvalues) in Hartree units, where HEh and LEh represent the HOMO energy in Hartree units and the LUMO energy in Hartree units, respectively. From this, the HOMO and LUMO values ​​in electronvolts, calibrated using cyclic voltammetry measurements, are determined as follows:

[0215] HOMO(calc) = 0.90603 * HEh * 27.211385 - 0.84836

[0216] LUMO(calc) = 0.99687 * LEh * 27.211385 - 0.72445

[0217] The triplet level T1 of a material is defined as the excitation energy (in eV) into the lowest excited state with multiplicity 3 (triplet), which results from the quantum chemical TD-DFT calculation.

[0218] The singlet level S1 of a material is defined as the excitation energy (in eV) into the lowest excited state with multiplicity 1 (singlet), which results from the quantum chemical TD-DFT calculation.

[0219] The lowest energy singlet state is called SO.

[0220] The method described here is independent of the software package used and always produces the same results. Examples of commonly used programs for this purpose are "Gaussian09" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.). In this case, the program package "Gaussian16 (Rev. B.01)" is used to calculate the energies.

[0221] Synthesis examples

[0222] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The compounds can be prepared using synthesis methods known to those skilled in the art.

[0223] 1) 2-Dibenzofuran-1-yl-4,6-diphenyl-[1,3,5]triazine

[0224] [3842-55-5]

[0225] 23 g (110.0 mmol) of dibenzofuran-1-boronic acid, 29.5 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 and then 112 mg (0.5 mmol) of palladium(II) acetate were added to this suspension, and the reaction mixture was heated under reflux for 16 h. After cooling, the organic phase was separated, filtered through silica gel, washed three times with 200 mL of water, and then evaporated to dryness. The residue was recrystallized from toluene and dichloromethane / heptane. The yield is 37 g (94 mmol), corresponding to 87% of theory.

[0226] 2) 2-(8-Bromo-dibenzofuran-1-yl)-4,6-diphenyl-[1,3,5]triazine

[0227] 70 g (190.0 mmol) of 2-dibenzofuran-1-yl-4,6-diphenyl-[1,3,5]triazine are suspended in 2000 mL of acetic acid (100%) and 2000 mL of sulfuric acid (95-98%). 34 g (190 mmol) of NBS are added portionwise to this suspension and stirred for 2 hours in the dark. Water / ice is then added, and the solid is separated and washed with ethanol. The residue is recrystallized from toluene. The yield is 80 g (167 mmol), corresponding to 87% of theory.

[0228] 3) 2,4-Diphenyl-6-[8-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-dibenzofuran-1-yl]-

[0229] [1,3,5]triazine

[0230] In a 500 ml flask, 60 g (125 mmol) of 2-(8-bromodibenzofuran-1-yl)-4,6-diphenyl-[1,3,5]triazine and 39 g (1051 mmol) of bis(pinacolato)diborane (CAS 73183-34-3) are dissolved in 900 ml of dry DMF under protective gas and degassed for 30 minutes. Subsequently, 37 g (376 mmol) of potassium acetate and 1.9 g (8.7 mmol) of palladium acetate are added, and the mixture is heated to 80 °C overnight. After the reaction is complete, the mixture is diluted with 300 ml of toluene, and the mixture is extracted with water. The solvent is removed on a rotary evaporator and recrystallized from heptane. Yield: 61 g (117 mmol), 94% of theory. Analogously, the following connections are made: 4) 2,4-Diphenyl-6-[8-(2,4-Diphenyl-[1,3,5]triazin-2-yl)-dibenzofuran-1-yl]-[1,3,5]triazine

[0231] 68.7 g (110.0 mmol) of 2,4-diphenyl-6-[8-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-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 and then 112 mg (0.5 mmol) of palladium(II) acetate were added to this suspension, and the reaction mixture was heated under reflux for 16 h. After cooling, the organic phase is separated, filtered through silica gel, washed three times with 200 mL of water, and then evaporated to dryness. The product is purified by column chromatography on silica gel using toluene / CHCl3 (1:1) and finally evaporated under high vacuum (p = 5 x 10'). 7 mbar) (purity 99.9%). The yield is 51 g (81 mmol), corresponding to 74% of theory.

[0232] Analogously, the following connections are made: 5) 5,8-Dihydro-5-phenyl-8-(2-triphenylenyl)indolo[2,3-c]carbazol -d26

[0233] H3

[0234] 21.3 g (38.4 mmol; 1.00 eq) of 5,8-dihydro-5-phenyl-8-(2-triphenylenyl)indolo[2,3-c]carbazole is suspended in 520 mL (120 eq) of toluene-d8 [CAS 2037-26-5]. 12.28 mL (6.00 eq) of trifluoromethanesulfonic acid is added to this mixture while cooling. The reaction mixture is stirred at ambient temperature for 6 hours. Subsequently, 96 mL (130 eq) of deuterium oxide [CAS 7789-20-0] is added dropwise at 0°C. After neutralization with potassium sulfate solution, the mixture is extracted with toluene, and the combined organic phases are washed with brine and dried over sodium sulfate. After filtration, the solvent is removed under reduced pressure. 17 g (29 mmol, 76% of theory) of the product shown above in a mixture with portions of H / D isotopomers and H / D isotopologues are obtained after chromatographic purification and finally concentrated in high vacuum (p = 5 x 10' 7 mbar) sublimated (purity 99.9%).

[0235] Similarly, the following products can be obtained:

[0236]

[0237] Production of OLEDs

[0238] The following examples C1 to C8 and Ex1-1 to Ex8-1 (see Tables 7 and 8) present data for various OLEDs. Examples Ex1-1 to Ex8-1 show data for OLEDs according to the invention, while examples C1 to C8 show corresponding comparative examples according to the prior art. Glass plates coated with structured ITO (indium tin oxide) with a thickness of 50 nm are used as the substrate for the OLEDs in Table 7. The exact structure of the OLEDs can be found in Table 7. The materials required for the production of the OLEDs are shown in Table 9, unless previously described.

[0239] All materials are thermally evaporated in a vacuum chamber. The emission layer always consists of at least one matrix material (also called host material) and an emitting dopant (dopant, emitter), which is mixed into the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as E13:H2:TEG3 (24%:70%:6%) 40nm means that the material E13 is present in a volume fraction of 24% as host material 1, the compound H2 as host material 2 in a volume fraction of 70%, and TEG3 in a volume fraction of 6% in a 40nm thick layer. Similarly, the hole injection layer (HIL) and the electron transport layer (ETL), for example, can also consist of a mixture of two materials.

[0240] The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra and current-voltage-luminance characteristics (IUL characteristics) are measured, from which the EQE is calculated. The calculation assumes a Lambertian radiation pattern. The voltage required for a current density of 10 mA / cm 2 required is referred to here as U10. EQE10 denotes the external quantum efficiency at a current density of 10 mA / cm 2 .

[0241] For each example, the relative EQE and the relative voltage are calculated in comparison to the corresponding comparison example: rel. U (Ex) = 100 * (U10(Ex) / U10(V)) rel. EQE (Ex) = 100 * (EQE10(Ex) / EQE10(V)).

[0242] The lifetime LT90 is defined as the time after which the luminance when operated at a constant current density jo in mA / cm 2 from a starting luminance L0 (in cd / m 2) drops to 90% of this starting luminance. In the examples shown here, the current density used is 60mA / cm 2 .

[0243] For each example, the relative LT is calculated in comparison to the corresponding comparison example: rel. LT (Ex) = 100 * (LT90(Ex) / LT90(V)).

[0244] Use of mixtures according to the invention in OLEDs The compounds or material combinations according to the invention can be used in the emission layer in phosphorescent green OLEDs.

[0245] The data for the various OLEDs are summarized in Table 8. Examples C1 to C8 are comparative examples according to the prior art, while examples Ex1-1 to Ex8-1 show data for OLEDs according to the invention. The inventive examples demonstrate, in particular, a significant advantage in the device's lifetime.

[0246] Table 7: Structure of the OLEDs

[0247] Table 8:

[0248] Table 9: Materials used, unless previously described

Claims

Patent 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), where the symbols and indices used are: Q X independently represents N or CR, where at least one X represents N; Z is selected from a bivalent group Z-1 to Z-23, where the Groups Z-1 to Z-23 with one or more substituents R 7 may be substituted and where the dashed bonds each bind to Li or l_2; W is O or S; An, Ar2, Ars, AR are the same or different independently of one another an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which with one or more radicals R 7can be substituted; Ars is, the same or different at each occurrence, independently of one another, an aromatic or an electron-rich heteroaromatic ring system with 5 to 40 ring atoms, which is substituted by one or more radicals R 7 can be substituted, excluding indolocarbazolyl as an electron-rich heteroaromatic ring system; R 6 is at each occurrence, identically or differently, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted with one or more radicals R 7 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7may be replaced, or an aromatic ring system with 6 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; R 1 , R 7 are the same or different at each occurrence D, F, CI, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 8 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted; two or more radicals R 7 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R 7 no such ring system; R 8 is, on each occurrence, the same or different, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may also be replaced by F; s is, on each occurrence, the same or different, 0, 1, 2, 3 or 4; u is, on each occurrence, the same or different, 0, 1 or 2, where the compounds of the formula (2) contain at least one deuterium.

2. Organic electronic device according to claim 1, wherein the compound of formula (2) corresponds to one of formulas (2a) to (2e), Formula (2a), where the symbols and indices used are Ars, R 6 , s and u have a meaning as in claim 1.

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

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

5. Organic electronic device according to one or more of claims 1 to 4, wherein the electronic device is selected from organic integrated circuits (OLCs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors or organic photoreceptors.

6. 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 it is selected from the group consisting of organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), and organic light-emitting diodes (OLEDs).

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

9. Organic electronic device according to claim 8, wherein the light-emitting layer contains at least one further compound selected from the group of matrix materials, phosphorescent emitters, 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 contains a phosphorescent emitter.

11. Organic electronic device according to one or more of claims 1 to 10, wherein the organic layer contains, 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 charge generation layers.

12. A method for producing 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 solution.

13. A mixture containing at least one compound of formula (1) and at least one compound of formula (2), where the symbols and indices used are: Q X independently represents N or CR, where at least one X represents N; Z is selected from a bivalent group Z-1 to Z-23, Groups Z-1 to Z-23 with one or more substituents R 7 may be substituted and where the dashed bonds each bind to Li or l_2; W is O or S; Li is an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which is linked by one or more radicals R 1 can be substituted; L2 is a single bond or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which is linked by one or more radicals R 1 can be substituted; An, Ar2, Ars, AR are the same or different independently of one another an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which with one or more radicals R 7 can be substituted; Ars is, the same or different at each occurrence, independently of one another, an aromatic or an electron-rich heteroaromatic ring system with 5 to 40 ring atoms, which is substituted with one or more radicals R 7 can be substituted, excluding indolocarbazolyl as an electron-rich heteroaromatic ring system; R 6 is at each occurrence, the same or different, D, F, CN, a straight-chain Alkyl group with 1 to 20 C atoms or an alkenyl or alkynyl group with 2 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 and wherein one or more non-adjacent CFh groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7may be replaced, or an aromatic ring system with 6 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; R 1 , R 7 are the same or different at each occurrence D, F, CI, 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 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 8 may be substituted, with one or more non-adjacent CFL groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted; two or more radicals R 7 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R 7 no such ring system; R 8 is, on each occurrence, the same or different, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may also be replaced by F; s is, on each occurrence, the same or different, 0, 1, 2, 3 or 4; u is, on each occurrence, the same or different, 0, 1 or 2, where the compounds of the formula (2) contain at least one deuterium.

14. A mixture according to claim 13, wherein the mixture contains a further compound and / or a solvent.

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

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