Organic electronic device

Abstract

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

Description

Technical Field

[0001] The present invention relates to an organic electronic device, particularly an organic electroluminescent device, the organic electronic device comprising an organic layer comprising a first compound of formula (1) and a second compound of formula (2), and the present invention relates to a mixture or formulation comprising compounds of formula (1) and (2), wherein the compound of formula (1) is selected from compounds containing two triazine units, and the compound of formula (2) is selected from indobenzocarbazoles. Background Technology

[0002] The structures of organic electronic devices, including electroluminescent devices (such as OLEDs – organic light-emitting diodes or OLECs – organic light-emitting electrochemical cells), are well-known, using organic semiconductors as functional materials. In addition to phosphorescent emitters, the luminescent materials used here are increasingly organometallic complexes that exhibit phosphorescence rather than fluorescence. For quantum mechanical reasons, using organometallic compounds as phosphorescent emitters can achieve up to four times improvements in energy efficiency and power efficiency. However, overall, OLEDs, especially those exhibiting triplet emission (phosphorescence), still require improvement, for example, in terms of efficiency, operating voltage, and lifetime. Device performance depends not only on the triplet emitter used. More specifically, other materials used, such as the matrix material, are also particularly important. Therefore, improvements to these materials can also lead to significant improvements in OLED performance.

[0003] The host materials used in organic electronic devices are well known to those skilled in the art. When referring to host materials used in phosphorescent emitters, the term "matrix material" is frequently used in the prior art. This usage of the term also applies to this invention. Currently, various host materials have been developed for both fluorescent and phosphorescent electronic devices.

[0004] Another way to improve the performance data of electronic devices, especially organic electroluminescent devices, is to use a combination of two or more materials, particularly a combination of host or matrix materials.

[0005] KR 20100131745 A, WO 2012048779 A1, JP 2015106658 A, WO 2015169412 A1, WO2015014434 A1, US 2016329502 A, WO 17178311 A1, CN 108250189 A, WO 19132545 A1, WO19066315 A2, US 2019312215 A, WO 20235976 A1, and WO 2021052921 A1 disclose bistriazine compounds as host materials, which can also be used in combination with other host materials.

[0006] US Patent 20140299192 discloses bistriazine compounds as electron transport materials or host materials.

[0007] These materials, especially when used as matrix materials, generally still require improvement. Therefore, one object of the present invention is to provide a matrix material suitable for use in organic electronic devices, particularly for fluorescent or phosphorescent OLEDs, resulting in good device performance, especially in improving device lifetime, and to provide corresponding electronic devices. This is especially true when used in combination with low to moderate emitter concentrations, i.e., 3% to 20%, particularly 3% to 15%, more preferably 4% to 10%, and most preferably 4% to 8%, as device lifetime is particularly limited in these cases.

[0008] It has now been found that electronic devices containing the following compounds (1) and (2) have improvements over the prior art, especially when the compounds are used as matrix materials for phosphorescent dopants.

[0009] It has also been discovered that in the light-emitting layer of organic electronic devices, especially organic electroluminescent devices, this objective is achieved and the drawbacks of the prior art are eliminated by combining at least one compound of formula (1) as a first host material and at least one compound of formula (2) as a second host material. Using this material combination to manufacture the light-emitting layer in organic electronic devices results in devices with excellent performance, especially in terms of lifetime, and particularly at equal or improved operating voltages and comparable efficiencies. Summary of the Invention

[0010] The present invention first provides an organic electronic device comprising an anode, a cathode, and at least one organic layer comprising at least one compound of formula (1) and at least one compound of formula (2). Equation (1), Equation (2), The symbols and markings used are as follows: X is independently N or CR 8 Where at least one X is N; Z is selected from divalent groups Z-1 to Z-23. The groups Z-1 to Z-23 may be replaced by one or more substituents R. 7 Replace and wherein the dashed bonds are each bonded to L1 or L2; W represents O or S; L1 consists of 5 to 40 ring atoms and can be generated by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups; L2 is a single bond or has 5 to 40 ring atoms and can be bonded by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups; Ar1, Ar2, Ar3, and Ar4 are the same or different and are independently composed of 5 to 40 ring atoms and can be denoted by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituted groups; Ar5 is the same or different in each case and independently has 5 to 40 ring atoms and can be generated by one or more R atoms. 7 Aromatic or electron-rich heteroaromatic ring systems with substituent groups, excluding indo-carbazolyl as an electron-rich heteroaromatic ring system; R 6 In each case, the same or different and being D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 7 The group is substituted and one or more of the non-adjacent CH2 groups can be replaced by Si(R) 72. C=O, NR 7 O, S or CONR 7 Instead, or having 6 to 60 ring atoms and in each case being able to be one or more R 7 Aromatic ring systems with substituted groups; R 1 R 7 The same or different in each case and for D, F, Cl, Br, I, N(R) 8 )2, CN, NO2, OR 8 SR 8 ,Si(R 8 )3, B(OR 8 )2,C(=O)R 8 , P(=O)(R 8 )2,S(=O)R 8 S(=O)2R 8 OSO2R 8 A straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or ynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or ynyl group in each case may be one or more R 8 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 8 2. C=O, NR 8 O, S or CONR 8 Instead, or having 5 to 40 ring atoms and in each case being one or more R 8 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 7 The groups together can form aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring systems; preferably, R 7 The group does not form any such ring system; R 8 In each case, the same or different and are H, D, F or aliphatic, aromatic or heteroaromatic organic groups, especially hydrocarbon groups, having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may be replaced by F; s is the same or different in each case and is 0, 1, 2, 3 or 4; u is the same or different in each case and is 0, 1 or 2.

[0011] The present invention also provides a method for manufacturing organic electronic devices, preferably electroluminescent devices, as described above or preferably below, wherein an organic layer is applied by vapor deposition or by solution.

[0012] The present invention also provides a mixture comprising at least one compound of formula (1) as described above or preferred later, and at least one compound of formula (2) as described above or preferred later, and optionally containing other compounds, and / or a solvent, said other compounds being selected from phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0013] The corresponding preferred embodiments described below also form part of the subject matter of this invention. Surprisingly advantageous effects are achieved through the specific selection of compounds of formula (1) and formula (2). Detailed Implementation

[0014] In this patent application, "D" refers to deuterium.

[0015] The organic electronic devices of the present invention are preferably selected from organic integrated circuits (OIC), organic field-effect transistors (OFET), organic thin-film transistors (OTFT), organic electroluminescent devices, organic solar cells (OSC), organic optical detectors, and organic photosensors.

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

[0017] The organic electroluminescent device of the present invention, or the equivalent organic electroluminescent device or organic light-emitting device, includes, for example, an organic light-emitting transistor (OLET), an organic field quenching device (OFQD), an organic light-emitting electrochemical cell (OLEC), an organic laser diode (O-laser), or an organic light-emitting diode (OLED). The organic electroluminescent device of the present invention is particularly an organic light-emitting diode or an organic light-emitting electrochemical cell. The device of the present invention is more preferably an OLED.

[0018] In one embodiment of the present invention, the organic layer of the organic electronic device of the present invention comprises a light-emitting layer containing at least one compound of formula (1) as described above or preferably described below and a compound of formula (2).

[0019] The organic layer of the device of the present invention (containing a light-emitting layer comprising a material combination of at least one compound of formula (1) as described above or below and at least one compound of formula (2)) preferably includes, in addition to the light-emitting layer (EML), a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), an exciton blocking layer, an electron blocking layer, and / or a charge generation layer. The device of the present invention may also include two or more layers from this group, preferably selected from EML, HIL, HTL, ETL, EIL, and HBL. Similarly, an intermediate layer having, for example, an exciton blocking function may be introduced between two light-emitting layers.

[0020] If multiple emitting layers are present, these emitting layers preferably have a total of multiple emission peaks between 380 nm and 750 nm, resulting in overall white emission; in other words, multiple luminescent or phosphorescent compounds are used in the emitting layers. Two or more fluorescent and / or phosphorescent compounds may also be present in the emitting layers. A system with three emitting layers is particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission. As an alternative to the combination described above, the emitting layers may also exhibit yellow emission. Such combinations are known to those skilled in the art. The organic electroluminescent device of the present invention can also be a tandem electroluminescent device, especially for white emitting OLEDs.

[0021] The device may also contain inorganic materials, or other layers formed entirely of inorganic materials.

[0022] The luminescent layer preferably comprises at least one compound of formula (1) and at least one compound of formula (2) and comprises at least one other compound selected from matrix materials, phosphors, fluorescents and / or luminescent materials exhibiting TADF (thermally activated delayed fluorescence).

[0023] A phosphorescent layer comprising at least one compound of formula (1) and at least one compound of formula (2) is particularly preferred, characterized in that, in addition to the host material combination comprising the compounds of formula (1) and formula (2) as described above, it also comprises at least one phosphorescent emitter. Suitable selection of emitters and preferred emitters are described below.

[0024] In the context of this invention, aryl groups contain 6 to 40 ring atoms, preferably carbon atoms. Heteroaryl groups in the context of this invention contain 5 to 40 ring atoms, wherein the ring atoms include carbon atoms and at least one heteroatom, provided that the sum of the carbon atoms and heteroatoms is at least 5. Heteroatoms are preferably selected from N, O, and / or S. Here, aryl groups or heteroaryl groups refer to: simple aromatic rings, i.e., phenyl, derived from benzene; or simple heteroaryl rings, for example derived from pyridine, pyrimidine, or thiophene; or fused aryl or heteroaryl groups, for example derived from naphthalene, anthracene, phenanthrene, quinoline, or isoquinoline. Therefore, aryl groups having 6 to 18 carbon atoms are preferably phenyl, naphthyl, phenanthrene, or biphenylidene, and there is no limitation on the connection of aryl groups as substituents. In the context of this invention, aryl or heteroaryl groups may contain one or more groups, wherein suitable groups are described below. If such groups are not described, the aryl or heteroaryl group is unsubstituted.

[0025] In the context of this invention, aromatic ring systems contain 6 to 60 or 6 to 40 ring atoms, preferably carbon atoms. Aromatic ring systems also include aryl groups as described above.

[0026] The aromatic ring system having 6 to 18 carbon atoms is preferably selected from phenyl, biphenyl, naphthyl, phenanthryl and triphenylide.

[0027] In the context of this invention, heteroaromatic ring systems contain 5 to 40 ring atoms and at least one heteroatom. Preferred heteroaromatic ring systems have 9 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system also includes heteroaryl groups as described above. The heteroatom in the heteroaromatic ring system is preferably selected from N, O, and / or S.

[0028] In the context of this invention, aromatic or heteroaromatic ring systems refer to systems that do not necessarily contain only aryl or heteroaromatic groups, but in which multiple aryl or heteroaromatic groups may be interrupted by non-aromatic units (preferably less than 10% of non-H atoms), such as carbon or oxygen atoms or carbonyl groups. For example, systems such as 9,9'-spirodifluorene, 9,9-diarylfluorene, 9,9-dialkylfluorene, diaryl ethers, piracene, etc., should thus also be considered aromatic or heteroaromatic ring systems in the context of this invention, as well as systems in which two or more aryl groups are interrupted by, for example, straight-chain or cyclic alkyl groups or by silyl groups. Furthermore, systems in which two or more aryl or heteroaromatic groups are directly bonded to each other, such as biphenyl, terphenyl, tetraphenyl, or bipyridine, are also included in the definition of aromatic or heteroaromatic ring systems.

[0029] Aromatic or heteroaromatic ring systems having 5 to 40 or 6 to 60 ring atoms and being linked at any position via an aromatic or heteroaromatic system refer to groups derived, for example, from the following substances: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, celestane, perylene, fluoranthene, benzo[a]fluoranthene, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, diphenylenexide, terphenyl, diphenylenexide, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indo[a]fluorene, cis or trans monobenzo[a]indo[a]fluorene, cis or trans dibenzo[a]indo[a]fluorene, trimer indo[a]fluorene, Isotriin, spirotriin, spiroisotriin, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indole-carbazole, indole-carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenothiazine, pyrazole, indazole, imidazole, benzimidazole, naphthiamidazole, phenanthrenemidazole, pyridinium pyrazinium pyridimazole, quinoxaline pyridimazole , benzo[a]azole, naphtho[a]azole, anthraxazole, phenanthrene[a]azole, iso[a]azole, 1,2-thiazole, 1,3-thiazole, benzo[a]thiazole, pyridazine, benzo[a]pyridazine, pyrimidine, benzo[a]pyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenothiazine, phenanthrene, fluorescein ring, naphthidine, azacarbazole, benzo[a]carbline, phenanthrene, 1,2,3- Triazoles, 1,2,4-triazoles, benzotriazoles, 1,2,3-diazoles, 1,2,4-diazoles, 1,2,5-diazoles, 1,3,4-diazoles, 1,2,3-thiadiazoles, 1,2,4-thiadiazoles, 1,2,5-thiadiazoles, 1,3,4-thiadiazoles, 1,3,5-triazines, 1,2,4-triazines, 1,2,3-triazines, tetrazolium, 1,2,4,5-tetraazines, 1,2,3,4-tetraazines, 1,2,3,5-tetraazines, purines, pteridines, indoleazines, and benzothiadiazoles.

[0030] The electron-rich heteroaryl ring system is characterized by containing at least one electron-rich heteroaryl group, and is particularly preferred to have no electron-deficient heteroaryl groups.

[0031] Electron-deficient heteroaryl groups are six-membered heteroaryl groups having at least one nitrogen atom or five-membered heteroaryl groups having at least two heteroatoms, one of which is a nitrogen atom and the other is an oxygen, sulfur, or substituted nitrogen atom, wherein in each case other aryl or heteroaryl groups may also be fused to these groups. Conversely, electron-rich heteroaryl groups are five-membered heteroaryl groups having exactly one heteroatom selected from oxygen, sulfur, and substituted nitrogen, which may be fused to other aryl groups and / or other electron-rich five-membered heteroaryl groups. Thus, examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, or indocarbazole. Electron-rich heteroaryl groups are also called electron-rich heteroaromatic groups.

[0032] The abbreviations Ar1, Ar2, Ar3, and Ar4 may be the same or different in each case and represent the presence of 5 to 40 ring atoms and can be determined by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituent groups, wherein R 7 Group or substituent R 7 As defined above or below. Preferred definitions of Ar1, Ar2, Ar3, and Ar4 are described below.

[0033] The abbreviation Ar5 may be the same or different in each case and is for atoms with 5 to 40 ring atoms and can be generated by one or more R atoms. 7 Aromatic or electron-rich heteroaromatic ring systems with substituent groups, excluding indolocarbazolyl as electron-rich heteroaromatic ring systems, and wherein R 7 Group or substituent R 7 As defined above or as described below. A preferred definition of Ar5 is described below.

[0034] In the context of this specification, the phrase "two or more groups together can form an aromatic, heteroaromatic, aliphatic, or heteroaliphatic ring system" should specifically refer to the fact that the two groups are connected to each other by chemical bonds in the event of formal elimination of two hydrogen atoms. This is illustrated by the following scheme: .

[0035] However, the above wording should also refer to the fact that if one of the two groups is hydrogen, the second group bonds to the hydrogen atom at the bonding site, thereby forming a ring. This will be illustrated by the following scheme: .

[0036] In the context of this invention, cyclic alkyl groups should be understood to refer to monocyclic, bicyclic, or polycyclic groups.

[0037] In the context of this invention, straight-chain, branched, or cyclic C1- to C1- are... 20-alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl. 1-Methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl-n-octyl- 1-yl, 1,1-dimethyl-n-decane-1-yl, 1,1-dimethyl-n-dodecane-1-yl, 1,1-dimethyl-n-tetradecane-1-yl, 1,1-dimethyl-n-hexadecane-1-yl, 1,1-dimethyl-n-octadecane-1-yl, 1,1-diethyl-n-hexane-1-yl, 1,1-diethyl-n-heptane-1-yl, 1,1-diethyl-n-octane-1-yl, 1,1-diethyl-n-decane-1-yl 1,1-Diethyl-n-dodecane-1-yl, 1,1-Diethyl-n-tetradecane-1-yl, 1,1-Diethyl-n-hexadecane-1-yl, 1,1-Diethyl-n-octadecane-1-yl, 1-(n-propyl)-cyclohexyl-1-yl, 1-(n-butyl)-cyclohexyl-1-yl, 1-(n-hexyl)-cyclohexyl-1-yl, 1-(n-octyl)-cyclohexyl-1-yl and 1-(n-decyl)-cycloyl-1-yl groups.

[0038] The alkenyl group is an alkyl group as described above that contains at least one double bond.

[0039] The alkynyl group is an alkyl group as described above that contains at least one triple bond.

[0040] In the context of this invention, phosphorescent emitters are compounds that exhibit luminescence from excited states having high spin multiplicity, i.e., spin states > 1, particularly from excited triplet states. In the context of this application, all luminescent complexes containing transition metals or lanthanides should be considered phosphorescent emitters. More precise definitions are given below.

[0041] When the host material of the luminescent 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 is used in a phosphorescent emitter, it is preferable that its triplet energy is not significantly lower than that of the phosphorescent emitter. Regarding the triplet energy level, it is preferable that T1(emissor) – T1(matrix) ≤ 0.2 eV, more preferably ≤ 0.15 eV, and most preferably ≤ 0.1 eV. Here, T1(matrix) is the triplet energy level of the matrix material in the luminescent layer, and this condition applies to each of the two matrix materials, and T1(emissor) is the triplet energy level of the phosphorescent emitter. If the luminescent layer contains more than two matrix materials, the above relationship preferably also applies to each of the other matrix materials.

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

[0043] When the host material of the luminescent layer comprising at least one compound of formula (1) as described above or preferred below and at least one compound of formula (2) as described above or preferred below is used in a phosphorescent emitter, the preferred HOMO (highest occupied molecular orbital) energy of the hole transport material of formula (2) as described above or preferred below, hTMM-HOMO(calc), calculated by the method described in the experimental section, and the HOMO energy of the phosphorescent emitter as preferred below, hereinafter abbreviated as emitter-HOMO(calc), satisfy the following conditions: The luminescent material -HOMO(calc)–hTMM-HOMO(calc) ≤ 0.35 eV, preferably ≤ 0.23 eV, and more preferably ≤ 0.15 eV.

[0044] The following describes compounds of formula (1) and preferred embodiments thereof in the devices of the present invention. These preferred embodiments also apply to mixtures or formulations of the present invention.

[0045] The preferred compounds of formula (1) are those of formulas (1a), (1b) and (1c). Equation (1a), Equation (1b), Equation (1c), Where R 8 L1, L2, Z, Ar1, Ar2, Ar3 and Ar4 have the definitions given above or preferably given below.

[0046] The R in the pyrimidine group of the compounds of formulas (1b) and (1c) 8 The groups may be the same or different in each case and are preferably H, D, F, straight-chain alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms and being substituted by F or D in each case, or aromatic ring systems having 6 to 20 carbon atoms and being substituted by F or D in each case. The R in the pyrimidine group of the compounds of formulas (1b) and (1c) 8 The group may be the same or different in each case, and more preferably D, a deuterated straight-chain alkyl group having 1 to 20 carbon atoms, or a deuterated branched or cyclic alkyl group having 3 to 20 carbon atoms, or a deuterated aromatic ring system having 6 to 20 carbon atoms. R in the pyrimidine group of the compounds of formulas (1b) and (1c) 8 The functional groups may be the same or different in each case, and are more preferably D, CD3, C6D6 or C. 12 D 12 .

[0047] The compound of formula (1a) is a particularly preferred embodiment of the compound of formula (1), wherein L1, L2, Z, Ar1, Ar2, Ar3 and Ar4 have the definitions given above or preferably given below.

[0048] In preferred embodiments of the 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%, more preferably 20% to 80%, and most preferably 30% to 70%. The degree of deuteration is reported in mol%.

[0049] In one embodiment of the compounds of formulas (1), (1a), (1b) and (1c), the divalent Z group is preferably a divalent group Z-1 to Z-15, wherein W and R 7 With the definitions given above or preferably given below, Z-1, Z-4, Z-5, Z-7, Z-9, Z-10, and Z-11 are preferred. In one embodiment, the divalent Z group is preferably selected from Z-1 to Z-10, wherein W and R 7It has the definition given above or preferably given below. In one embodiment, the divalent Z group is preferably selected from Z-1, Z-4, Z-5, Z-7, Z-9 and Z-10, wherein W and R 7 It has the definition given above or preferably given below. In this embodiment, the divalent Z group is alternatively, more preferably, selected from Z-1, Z-4, Z-7, and Z-9, wherein W and R 7 It has the definition given above or preferably given below. Z-1 is very particularly preferred. Z-9 is very particularly preferred.

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

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

[0052] R in divalent groups Z-1 to Z-23 7 The functional groups may be the same or different in each case and are preferably D, F, CN, or an aromatic ring system having 6 to 20 carbon atoms and being substituted with D or F in each case. The R in the divalent groups Z-1 to Z-23 of the compounds of formulas (1), (1a), (1b), and (1c) 7 The functional groups may be the same or different in each case, and more preferably D or a deuterated aromatic ring system having 6 to 20 carbon atoms. The R in the divalent groups Z-1 to Z-23 of the compounds of formulas (1), (1a), (1b), and (1c) 7 The functional groups may be the same or different in each case, and are more preferably D, C6D6 or C. 12 D 12 The optimal choice is D.

[0053] In one embodiment of the compounds of formulas (1), (1a), (1b), and (1c), the divalent L1 group is preferably one of formulas L1-1 to L1-8, which can be represented by one or more R groups. 1 Group substitution, wherein R 1 As defined above or below,

[0054] in

[0055] V1 is O, S, or Se. Y is independently N, C, or CR in each case. 8 In which at least one Y is N, no more than two Ys are N and adjacent Ys cannot both be N, and the dashed line indicates the connection with the rest of the equation (1), (1a), (1b) or (1c).

[0056] Therefore, the present invention also provides an organic electroluminescent device as described above or as preferably described, wherein at least one compound of formula (1), (1a), (1b) or (1c) contains a linker L1 conforming to one of formulas L-1-1 to L-1-8 as described above or as preferably described below.

[0057] In formulas L1-3, L1-4, L1-7 and L1-8, V1 is preferably O or S, more preferably O.

[0058] In equation L1-7, two Ys are preferably N, and one Y is CR. 8 And one is C, where R 8 It has the definition given above or preferably given below.

[0059] In equation L1-8, both Y are preferably N and both Y are preferably CR. 8 , where R 8 It has the definition given above or preferably given below.

[0060] R in L1-7 and L1-8 8 The groups may be the same or different in each case and are preferably H, D, F; straight-chain alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms and being substituted by F or D in each case; and aromatic ring systems having 6 to 20 carbon atoms and being substituted by F or D in each case. R in L1-7 and L1-8 8 The group may be the same or different in each case, and more preferably D, a deuterated straight-chain alkyl group having 1 to 20 carbon atoms, or a deuterated branched or cyclic alkyl group having 3 to 20 carbon atoms, or a deuterated aromatic ring system having 6 to 20 carbon atoms. R in L1-7 and L1-8 8 The functional groups may be the same or different in each case, and are more preferably D, CD3, C6D6 or C. 12 D 12 The optimal choice is D.

[0061] In one embodiment of the compounds of formulas (1), (1a), (1b), and (1c), the divalent L1 group is more preferably one of formulas L-1 to L-26, which can be represented by one or more R... 1 Group substitution, wherein R 1 As defined above or below, in V1 is O, S, or Se. The dashed lines indicate connections to the rest of equations (1), (1a), (1b), and (1c).

[0062] In formulas L-14 to L-26, V1 is preferably O or S, more preferably O.

[0063] R in L1 of compounds of formulas (1), (1a), (1b) and (1c) 1 The functional groups may be the same or different in each case and are preferably D, F, CN, Si(R) 8 3. A straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, each of which may be substituted with F or D; an aromatic ring system having 6 to 20 carbon atoms, each of which may be substituted with F or D. R in L1 of the compounds of formulas (1b) and (1c) 1 The functional groups may be the same or different in each case, and are more preferably D, CN, or a deuterated aromatic ring system having 6 to 20 carbon atoms. The R in L1 of the compounds of formulas (1), (1a), (1b), and (1c) 1 The functional groups may be the same or different in each case, and are more preferably D, C6D6 or C. 12 D 12 The optimal choice is D.

[0064] Si(R 8 R in )3 8 Preferably, it is an aromatic ring system having 6 to 20 ring atoms and being substituted with one or more D or F groups, more preferably D-substituted. In Si(R 8 In )3, R 8 More preferably, it is selected from non-deuterated, partially deuterated, or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl, or 1,2-biphenyl.

[0065] In one embodiment of the compounds of formulas (1), (1a), (1b), and (1c), the divalent L1 group is more preferably one of formulas L-2, L-3, and L-14 to L-26, which may be generated by one or more R 1 Group substitution, wherein R 1 V1 has the definition given above or preferably given above.

[0066] Among the groups from L-14 to L-26, L-15, L-16, L-18, L-19, L-20 or L-22 are preferred.

[0067] In one embodiment of the compounds of formulas (1), (1a), (1b), and (1c), the divalent L1 group is more preferably one of formulas L-2 and L-3, which can be generated by one or more R 1 Group substitution, wherein R 1 It has the definition given above or preferably given above.

[0068] In one embodiment of the compounds of formulas (1), (1a), (1b), and (1c), the divalent L1 group is preferably a single bond or one of formulas L-1 to L-26, which may be generated by one or more R 1 Group substitution, wherein L-1 to L-26 and R 1 It has the definition given above or preferably given above.

[0069] R in L2 of compounds of formulas (1), (1a), (1b) and (1c) 1 The functional groups may be the same or different in each case and are preferably D, F, CN, Si(R) 8 3. A straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, each of which may be substituted with F or D; an aromatic ring system having 6 to 20 carbon atoms, each of which may be substituted with F or D. R in L2 of the compounds of formulas (1b) and (1c) 1The functional groups may be the same or different in each case, and are more preferably D, CN, or a deuterated aromatic ring system having 6 to 20 carbon atoms. The R in L2 of the compounds of formulas (1), (1a), (1b), and (1c) 1 The functional groups may be the same or different in each case, and are more preferably D, C6D6 or C. 12 D 12 The optimal choice is D.

[0070] In one embodiment of the compounds of formulas (1), (1a), (1b) and (1c), the divalent L1 group is more preferably a single bond.

[0071] In compounds of formulas (1), (1a), (1b), and (1c), or preferably compounds of formulas (1), (1a), (1b), and (1c), Ar1, Ar2, Ar3, and Ar4 are the same or different and preferably have 5 to 40 ring atoms and can be substituted by one or more R atoms. 7 Aromatic or heteroaromatic ring systems with substituent groups, wherein R 7 It has the definition given above or preferably given above.

[0072] In compounds of formulas (1), (1a), (1b), and (1c), or preferably compounds of formulas (1), (1a), (1b), and (1c), Ar1, Ar2, Ar3, and Ar4 may be the same or different and are preferably aromatic or heteroaromatic ring systems having 5 to 40 ring atoms from Ar-1 to Ar-28. , in Y 3 In each case, the same or different and for O, S, NAr, or C(R)2, R is methyl or phenyl. R 3 For H or R 7 ; Dashed keys indicate keys that connect to the rest of equations (1), (1a), (1b), and (1c); and When Ar appears, Ar is an aromatic or heteroaromatic ring system with 5 to 40 ring atoms that can be substituted by D; m is 0 or 1, where m=0 means that there is no Ar group, and R 7 It has the definition given above.

[0073] Y 3 Preferably, it contains O, S, NAr, or C(CH3)2. 3 O or S is preferred, with O being the most preferred.

[0074] Ar is preferably a divalent phenyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl, triphenylimide, dibenzofuranyl, or dibenzothiopheneyl, which may be partially or fully deuterated. Ar is more preferably a phenyl, 1,2-biphenyl, 1,3-biphenyl, or 1,4-biphenyl, which may be partially or fully deuterated.

[0075] In structures Ar-1 to Ar-28, the substituent R 3 Preferably, the same or different in each case and selected from H, D, F, CN, or aromatic ring systems having 6 to 30 ring atoms and being deuteratizable. In structures Ar-1 to Ar-28, the substituent R 3 More preferably, in each case, the same or different and selected from H, D, undeuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl, or 1,2-biphenyl. In structures Ar-1 to Ar-28, the substituent R... 3 The optimal choice is either the same or different in each case and is selected from H and D.

[0076] In the compounds of formulas (1), (1a), (1b), and (1c), or preferably the compounds of formulas (1), (1a), (1b), and (1c), Ar1, Ar2, Ar3, and Ar4 may be the same or different in each case and are preferably selected from Ar-1 to Ar-4 and Ar-12 to Ar-16 as described above, wherein Y 3 Ar, m, R 3 It has the definition given above or preferably given above.

[0077] In one embodiment of the invention, the Ar1 in the preferred compound of formula (1), (1a), (1b) or (1c) is an Ar-1 to Ar-3 or Ar-12 to Ar-16 group as described above, wherein Y3 For O or S, when Ar is present, Ar is phenyl, 1,2-biphenyl, 1,3-biphenyl, or 1,4-biphenyl, which can be partially or fully deuterated, and m and R 3 It has the definition given or preferably given above. More preferably, when Ar is present, Ar is a phenylene group, which may be partially or fully deuterated.

[0078] In one embodiment of the invention, the Ar2 in the preferred compounds of formulas (1), (1a), (1b), or (1c) is an Ar-1 to Ar-34 or Ar-12 to Ar-16 group as described above, wherein Y 3 For O or S, when Ar is present, Ar is phenyl, 1,2-biphenyl, 1,3-biphenyl, or 1,4-biphenyl, which can be partially or fully deuterated, and m and R 3 It has the definition given above or preferably given above.

[0079] In one embodiment of the invention, the Ar3 in the preferred compounds of formulas (1), (1a), (1b) or (1c) is an Ar-1 to Ar-3 or Ar-12 to Ar-16 group as described above, wherein Y 3 For O or S, when Ar is present, Ar is phenyl, 1,2-biphenyl, 1,3-biphenyl, or 1,4-biphenyl, which can be partially or fully deuterated, and m and R 3 It has the definition given above or preferably given above.

[0080] In one embodiment of the invention, the Ar4 in the preferred compounds of formulas (1), (1a), (1b), or (1c) is an Ar-1 to Ar-3 or Ar-12 to Ar-16 group as described above, wherein Y 3 For O or S, when Ar is present, Ar is a divalent phenyl, 1,2-biphenyl, 1,3-biphenyl, or 1,4-biphenyl, which can be partially or fully deuterated, and m and R 3 It has the definition given above or preferably given above.

[0081] In one embodiment of the invention, in one of preferred formulas (1), (1a), (1b), and (1c), at least Ar1 or at least Ar3 is an Ar-2 or Ar-13 group, wherein R 3 It has the definition given above or preferably given above.

[0082] In one embodiment of the invention, it is particularly preferred that at least one substituent selected from Ar1 to Ar4 has a different definition from the other substituents selected from Ar1 to Ar4.

[0083] In one embodiment of the invention, it is particularly preferred that at least two substituents selected from Ar1 to Ar4 have different definitions from the remaining substituents selected from Ar1 to Ar4.

[0084] In one embodiment of the invention, it is particularly preferred that at least one substituent selected from Ar1 to Ar4 has a different definition than the other substituents selected from Ar1 to Ar4, and that the two substituents Ar1 and Ar2 have different definitions compared to the two substituents Ar3 and Ar4.

[0085] Examples of suitable compounds of formulas (1), (1a), (1b) and (1c) are the structures shown in Table 1 below.

[0086] Table 1:

[0087] The compounds of formulas (1), (1a), (1b) and (1c) that are particularly suitable are compounds E1 to E39 in Table 2.

[0088] Table 2:

[0089] The preparation of compounds of formulas (1), (1a), (1b), and (1c), or the preferred compounds in Table 1, and the preparation of compounds E1 to E39 are known to those skilled in the art. These compounds can be prepared by synthetic steps known to those skilled in the art, such as halogenation, preferably bromination, and subsequent organometallic coupling reactions, such as Suzuki coupling, Heck coupling, or Hartwig-Buchwald coupling. The preparation of compounds of formula (1), or the preferred compounds in Table 1, and the preparation of compounds E1 to E39 can be particularly derived from US 20160329502 A, WO 2017178311 A1, and WO2021052921 A1. In particular, in WO 2017178311 A1, reference should be made to the synthetic examples on pages 46 and 81 to 106 of the specification. In particular, in WO 2021052921 A1, the synthesis examples on pages 32 and 116 to 125 of the instruction manual should be consulted.

[0090] The compound of formula (1) can be prepared according to the following scheme 1, wherein L1, L2, Z, Ar1, Ar2, Ar3 and Ar4 have one of the definitions given or preferably given above.

[0091] Option 1:

[0092] Detailed reaction conditions are known from the prior art or described in the Examples section.

[0093] These methods, if necessary, can then be followed by purification, such as recrystallization or sublimation, to obtain the compound of formula (1) with high purity, preferably greater than 99% (using [methods]). 1 (H NMR and / or HPLC determination).

[0094] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for deuterium atoms is to treat the compound to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound containing one or more deuterium atoms that is capable of releasing them under suitable conditions.

[0095] The platinum catalyst is preferably carbon-supported dry platinum, more preferably 5% carbon-supported dry platinum. The palladium catalyst is preferably carbon-supported dry palladium, more preferably 5% carbon-supported dry palladium. Suitable deuterium sources are D₂O, benzene-d₆, chloroform-d, acetonitrile-d₃, acetone-d₆, acetic acid-d₄, methanol-d₄, or toluene-d₈. Preferred deuterium sources are D₂O or a combination of D₂O and a fully deuterated organic solvent. Particularly preferred deuterium sources are combinations of D₂O and fully deuterated organic solvents, with no limitation on the fully deuterated solvent. Particularly suitable fully deuterated solvents are benzene-d₆ and toluene-d₈. Particularly preferred deuterium sources are combinations of D₂O and toluene-d₈. The reaction is preferably carried out under heating, more preferably at a temperature between 100°C and 200°C. Furthermore, the reaction is preferably carried out under pressure.

[0096] The following describes the compound of formula (2) (body material 2) and its preferred embodiments in the device of the present invention. The preferred embodiments of body material 2 of formula (2) are also applicable to the mixtures and / or formulations of the present invention.

[0097] The preferred compounds of formula (2) are compounds of formulas (2a), (2b), (2c), (2d), and (2e). Equation (2a), Equation (2b), Equation (2c), Equation (2d), Equation (2e), Among them, Ar5, R 6 , s and u have the definitions given above or preferably given later.

[0098] The compounds of formulas (2a), (2b), (2d), and (2e) are particularly preferred embodiments of the compounds of formula (2), wherein Ar5, R 6 , s and u have the definitions given above or preferably given later.

[0099] The compounds of formulas (2a) and (2e) are very particularly preferred embodiments of the compounds of formula (2), wherein Ar5, R 6 , s and u have the definitions given above or preferably given later.

[0100] The compound of formula (2a) is a particularly preferred embodiment of the compound of formula (2), wherein Ar5, R 6 , s and u have the definitions given above or preferably given later.

[0101] Therefore, the present invention also provides an organic electroluminescent device as described above or as preferably described, wherein at least one compound of formula (2) corresponds to a compound of formula (2a), (2b), (2c), (2d) or (2e).

[0102] In a preferred embodiment of the compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), the compounds are partially or fully deuterated, wherein the degree of deuteration of the compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e) is preferably at least 10% to 100%, more preferably 50% to 95%, and most preferably 70% to 90%. The degree of deuteration is reported in mol%.

[0103] Therefore, the present invention also provides an organic electronic device as described above, wherein at least one compound of formula (2) is partially or completely deuterated.

[0104] If the deuterated matrix material 1 or 2 is a deuterated compound, it is feasible for the at least one matrix material 1 or 2 to be a mixture of deuterated compounds with the same chemical basic structure, differing only in the position of the deuterium atom in the chemical basic structure.

[0105] As described above, the corresponding deuteration methods are known to those skilled in the art, or are described, for example, in KR2016041014 A, WO 2017 / 122988 A1, KR 2020052820 A, KR 101978651 B1 and WO 2018 / 110887 A1, or in the Bulletin of the Chemical Society of Japan, 2021, 94(2), 600-605 or the Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071.

[0106] In one embodiment of the invention, for the device of the invention, compounds of formula (2), (2a), (2b), (2c), (2d) or (2e) as described above are selected, and these are used in an organic layer, preferably in a light-emitting layer, together with compounds of formula (1) as described above or preferably as described above, or together with compounds from Table 1 or compounds E1 to E39.

[0107] In the compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), R 6 Preferably D, CN, or having 6 to 60 ring atoms and in each case can be one or more R 7Aromatic ring systems with substituent groups, wherein R 7 Having the definition given or preferably given above. In the compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), R 6 In each case, D is preferred, which is partially or fully deuterated phenyl, naphthyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl or triphenylimides.

[0108] In a preferred embodiment of the compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), R 6 Preferably, D and s is 4 and u is 2 in each case, that is, the compound is a compound of formula (2), (2a), (2b), (2c), (2d) and (2e) whose indolocarbazole-based skeleton is fully deuterated, wherein Ar5 has the definition given above or preferably given below.

[0109] In compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), or preferably compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), Ar5 may be the same or different in each case and is preferably an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, such as Ar-1 to Ar-28, or Ar-29 to Ar-36 as described above.

[0110] Where Y 3 Ar, m, R 3 It has the definition given above or preferably given above and V2 is O or S.

[0111] V2 is preferably O.

[0112] In structures Ar-29 to Ar-36, the substituent R 3 Preferably, the same or different in each case and selected from H, D, F, CN, or an aromatic ring system having 6 to 30 ring atoms and being deuteratizable. In structures Ar-29 to Ar-36, the substituent R 3 More preferably, in each case, the same or different and selected from H, D, undeuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl, or 1,2-biphenyl. In structures Ar-29 to Ar-36, the substituent R... 3The optimal choice is either the same or different in each case and is selected from H and D.

[0113] In compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), or preferably compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), Ar5 may be the same or different in each case and is preferably selected from Ar-1, Ar-2 to Ar-7, Ar-12 to Ar-16, Ar-21, Ar-22, and Ar-29 to Ar-32 as described above, wherein Y 3 Ar, m, R 3 It has the definition given above or preferably given above.

[0114] In compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), or preferably compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), Ar5 is the same or different in each case and more preferably selected from Ar-1, Ar-2, Ar-3, Ar-4, Ar-5, Ar-12, Ar-13, Ar-14, Ar-15, Ar-16, Ar-22, Ar-29, Ar-30, Ar-31, and Ar-32 as described above, wherein Y 3 Ar, m, R 3 It has the definition given above or preferably given above.

[0115] Preferably, the substituent Ar5 is also at least partially or completely deuterated as described above or as preferably stated.

[0116] In a preferred embodiment of the compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), R 6 Preferably, it is a D or partially or fully deuterated phenyl, naphthyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl, or triphenylimide, and s is 4 and u is 2 in each case, i.e., however, at least one of the substituents R 6 And preferably one substituent R 6 It is not D.

[0117] In a preferred embodiment of the compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), s and u are each 0, meaning that the indolocarbazole basic skeleton does not contain any substituent R. 6 .

[0118] In the compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), when R 6 When the group is not D, s is preferably 0 or 1.

[0119] In the compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e), when R 6 When the group is not D, u is preferably 0 or 1, or more preferably 0.

[0120] Examples of suitable compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e) for use in combination with compounds of formula (1) as described above or preferably, are those described on pages 28 to 47 of WO 19066315 A2.

[0121] Examples of suitable compounds of formulas (2), (2a), (2b), (2c), (2d), and (2e) for use in combination with compounds of formula (1) as described above or preferably, are indolecarbazole compounds described on pages 34 to 62 of WO 22038066 A1.

[0122] Examples of suitable host materials of formulas (2), (2a), (2b), (2c), (2d) and (2e) selected and preferably combined with at least one compound of formula (1) for use in the electronic devices of the present invention are the structures given in Table 3 below.

[0123] The designations D1-Dx for the compounds in Tables 3 and 4, such as D1 to D20, indicate the presence of 1 to x deuterium atoms in the corresponding compounds, for example, 1 to 20 deuterium atoms. The symbol x in Dx represents the maximum possible number of deuteration positions given in the following molecules.

[0124] Table 3:

[0125] The compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e) that are particularly suitable for use in the electronic devices of the present invention in combination with at least one compound of formula (1) are compounds H1 to H36 in Table 4.

[0126] Table 4;

[0127] The preparation of compounds of formula (2), or preferably compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e), as well as compounds from Tables 3 and 4, is known to those skilled in the art. Some of the compounds of formula (2) are commercially available. Suitable synthesis is derived from the synthetic examples on pages 86 to 91 of WO 19066315 A2.

[0128] The appropriate deuteration methods have been described above and are applicable accordingly.

[0129] The compounds of formula (1) above, as well as the preferred embodiments described therein or the compounds and compounds E1 to E39 from Table 1, can be combined in the device of the present invention, as needed, with the compounds of formulas (2), (2a), (2b), (2c), (2d) and (2e) mentioned therein, as well as the preferred embodiments described therein or the compounds or compounds H1 to H36 from Table 3.

[0130] The specific combination of the main material of formula (1) and the main material of formula (2) is preferably as described above. Preferred combinations of main materials are also described below.

[0131] The present invention also provides a mixture comprising at least one compound of formula (1) and its preferred embodiments or compounds from Table 1 and compounds E1 to E39, and at least one compound of formulas (2), (2a), (2b), (2c), (2d) and (2e) and its preferred embodiments or compounds from Table 3 or compounds H1 to H36.

[0132] A very particularly preferred mixture of the compound of formula (1) and the compound of formula (2) used in the device of the present invention is obtained by combining compounds E1 to E39 with compounds H1 to H36, as shown in Table 5 below. For example, the first mixture M1 is a combination of compounds E1 and H1.

[0133] Table 5:

[0134] In the mixture of the present invention or in the organic layer or light-emitting layer of the device of the present invention, the concentration of the main material of formula (1) as described above or preferably as described above is generally in the range of 5 wt% to 90 wt% based on the overall mixture or based on the overall composition of the organic layer / light-emitting layer, preferably in the range of 10 wt% to 85 wt%, more preferably in the range of 20 wt% to 85 wt%, even more preferably in the range of 30 wt% to 80 wt%, very particularly preferably in the range of 20 wt% to 60 wt%, and most preferably in the range of 30 wt% to 50 wt%.

[0135] In the mixture of the present invention or in the organic layer or light-emitting layer of the device of the present invention, the concentration of the main material of formula (2) as described above or preferably as described above is in the range of 10 wt% to 95 wt% based on the total mixture or the total composition of the organic layer or light-emitting layer, preferably in the range of 15 wt% to 90 wt%, more preferably in the range of 15 wt% to 80 wt%, even more preferably in the range of 20 wt% to 70 wt%, very particularly preferably in the range of 40 wt% to 80 wt%, and most preferably in the range of 50 wt% to 70 wt%.

[0136] The present invention also relates to a mixture, which, in addition to containing the main materials 1 and 2 of formulas (1) and (2) mentioned above or preferably as described above, especially mixtures M1 to M1404, contains at least one other compound and / or solvent.

[0137] The present invention also relates to a mixture comprising, in addition to the main materials 1 and 2 of formulas (1) and (2) mentioned above or preferably as described above, particularly mixtures M1 to M1404, at least one other compound selected from matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0138] For processing the mixtures of the present invention by liquid phase, for example by spin coating or printing, a formulation of the mixtures of the present invention is required. These formulations may be, for example, solutions, dispersions, or emulsions. The solvent used may preferably be a mixture of two or more solvents. Suitable and preferred solvents include, for example: toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, naphthalene, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dimethylbenzene, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenazine, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methyl anisole, 4-methyl anisole, 3,4-dimethyl anisole, 3,5-dimethyl anisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol Cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-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, cyclohexyl hexanoate, or mixtures of these solvents.

[0139] If the mixture of compounds of formulas (1) and (2) as described above is used as a matrix material or a synonymous host material in the luminescent layer, it is preferable to use it in combination with other compounds, for example, in combination with other matrix materials, as a combination of three host materials.

[0140] In the light-emitting layer of the device of the present invention, the total concentration of all the main materials is generally in the range of 10 wt% to 95 wt% based on the overall composition of the light-emitting layer, preferably in the range of 15 wt% to 90 wt%, more preferably in the range of 15 wt% to 80 wt%, even more preferably in the range of 20 wt% to 70 wt%, very particularly preferably in the range of 40 wt% to 80 wt%, and most preferably in the range of 50 wt% to 70 wt%.

[0141] Suitable matrix materials and light emitters that can be used in the mixtures or organic layers of the present invention are described below.

[0142] Those skilled in the art will readily consider the various materials known in the prior art to select suitable materials for the aforementioned layers in organic electroluminescent devices. Here, those skilled in the art will reflect the chemical and physical properties of the materials in a conventional manner, as they know that materials in organic electroluminescent devices interact with each other. This involves, for example, orbital energy levels (HOMO, LUMO) or other triplet and singlet energy levels, as well as other material properties.

[0143] Suitable matrix materials that can be used in combination with the compounds of the present invention include: aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, biscarbazoles, indoloxacarbazole derivatives, indoxacarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, borazine or borate esters, triazine derivatives, zinc complexes, diazacyclopentane or tetrazacyclopentane derivatives, phosphazacyclopentane derivatives, bridged carbazole derivatives, biphenylide derivatives, or dibenzofuran derivatives. It is also feasible to include other phosphorescent emitters with shorter emission wavelengths than the actual emitters as co-hosts in the mixture, or compounds that do not participate significantly in charge transport, such as wide-bandgap compounds.

[0144] In this document, wide bandgap material refers to the material disclosed in US 7,294,849, characterized by a bandgap of at least 3.5 eV, where bandgap refers to the gap between the HOMO and LUMO energy levels of the material.

[0145] The present invention also relates to a mixture, which, in addition to containing the main materials of formulas (1) and (2) mentioned above or preferably as described above, especially mixtures M1 to M1404, also contains at least one phosphorescent luminescent material.

[0146] The present invention also relates to an organic electroluminescent device as described above or as preferably described, wherein the light-emitting layer comprises, in addition to the host materials of formulas (1) and (2) mentioned above, especially material combinations M1 to M1404, at least one phosphorescent material.

[0147] The term "phosphorescent luminescent material" generally encompasses compounds that emit light through spin-forbidden transitions from excited states with higher spin multiplicity, i.e., spin states > 1, such as compounds that emit light through transitions from triplet states or states with higher spin quantum numbers, such as quintet states. This preferably refers to transitions from triplet states.

[0148] Suitable phosphorescent emitters (= triplet emitters) are, in particular, compounds that emit light when properly excited, preferably in the visible light region; and that also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially containing a metal having such an atomic number. Preferred phosphorescent emitters are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, particularly compounds containing iridium or platinum. In the context of this invention, all luminescent compounds containing the metals mentioned above are considered phosphorescent emitters.

[0149] Generally, any phosphorescent complex known to those skilled in the art for use in phosphorescent OLEDs and organic electroluminescent devices is suitable.

[0150] According to the preferred phosphorescent emitter formula (IX) of the present invention, Equation (IX), The symbols and notations for this formula (IX) are defined as follows: When n+m is 3, n is 1 or 2, and m is 2 or 1. X is the same or different in each case and is N or CR. R is the same or different in each case and is H, D, F, CN, or a branched or straight alkyl group having 1 to 10 carbon atoms, or a partially or fully deuterated branched or straight alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 7 carbon atoms that can be partially or fully substituted with deuterium, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms that can be partially or fully substituted with deuterium.

[0151] Therefore, the present invention also provides an organic electroluminescent device as described above or as preferably described, characterized in that the light-emitting layer, in addition to comprising the host materials 1 and 2, also comprises at least one phosphorescent material conforming to formula (IX) as described above.

[0152] In the light emitter of formula (IX), n is preferably 1 and m is preferably 2.

[0153] In the light emitter of formula (IX), preferably, one X is selected from N and the other X are CR, or all X are the same or different in each case and are CR.

[0154] In the light emitter of formula (IX), at least one R is preferably different from H. In the light emitter of formula (IX), preferably two Rs are different from H and have one of the other definitions given above for the light emitter of formula (IX).

[0155] Preferred phosphorescent emitters according to the present invention conform to formulas (I), (II), (III), (IV) or (V). Formula (I) , Equation (II) , Equation (III) , Formula (IV) , Formula (V) , The symbols and notations for these equations (I), (II), (III), (IV), and (V) are defined as follows: R1 is H or D, R2 is H, D, F, CN, or a branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a partially or fully deuterated branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms that can be partially or fully substituted by deuterium.

[0156] According to the present invention, the preferred phosphorescent emitter conforms to formula (VI), (VII) or (VIII), Formula (VI) , Equation (VII) , Formula (VIII) , The symbols and notations for these equations (VI), (VII), and (VIII) are defined as follows: R1 is H or D, R2 is H, D, F, CN, or a branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a partially or fully deuterated branched or straight-chain alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms that can be partially or fully substituted by deuterium.

[0157] Preferred examples of phosphorescent emitters are described in Table 5 on pages 120 to 126 and Table 6 on pages 127 to 129 of WO 2019 / 007867. These emitters are incorporated herein by reference.

[0158] Particularly preferred examples of phosphorescent luminescent materials are listed in Table 6 below.

[0159] Table 6:

[0160] In the mixtures of the present invention or in the light-emitting layer of the device of the present invention, it is preferable to combine any mixture selected from the sum of mixtures M1 to M1404 with compounds of formulas (I) to (IX) or compounds from Table 6.

[0161] The light-emitting layer of the organic electroluminescent device of the present invention, which contains at least one phosphorescent light-emitting element, is preferably an infrared light-emitting layer, or a yellow, orange, red, green, or blue light-emitting layer, or an ultraviolet light-emitting layer, more preferably a yellow or green light-emitting layer, and most preferably a green light-emitting layer.

[0162] Here, a yellow emitting layer refers to a layer with a photoluminescence peak value in the range of 540 nm to 570 nm. An orange emitting layer refers to a layer with a photoluminescence peak value in the range of 570 nm to 600 nm. A red emitting layer refers to a layer with a photoluminescence peak value in the range of 600 nm to 750 nm. A green emitting layer refers to a layer with a photoluminescence peak value in the range of 490 nm to 540 nm. A blue emitting layer refers to a layer with a photoluminescence peak value in the range of 440 nm to 490 nm. Here, the photoluminescence peak value of a layer with a thickness of 50 nm is determined by measuring the photoluminescence spectrum of the layer at room temperature, wherein the layer comprises: the present invention combination of a host material 1 of formula (1), (1a), (1b), or (1c) and a host material 2 composed of at least one of formulas (2), (2a), (2b), (2c), (2d), and (2e), and a corresponding emitting body.

[0163] The photoluminescence spectrum of the layer is recorded, for example, using a commercial photoluminescence spectrometer.

[0164] Typically at room temperature, 10 -5 The photoluminescence spectrum of the selected luminescent material is measured in a molar amount of anaerobic solution. A suitable solvent is any solvent in which the selected luminescent material is dissolved at the mentioned concentration. Particularly suitable solvents are typically toluene or 2-methyl-THF, but dichloromethane may also be used. Measurements are performed using a commercial photoluminescence spectrometer. The triplet energy T1, in eV, is determined from the photoluminescence spectrum of the luminescent material. First, the peak value Plmax (in nm) of the photoluminescence spectrum is determined. Then, the peak value Plmax (in nm) is converted to eV using: E(T1, in eV) = 1240 / E(T1, in nm) = 1240 / PLmax (in nm).

[0165] Therefore, the preferred phosphorescent emitter is a yellow phosphorescent emitter, preferably those of formulas (I) to (IX) or those from Table 6, with a triplet energy T1 preferably of about 2.3 eV to about 2.1 eV.

[0166] Therefore, the preferred phosphorescent emitter is a green phosphorescent emitter, preferably those of formulas (I) to (IX) or from Table 6, with a triplet energy T1 preferably of about 2.5 eV to about 2.3 eV.

[0167] Therefore, the particularly preferred phosphorescent emitter is a green phosphorescent emitter, preferably those of formulas (I) to (IX) as described above or those from Table 6, with a triplet energy T1 preferably of about 2.5 eV to about 2.3 eV.

[0168] Phosphorescent emitters that satisfy the energy level conditions specified above and are selected as the hTMM of formula (2) are preferred, especially those of formulas (I) to (IX) as described above or those from Table 6: The luminescent material - HOMO(calc) – hTMM-HOMO(calc) ≤ 0.35 eV, preferably ≤ 0.23 eV, and more preferably ≤ 0.15 eV.

[0169] Alternatively, the fluorescent emitter may be present in the light-emitting layer of the device of the present invention or in the mixture of the present invention.

[0170] Preferred fluorescent compounds are selected from arylamines, wherein at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, more preferably having at least 14 ring atoms. Preferred examples of these compounds are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyreneamines, aromatic pyrene diamines, aromatic pyrine amines, or aromatic pyrine diamines. An aromatic anthraceneamine is a compound in which a diaryl amino group is directly bonded to an anthracene group, preferably directly bonded at the 9 position. An aromatic anthracene diamine is a compound in which two diaryl amino groups are directly bonded to an anthracene group, preferably directly bonded at the 9th or 10th position. Aromatic pyreneamines, pyrene diamines, pyrine amines, and pyrine diamines are similarly defined, wherein the diaryl amino groups are preferably bonded to pyrene at the 1st or 1,6th position. Other preferred luminescent compounds are indene-fluoreneamine or indene-fluorene diamine, benzo[a]indene-fluoreneamine or benzo[a]indene-fluorene diamine, and dibenzo[a]indene-fluoreneamine or dibenzo[a]indene-fluorene diamine, as well as indene-fluorene derivatives having fused aryl groups. Pyrene arylamines are also preferred. Benzo[a]indene-fluoreneamine, benzo[a]fluoreneamine, extended benzo[a]indene, phenazine, and fluorene derivatives linked to furan or thiophene units are also preferred. The luminescent devices or mixtures of the present invention may further comprise materials exhibiting TADF (thermally activated delayed fluorescence).

[0171] In another preferred embodiment of the invention, at least one light-emitting layer of the organic electroluminescent device may have three or four different matrix materials, preferably three different matrix materials. These corresponding hybrid matrix systems may consist of the matrix materials described in host material 1 and host material 2, but in addition to host material 1 or host material 2, they may also include, for example, a wide-bandgap material, a bipolar host material, an electron transport material (ETM), or a hole transport material (HTM) as a third or fourth matrix material.

[0172] Preferably, the mixed matrix system is optimized for one of the light emitters of formulas (I) to (IX) or for the light emitters from Table 6.

[0173] In one embodiment of the invention, the mixture contains no other components, i.e., functional materials, besides the main material and main material 2 as described above or preferably as shown in formula (1). These are material mixtures used as is for the manufacture of the light-emitting layer. These mixtures, also known as premixed systems, are the sole material source for vapor deposition of the main material of the light-emitting layer and maintain a constant mixing ratio during vapor deposition. In this way, vapor deposition of a layer with uniformly distributed components can be achieved simply and quickly without the need for precise control of multiple material sources.

[0174] In an alternative embodiment of the invention, in addition to comprising the components of formula (1) and formula (2) 2 as described above or preferably, the mixture also comprises the phosphorescent emitter as described above. In vapor deposition, this mixture can also be used as the sole source of materials, provided the mixing ratio is appropriate.

[0175] Preferred is a premixed system consisting of two matrix materials, namely a compound of formula (1), (1a), (1b) or (1c) and a compound of formula (2), (2a), (2b), (2c), (2d) or (2e).

[0176] The components or ingredients of the organic layer of the device of the present invention can thus be obtained by vapor deposition or solution processing. In the case of solution processing, the host materials 1 and 2 as described above or preferably, optionally in combination with the phosphorescent emitter as described above or preferably, are provided in a formulation containing at least one solvent. Suitable formulations have been described above.

[0177] According to preferred embodiments and luminescent compounds, the luminescent layer in the device of the present invention preferably contains a matrix material with an overall composition of 99.9 vol% to 1 vol%, more preferably 99 vol% to 10 vol%, particularly preferably 98 vol% to 60 vol%, and very particularly preferably 97 vol% to 80 vol%, based on the total composition of the luminescent material and the matrix material. The matrix material is composed of at least one compound of formula (1), (1a), (1b), or (1c) and at least one compound of one of (2), (2a), (2b), (2c), (2d), or (2e) according to preferred embodiments. Accordingly, the luminescent layer in the device of the present invention preferably contains a luminescent material with an overall composition of 0.1 vol% to 99 vol%, more preferably 1 vol% to 90 vol%, more preferably 2 vol% to 40 vol%, and most preferably 3 vol% to 20 vol%. If the compound is processed by solution, it is preferable to use an amount in weight % rather than the amount in volume % as specified above.

[0178] The present invention also relates to an organic electroluminescent device as described above or as preferably described, wherein the organic layer comprises a hole injection layer (HIL) and / or a hole transport layer (HTL), wherein the hole injection material and the hole transport material belong to the arylamine class.

[0179] The preferred layer order in the organic electroluminescent device of the present invention is as follows: Anode / hole injection layer / hole transport layer / light emission layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0180] This layer order is the preferred order.

[0181] At the same time, it should be pointed out again that not all of the mentioned layers must exist, and / or other layers may exist.

[0182] The material used for the electron transport layer can be any material that serves as the electron transport material in the electron transport layer according to existing technology. Particularly suitable are aluminum complexes such as Alq3, zirconium complexes such as Zrq4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, diazole derivatives, aromatic ketones, lactams, boranes, phosphazacyclopentane derivatives, and phosphine oxide derivatives.

[0183] The present invention also relates to an organic electroluminescent device as described above or as preferably described, wherein the organic layer comprises an electron injection layer (EIL) and / or an electron transport layer (ETL) and / or a hole blocking layer, wherein the electron injection material and / or electron transport material is selected from compounds of formulas (1), (1a), (1b) and (1c) as described above or as preferably described.

[0184] Suitable cathodes for the devices of the present invention are metals with low work function, metal alloys composed of various metals, or multilayer structures, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Yb, Sm, etc.). Also suitable are alloys composed of alkali metals or alkaline earth metals and silver, such as alloys composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, other metals with relatively high work function, such as Ag or Al, can also be used. In this case, combinations of said metals are typically used, such as Ca / Ag, Mg / Ag, or Ba / Ag. It is also preferable to introduce a thin interlayer of material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials useful for this purpose are alkali metal fluorides or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.). Lithium quinoline (LiQ) can also be used for this purpose. The layer thickness is preferably between 0.5 nm and 5 nm.

[0185] The preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, for this purpose, metals with high redox potentials are suitable, such as Ag, Pt, or Au. Secondly, metal / metal oxide electrodes (e.g., Al / Ni / NiO) are also preferred. x Al / PtO x For some applications, at least one of the electrodes must be transparent or partially transparent to allow for the illumination of organic materials (organic solar cells) or the coupling of output light (OLEDs, O-lasers). The preferred anode material is a conductive mixed metal oxide. Indium tin oxide (ITO) or indium zinc oxide (IZO) is particularly preferred. Conductive doped organic materials, especially conductive doped polymers, are also preferred. Furthermore, the anode may consist of two or more layers, for example, an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide, or vanadium oxide.

[0186] Since the presence of water and / or air can shorten the lifespan of the device of the present invention, the organic electroluminescent device of the present invention is appropriately structured, has contact connections set, and is finally sealed during the manufacturing process (depending on the application).

[0187] The manufacture of the device of the present invention is not limited herein. One or more organic layers, including a light-emitting layer, can be coated by sublimation. In this case, by sublimation in a vacuum sublimation system at less than 10 -5 millibars, preferably less than 10 -6 Material is applied via vapor deposition at an initial pressure of millibars. However, in this case, even lower pressures, such as less than 10, are used. -7An initial pressure of millibars is also feasible.

[0188] The organic electroluminescent device of the present invention is preferably characterized in that one or more layers are coated by OVPD (organic vapor deposition) or by means of carrier gas sublimation. In this case, at 10 -5 The material is applied under a pressure between millibar and 1 bar. A special case of this method is OVJP (organic vapor phase inkjet printing), in which the material is applied directly through a nozzle, thereby structuring (e.g., MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0189] The organic electroluminescent device of the present invention is further preferably characterized by producing one or more organic layers comprising the composition of the present invention from a solution, for example, by spin coating, or by any printing method such as screen printing, flexographic printing, nozzle printing, or offset printing, but more preferably by LITI (photoinduced thermal imaging, thermal transfer) or inkjet printing. For this purpose, soluble host materials 1 and 2 and a phosphorescent emitter are required. The advantage of solution processing is, for example, that the luminescent layer can be applied in a very simple and inexpensive manner. This technique is particularly suitable for the large-scale production of organic electroluminescent devices.

[0190] Furthermore, a hybrid approach is feasible, for example, in which one or more layers are applied by a solution and one or more other layers are applied by vapor deposition.

[0191] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices.

[0192] Therefore, the present invention also provides a method for manufacturing an organic electroluminescent device as described above or as preferably described in the present invention, characterized by applying an organic layer, preferably a light-emitting layer, by vapor deposition, especially by sublimation and / or by OVPD (organic vapor deposition) and / or by sublimation with the aid of a carrier gas, or by solution, especially by spin coating or by printing.

[0193] In the case of fabrication using vapor deposition, there are, in principle, two methods to apply or vapor deposit the organic layer, preferably the luminescent layer, of the present invention onto any substrate or prior layer. First, the materials used are initially packaged individually in material sources and can ultimately be evaporated from different material sources (“co-evaporation”). Second, the various materials can be premixed (premixed system), the mixture initially packaged in a single material source and ultimately evaporated from there (“premixed evaporation”). In this way, vapor deposition of a luminescent layer with uniformly distributed components can be achieved simply and quickly without the need for precisely driving multiple material sources.

[0194] The following processes are feasible: A method for manufacturing the organic electronic device of the present invention as described above or as preferably described, characterized in that an organic layer, preferably a light-emitting layer, is applied by vapor deposition, especially by sublimation and / or by OVPD (organic vapor deposition) and / or by carrier gas sublimation, or by solution, especially by spin coating or by printing.

[0195] A method for manufacturing an organic electronic device of the present invention as described above or as preferably described, characterized in that an organic light-emitting layer is applied by vapor deposition, wherein at least one compound of formula (1), (1a), (1b) and (1c) and at least one compound of formula (2), (2a), (2b), (2c), (2d) and (2e) together with any other material forming the light-emitting layer are sequentially or simultaneously deposited from at least two material sources by vapor deposition.

[0196] A method for manufacturing the device of the present invention, characterized in that an organic light-emitting layer is applied by vapor deposition, wherein at least one compound of formula (1), (1a), (1b) and (1c), together with at least one compound of formula (2), (2a), (2b), (2c), (2d) and (2e) as a premix, is sequentially or simultaneously vapor-deposited with a light-emitting material selected from phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0197] Compared with the prior art, the electronic device of the present invention, especially the organic electroluminescent device, has one or more of the following surprising advantages: 1. A mixture or preferred embodiment of the compounds comprising formulas (1) and (2) described above and below, especially as a matrix material, for electronic devices, particularly organic electroluminescent devices, has a very good lifetime, especially at low emitter concentrations.

[0198] 2. Electronic devices, especially organic electroluminescent devices, that use mixtures of compounds of formulas (1) and (2) as described above and below, or preferred embodiments of the present invention as matrix materials, exhibit excellent efficiency. In this case, the compounds of formulas (1) and (2) of the present invention as described above and below, or the mixtures of the present invention as described in preferred embodiments, result in low operating voltages when used in electronic devices.

[0199] 3. The mixture of compounds of formulas (1) and (2) described above and below, or the preferred embodiments thereof, have excellent glass film formation.

[0200] These advantages were not accompanied by an unusually severe deterioration in other electronic properties.

[0201] It should be noted that variations of the embodiments described in this invention are covered by the scope of this invention. Unless expressly excluded, any feature disclosed in this invention may be exchanged for an alternative feature having the same or equivalent or similar purpose. Therefore, unless otherwise stated, any feature disclosed in this invention should be considered an example of a general series or an equivalent or similar feature.

[0202] Unless specific features and / or steps are mutually exclusive, all features of the invention can be combined with each other in any way. This is especially true for preferred features of the invention. Similarly, features that are not necessarily combined can be used individually (and not in combination).

[0203] The technical teachings disclosed in this invention can be refined and combined with other examples.

[0204] The present invention is illustrated in detail by means of the following embodiments, but is not intended to limit the present invention.

[0205] Example

[0206] General method: In all quantum chemical calculations, the Gaussian16 (version B.01) software package was used. The neutral singlet ground state was optimized at the B3LYP / 6-31G(d) level. The HOMO and LUMO values ​​were determined at the B3LYP / 6-31G(d) level for the ground state energy optimized at the B3LYP / 6-31G(d) level. Then, TD-DFT singlet and triplet excitations (vertical excitations) were calculated using the same method (B3LYP / 6-31G(d)) and the optimized ground state geometry. Standard SCF and gradient convergence settings were used.

[0207] The HOMO (calc) as the last occupied orbital (α occ. eigenvalue) and the LUMO (calc) as the first unoccupied orbital (α virt. eigenvalue) are obtained from energy calculations, in Hartree units, where HEh and LEh represent the HOMO energy and LUMO energy in Hartree units, respectively. This is used to determine the HOMO and LUMO values ​​in electron volts, calibrated by cyclic voltammetry, as follows: HOMO(calc)=0.90603×HEh×27.211385-0.84836 LUMO(calc)=0.99687×LEh×27.211385-0.72445 The triplet energy level T1 of a material is defined as the excitation energy (in eV) of the lowest excited state with a multiplicity of 3 (triple state) calculated by quantum chemical TD-DFT.

[0208] The singlet energy level S1 of a material is defined as the excitation energy (in eV) of the lowest excited state with a multiplicity of 1 (i.e., singlet state) calculated by quantum chemical TD-DFT.

[0209] The singlet state with the lowest energy is denoted as S0.

[0210] The method described in this article is independent of the software package used and always yields the same results. Examples of commonly used software for this purpose are "Gaussian09" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.). In this example, energy is calculated using the software package "Gaussian16 (version B.01)".

[0211] Synthesis example

[0212] Unless otherwise stated, all the following synthesis was carried out in a dry solvent under a protective gas atmosphere. The compounds can be prepared by synthetic methods known to those skilled in the art.

[0213] 1) 2-Dibenzofuran-1-yl-4,6-diphenyl[1,3,5]triazine

[0214] 23 g (110.0 mmol) of dibenzofuran-1-boric 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 was added to the suspension, followed by 112 mg (0.5 mmol) of palladium(II) acetate, and the reaction mixture was heated under reflux for 16 hours. After cooling, the organic phase was separated, filtered through silica gel, washed three times with 200 mL of water, and concentrated to dryness. The residue was recrystallized from toluene and dichloromethane / heptane. The yield was 37 g (94 mmol), equivalent to 87% of the theoretical value.

[0215] 2) 2-(8-bromodibenzofuran-1-yl)-4,6-diphenyl[1,3,5]triazine

[0216] 70 g (190.0 mmol) of 2-dibenzofuran-1-yl-4,6-diphenyl[1,3,5]triazine was suspended in 2000 ml of acetic acid (100%) and 2000 ml of sulfuric acid (95%–98%). 34 g (190 mmol) of NBS was added in portions to the suspension, and the mixture was stirred in the dark for 2 hours. Subsequently, water / ice was added, and the solids were removed and washed with ethanol. The residue was recrystallized in toluene. The yield was 80 g (167 mmol), equivalent to 87% of the theoretical yield.

[0217] 3) 2,4-Diphenyl-6-[8-(4,4,5,5-tetramethyl[1,3,2]dioxaborphane-2-yl)-dibenzofuran-1-yl][1,3,5]triazine

[0218] In a 500 mL flask under a protective atmosphere, 60 g (125 mmol) of 2-(8-bromodibenzofuran-1-yl)-4,6-diphenyl-[1,3,5]triazine and 39 g (1051 mmol) of pinacol diborate (CAS 73183-34-3) were dissolved in 900 mL of dry DMF, and the mixture was degassed for 30 min. Subsequently, 37 g (376 mmol) of potassium acetate and 1.9 g (8.7 mmol) of palladium acetate were added, and the mixture was heated to 80 °C overnight. After the reaction was complete, the mixture was diluted with 300 mL of toluene and extracted with water. The solvent was removed by rotary evaporation, and the mixture was recrystallized from heptane. Yield: 61 g (117 mmol), 94% of theoretical value.

[0219] 4) 2-[3-[9-(4,6-diphenyl-1,3,5-triazin-2-yl)-2-dibenzofuranyl]phenyl]-4,6-diphenyl-1,3,5-triazine

[0220] 57.7 g (110.0 mmol) of 2,4-diphenyl-6-[8-(4,4,5,5-tetramethyl-[1,3,2]dioxaborphane-2-yl)-dibenzofuran-1-yl]-[1,3,5]triazine, 42 g (110.0 mmol) of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine, and 21 g (210.0 mmol) of sodium carbonate were suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine was added to the suspension, followed by 112 mg (0.5 mmol) of palladium(II) acetate, and the reaction mixture was heated under reflux for 16 hours. After cooling, the organic phase was separated, filtered through silica gel, washed three times with 200 ml of water, and then concentrated to dryness. The product was purified by silica gel column chromatography using toluene / CHCl3 (1:1), and finally purified under high vacuum (p=5×10⁻⁶). -7 Sublimation at 1 mbar (purity 99.9%). Yield 54 g (76 mmol), equivalent to 70% of the theoretical value.

[0221] 5) 5,8-Dihydro-5-phenyl-8-(2-triphenylidene)indolo[2,3- c ] carbazole-d 26

[0222] H32 H3

[0223] 21.3 g (38.4 mmol; 1.00 equivalent) of 5,8-dihydro-5-phenyl-8-(2-triphenylidene)indolo[2,3- c Carbazole was suspended in 520 ml (120 equivalents) of toluene-d8 [CAS 2037-26-5]. 12.28 ml (6.00 equivalents) of trifluoromethanesulfonic acid was added to the mixture while cooling. The reaction mixture was stirred at room temperature for 6 hours. Subsequently, 96 ml (130 equivalents) of deuterated water [CAS 7789-20-0] was added dropwise at 0°C. The mixture was neutralized with potassium sulfate solution, followed by extraction with toluene, and the combined organic phases were washed with physiological saline and dried over sodium sulfate. After filtration, the solvent was removed under reduced pressure. Following chromatographic purification, 17 g (29 mmol, 76% of the theoretical value) of the mixture of H / D isotope isomers and H / D isotopes as described above was obtained, and finally purified under high vacuum (p=5×10⁻⁶). -7 Sublimation at 1000 mg / L (99.9% purity).

[0224] The following products can be obtained similarly:

[0225] OLED manufacturing

[0226] Data for each OLED are presented in the following embodiments V1 to V4 and Ex1 to Ex27 (see Tables 7 and 8).

[0227] Examples Ex1 to Ex27 show data for the OLED of the present invention. The substrate used for the OLED in Table 7 is a glass plate coated with a structured ITO (indium tin oxide) with a thickness of 50 nm.

[0228] The exact structure of an OLED can be found in Table 7. The materials required for OLED manufacturing, if not described above, are shown in Table 9.

[0229] All materials are applied in a vacuum chamber via thermal vapor deposition. In this case, the luminescent layer always consists of at least one matrix material (which is also the host material) and a luminescent dopant (emitting agent), which is added to the matrix material by co-evaporation in a specific volume ratio. Detailed information reported, such as in the form of E32:SdT-C:TEG2 (38%:50%:12%) 40 nm, indicates that material E32, as host material 1, is present in a 38% volume ratio, compound SdT-C, as host material 2, is present in a 50% ratio, and TEG2 is present in a 12% ratio in a 40 nm thick layer. Similarly, the hole injection layer (HIL) and electron transport layer (ETL) can also be composed of a mixture of the two materials.

[0230] OLEDs are characterized in a standard manner. For this purpose, electroluminescence spectra and current-voltage-luminescence density characteristics (IUL characteristics) are measured; these are used to calculate EQE. The calculations are performed under the assumption of Lambertian light emission characteristics. The electroluminescence spectrum is at 1000 cd / m². 2 The luminous density was measured and used to calculate the CIE 1931 x and y color coordinates. The parameter U10 in Table 8 represents 10 mA / cm². 2 The voltage required for the current density. EQE10 indicates 10 mA / cm². 2 External quantum efficiency at the working luminescence density.

[0231] Lifetime LT is defined as the time taken in mA / cm². 2 During operation with a constant current density j0, the luminous density changes from the initial luminous density L0 (unit: cd / m²). 2 The value decreases to a certain proportion L1 (unit: cd / m³). 2The time after L1 / L0 = 90% in Table 8 refers to the time (in hours) after the luminescent density reported in the LT column drops to 90% of its initial value (L0).

[0232] Use of the mixture of the present invention in OLEDs

[0233] The compounds or material combinations of the present invention can be used in the light-emitting layer of phosphorescent green OLEDs.

[0234] Data for each OLED is summarized in Table 8. Examples V1 to V4 are comparative examples according to the prior art; Examples Ex1 to E27 show data for the OLEDs of the present invention. The embodiments of the present invention show significant advantages, particularly in terms of device lifetime. This advantage is especially pronounced in mixtures with low emitting element concentrations.

[0235] Table 7: Structure of OLED

[0236] Table 8:

Claims

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

2. The organic electronic device according to claim 1, wherein L1 in the compound of formula (1) conforms to one of formulas L1-1 to L1-8, and formulas L1-1 to L1-8 can be generated by one or more R 1 Group substitution, wherein R 1 With the definition given in claim 1, in V1 is O, S, or Se. Y is independently N, C, or CR in each case. 8 , wherein at least one Y is N, no more than two Ys are N and adjacent Ys cannot both be N, and the dashed line indicates the connection with the rest of the equation (1).

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

4. The organic electronic device according to one or more of claims 1 to 3, wherein at least one compound of formula (2) is partially or fully deuterated.

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

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

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

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

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

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

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

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

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

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

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

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