Materials for organic electroluminescent devices

Abstract

The present invention relates to 4H-naphtho [1, 2, 3, 4-def] carbazoles, mixtures and formulations comprising these compounds, and electronic devices comprising these compounds, in particular organic electroluminescent devices comprising these compounds as matrix material, electron transport material or hole blocking material.

Description

Technical Field

[0001] The present invention relates to 4H-naphtho[1,2,3,4-def]carbazole, mixtures and formulations containing these compounds, and electronic devices containing these compounds, in particular organic light-emitting devices containing these compounds as host materials, electron transport materials or hole blocking materials.

[0002] State of the Art

[0003] Phosphorescent organometallic complexes are often used in organic light-emitting devices (OLEDs). In general, there is still a need to improve OLEDs, for example in terms of efficiency, operating voltage and lifetime. The performance of phosphorescent OLEDs depends not only on the triplet emitters used. More particularly, other materials used, such as host materials, are also particularly important here. Therefore, improving these materials can also significantly improve the performance of OLEDs.

[0004] According to the prior art, among the host materials for phosphorescent emitters there are carbazole derivatives, dibenzofuran derivatives, indolocarbazole derivatives, indolocarbazole derivatives, benzofuranocarbazole derivatives and benzothiophenocarbazole derivatives.

[0005] WO2012048781 A1, CN115626914 A and US2021119134 A1 in particular describe specific 4H-naphtho[1,2,3,4-def]carbazole derivatives as host materials.

[0006] CN113248477 A, US2019315759 A1, WO22038065 A1, US2022263031A1 in particular describe composite carbazole derivatives as host materials.

[0007] CN111978355 A and US20190051844 A1 describe 4H-naphtho[1,2,3,4-def]carbazole derivatives as ligands of emitters.

[0008] In general, there is still a need to improve these materials, especially when used as host materials. The problem solved by the present invention is to provide compounds that are particularly suitable for use as host materials, electron transport materials or hole blocking materials in phosphorescent OLEDs. More particularly, an object of the present invention is to provide host materials that can improve the lifetime. This is especially the case when using low to medium emitter concentrations, i.e. in the order of 3% to 20%, especially 3% to 15%, since the device lifetime is particularly limited in this case.

[0009] Electroluminescent devices containing the compound of formula (1) below have now been found to be improved compared to the prior art, especially when the compound is used as a host material for phosphorescent dopants.

[0010] It has also been found that by combining at least one compound of formula (1) as a first host material with at least one hole-transporting compound as other host materials in the light-emitting layer of an organic electronic device, especially an organic electroluminescent device, for example, with one or more compounds of formula (6), formula (7), formula (8), formula (9), formula (10) or formula (11), this problem is solved and the disadvantages of the prior art are eliminated. Summary of the Invention

[0011] The present invention first provides a material for an organic electronic device, which comprises at least one compound of formula (1):

[0012]

[0013] The symbols and notations used are as follows:

[0014] L is the same or different in each case and is a single bond or an aromatic or heteroaromatic ring system having 5 to 20 ring atoms and which may be substituted by one or more R 0 groups;

[0015] R 0 is the same or different in each case and is selected from the group consisting of: D, F, Cl, Br, I, CN, NO2, C(=O)R 2 , P(=O)(Ar)2, P(Ar)2, B(Ar)2, Si(Ar)3, Si(R 2 )3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, each of said groups being optionally substituted by one or more R 2 groups; wherein one or more non-adjacent CH2 groups may be replaced by R 2 C=CR 2 , Si(R 2 )2, C=O, C=S, C=NR 2 , P(=O)(R 2 ), SO, SO2, NR 2 , O, S or CONR 2 and wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or having 5 to 40 ring atoms and in each case optionally substituted by one or more R 2A group-substituted aromatic or heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms and optionally substituted by one or more R 2 groups, or an aralkyl or heteroaralkyl group having 5 to 40 ring atoms and optionally substituted by one or more R 2 groups;

[0016] Rx conforms to one of Formulas (1-2) to (1-16):

[0017]

[0018]

[0019] * represents the bond connected to L;

[0020] R a 、R b and R c represent mono-substitution, di-substitution, tri-substitution, maximum allowable substitution or no substitution,

[0021] R a 、R b and R c are each independently D;

[0022] V is O, S or N-Ar4;

[0023] R 1 is each independently H, D, CN, F or an undehydrogenated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl;

[0024] Ar is the same or different in each case and is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and optionally substituted by one or more R 2 groups;

[0025] Aryl is the same or different in each case and is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and optionally substituted by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups in the alkyl group may be replaced by O or S, and wherein one or more hydrogen atoms in the alkyl group may be replaced by D, F or CN;

[0026] Ar1 is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and optionally substituted by one or more R 2 groups,

[0027] Ar2 and Ar3 are the same or different in each case and are H, D, CN, F, an undehydrogenated or partially or fully deuterated alkyl group having 1 to 10 carbon atoms, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may be substituted by one or more R 2 groups; and

[0028] R 2 is the same or different in each case and is selected from: D, F, CN, Si(aryl)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, where one or more non-adjacent CH2 groups may be replaced by O or S, and where one or more hydrogen atoms may be replaced by D, F or CN,

[0029] wherein the compound of formula (1) is partially or fully deuterated.

[0030] The present invention also provides a mixture comprising at least one compound of formula (1) as described above or preferably described later, and at least one other compound selected from the group consisting of: a matrix material, a phosphorescent emitter, a fluorescent emitter and / or an emitter exhibiting TADF (thermally activated delayed fluorescence).

[0031] The present invention also provides a formulation comprising at least one compound of formula (1) as described above or preferably described later, or the mixture as described above, and at least one solvent.

[0032] The present invention also provides an organic electronic device, preferably an organic electroluminescent device, comprising an anode, a cathode and at least one organic layer, the organic layer comprising at least one compound of formula (1) as described above or preferably described later.

[0033] Description of the Invention

[0034] In this patent application, "D" or "D atom" means deuterium.

[0035] In the context of the present invention, an aryl group contains 6 to 40 ring atoms, preferably carbon atoms. In the context of the present invention, a heteroaryl group contains 5 to 40 ring atoms, where the ring atoms include carbon atoms and at least one heteroatom, provided that the sum of the carbon atoms and heteroatoms totals at least 5. The heteroatoms are preferably selected from N, O, and / or S. An aryl group or heteroaryl group herein refers to a simple aromatic ring derived from benzene, i.e., phenyl, or a simple heteroaromatic ring derived from, for example, pyridine, pyrimidine, or thiophene, or a fused aryl or heteroaryl group derived from, for example, naphthalene, anthracene, phenanthrene, quinoline, or isoquinoline. Thus, an aryl group having 6 to 18 carbon atoms is preferably phenyl, naphthyl, phenanthryl, or terphenylidene, and there is no restriction on the linkage when the aryl group is a substituent. In the context of the present invention, an aryl or heteroaryl group may bear one or more groups, and suitable groups are described below. If no such group is described, the aryl group or heteroaryl group is unsubstituted.

[0036] In the context of the present invention, an aromatic ring system contains 6 to 40 carbon atoms in the ring system. The aromatic ring system also includes an aryl group as described above.

[0037] An aromatic ring system having 6 to 18 carbon atoms is preferably selected from phenyl, fully deuterated phenyl, biphenyl, naphthyl, phenanthryl, and terphenylidene.

[0038] In the context of the present invention, a heteroaromatic ring system contains 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 a heteroaryl group as described above. The heteroatoms in the heteroaromatic ring system are preferably selected from N, O, and / or S.

[0039] In the context of the present invention, an aromatic or heteroaromatic ring system is not necessarily one that contains only aryl or heteroaryl groups, but rather a system in which multiple aryl or heteroaryl groups can also be interrupted by non-aromatic units (preferably less than 10% of the non-H atoms) such as carbon or oxygen atoms or carbonyl groups. For example, in the context of the present invention, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, 9,9-dialkylfluorene, diaryl ether, stilbene, etc. will thus be considered aromatic or heteroaromatic ring systems, and the same is true for systems in which two or more aryl groups are interrupted, for example, by a straight-chain or cyclic alkyl group or by a silyl group. In addition, systems in which two or more aryl or heteroaryl groups are directly bonded to each other, such as biphenyl, terphenyl, quaterphenyl, or bipyridine, are likewise encompassed by the definition of an aromatic or heteroaromatic ring system.

[0040] An aromatic or heteroaromatic ring system having 5 to 40 ring atoms and capable of being attached to an aromatic or heteroaromatic ring at any position is understood to mean, for example, a group derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzofluoranthene, tetracene, pentacene, benzopyrene, biphenyl, bibenzylidene, terphenyl, terbenzylidene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indeno[1,2-b]fluorene, cis- or trans-monobenzylindeno[1,2-b]fluorene, cis- or trans-dibenzylindeno[1,2-b]fluorene, triphenylene, isotriphenylene, spirotriphenylene, spiroisotriphenylene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indeno[1,2-b]carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phen azine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridineimidazole, pyrazineimidazole, quinoxalineimidazole, azole, benzo azole, naphtho azole, anthra azole, phenanthro azole, iso azole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaphenanthrene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phen azine, phenothiazine, fluoranthene ring, naphthyridine, azacarbazole, benzocarbazole, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- diazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0041] The abbreviations Ar, Ar1 and Ar4 are the same or different in each case and denote an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and capable of being substituted by one or more R 2 groups, where R 2 groups or substituents R 2has the definition as described in the context. Preferred definitions of Ar as well as Ar1 and Ar4 are described below.

[0042] The abbreviation "aryl" has the same or different meanings in each case and denotes an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and being optionally substituted by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where one or more non-adjacent CH2 groups in the alkyl group may be replaced by O or S, and where one or more hydrogen atoms in the alkyl group may be replaced by D, F or CN.

[0043] The abbreviations Ar2 and Ar3 have the same or different meanings in each case and denote H, D, CN, F, an undehydrogenated or partially or fully deuterated alkyl group having 1 to 10 carbon atoms, an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 5 to 40 ring atoms, the ring system being optionally substituted by one or more R 2 groups, where R 2 group or substituent R 2 has the definition as described in the context. Preferred definitions of Ar2 and Ar3 are described below.

[0044] The abbreviation Ar5 is the same or different in each case and is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and being optionally substituted by one or more R 7 groups, where R 7 group or substituent R 7 has the definition as described in the context. Preferred definitions of Ar5 are described below.

[0045] In the context of the present invention, a cyclic alkyl, alkoxy or thioalkyl group is a monocyclic, bicyclic or polycyclic group.

[0046] In the context of the present invention, a straight-chain, branched or cyclic C1 to C 20Alkyl refers to, for example, 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, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl-n-dec-1-yl, 1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl, 1,1-dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl, 1,1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1-diethyl-n-oct-1-yl, 1,1-diethyl-n-dec-1-yl, 1,1-diethyl-n-dodec-1-yl, 1,1-diethyl-n-tetradec-1-yl, 1,1-diethyl-n-hexadec-1-yl, 1,1-diethyl-n-octadec-1-yl, 1-(n-propyl)-cyclohex-1-yl, 1-(n-butyl)-cyclohex-1-yl, 1-(n-hexyl)-cyclohex-1-yl, 1-(n-octyl)-cyclohex-1-yl, and 1-(n-decyl)-cyclohex-1-yl groups.

[0047] The following describes the materials for organic electronic devices containing one or more compounds of formula (1) and the preferred embodiments of the compounds of formula (1). The preferred embodiments also apply to the mixtures of the present invention, the formulations of the present invention, and the organic electronic or electroluminescent devices of the present invention.

[0048] In the compound of formula (1), the substituent L-Rx can be bonded at any position.

[0049] Preferred compounds of formula (1) are the compounds of formula (1a) to formula (1j):

[0050]

[0051]

[0052] where Rx, L, R a , R b , R cAr1 has the definition given above or as a preferred definition below, and wherein the compounds of formula (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) are partially or fully deuterated.

[0053] Since the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) are deuterated compounds, in their preparation, when choosing to prepare by reacting an undeuterated compound of one of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) with a deuteration source or when choosing in the preparation that the starting compound for deuteration is a mixture of deuterated starting compounds, a mixture of deuterated products with the same chemical parent structure can be formed, which only differ in the degree of deuteration and / or the mode of deuteration.

[0054] Therefore, the present invention relates to a material for an organic electronic device comprising at least one compound of formula (1), wherein the at least one compound of formula (1) may comprise a mixture of deuterated products with the same chemical parent structure, wherein the deuterated compounds only differ in the degree of deuteration and / or the mode of deuteration.

[0055] Therefore, the present invention preferably relates to a material for an organic electronic device, which consists of a compound of formula (1) having a certain deuteration mode or consists of two or more compounds of formula (1) having the same chemical parent structure of formula (1), which only differ in the degree of deuteration and / or the mode of deuteration.

[0056] In a preferred embodiment of the material of the present invention for an electronic device comprising a compound of formula (1) as described above or preferably described, the average degree of deuteration is 20 mol% to 100 mol%, preferably 30 mol% to 90 mol%, more preferably 40 mol% to 80 mol%, and most preferably 50 mol% to 70 mol%.

[0057] The corresponding deuteration methods are known to those skilled in the art and are described in, for example, KR2016041014, WO2017 / 122988, KR202005282, KR101978651 and WO2018 / 110887, or in Bulletin of the Chemical Society of Japan, 2021, 94(2), 600 - 605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063 - 1071.

[0058] Particularly preferred compounds of formula (1) are compounds of formula (1a) and formula (1b), wherein Rx, L, R a , R b , R c and Ar1 have the definitions given above or as preferred definitions below, and they are partially or fully deuterated.

[0059] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is an aromatic or heteroaromatic ring system of formula L-1 to formula L-41, which may be substituted by one or more R 0 groups, wherein R 0 is D:

[0060]

[0061]

[0062] wherein the dashed line represents a bond connecting to Rx or to the remainder of formula (1) or to the remainder of formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j);

[0063] V1 and V2 are each independently O, S, Se or N-Ar4; and

[0064] Ar4 is in each case the same or different and is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and may be substituted by one or more R 2 groups, wherein the R 2 group or substituent R 2 has the definition as described in the context.

[0065] In a preferred embodiment of the present invention, L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is a single bond.

[0066] In a preferred embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from: linking groups L-1 to L-7 and linking groups L-14 to L-41, which may be substituted by one or more R 0 groups, wherein R 0It is D. In linkers L-18 to L-30 and L-35 to L-41, V1 is preferably O, S or N-Ar4, and Ar4 is preferably an aromatic ring system having 6 to 20 ring atoms and being substitutable by one or more R 2 groups. R in N-Ar4 2 is preferably D, F or CN, more preferably D. In linkers L-18 to L-30 and L-35 to L-41, Ar4 is more preferably selected, when it occurs, from non-deuterated, partially deuterated or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl.

[0067] In linkers L-18 to L-30 and L-35 to L-41, Ar4 is most preferably selected, when it occurs, from partially deuterated or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl.

[0068] In linkers L-18 to L-30 and L-35 to L-41, V1 is more preferably O or S. In linkers L-18 to L-30 and L-35 to L-41, V1 is most preferably O.

[0069] In linker L-35 to L-38, V2 is preferably O or S, more preferably O.

[0070] Substituent R 0 is the same or different when it occurs and is preferably selected from D, F, CN, Si(Ar)3 or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, where Ar has the definition given above. Substituent R 0 is preferably D when it occurs. Ar in Si(Ar)3 is preferably the same and is an aromatic ring system having 6 to 20 ring atoms and being substitutable by one or more R 2 groups. R in Ar 2 is preferably D, F or CN, more preferably D. In Si(Ar)3, Ar is more preferably selected from non-deuterated, partially deuterated or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl.

[0071] In one embodiment of the present invention, the linker L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linkers L-1 to L-3, which may be substituted by one or more R 0 groups, where R 0 is D.

[0072] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-1 to L-3, which are substituted by one or more R 0 groups, where R 0 is D.

[0073] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-4 to L-7, which may be substituted by one or more R 0 groups, where R 0 is D.

[0074] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-4 to L-7, which are substituted by one or more R 0 groups, where R 0 is D.

[0075] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-14 to L-17, which may be substituted by one or more R 0 groups, where R 0 is D.

[0076] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-14 to L-17, which are substituted by one or more R 0 groups, where R 0 is D.

[0077] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-18 to L-30, which may be substituted by one or more R 0 groups, where R0 is D, and V1 has the definition given above or as a preferred definition.

[0078] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-18 to L-30, which are substituted by one or more R 0 groups, where R 0 is D, and V1 has the definition given above or as a preferred definition.

[0079] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-31 to L-34, which may be substituted by one or more R 0 groups, where R 0 is D.

[0080] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-31 to L-34, which are substituted by one or more R 0 groups, where R 0 is D.

[0081] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-35 to L-38, which may be substituted by one or more R 0 groups, where R 0 is D, and V1 and V2 have the definitions given above or as preferred definitions.

[0082] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-35 to L-38, which are substituted by one or more R 0 groups, where R 0 is D, and V1 and V2 have the definitions given above or as preferred definitions.

[0083] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-39 to L-41, which may be substituted by one or more R 0 groups, where R 0 is D, and V1 has the definition given above or as a preferred definition.

[0084] In one embodiment of the present invention, the linking group L in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is selected from linking groups L-39 to L-41, which are substituted by one or more R 0 groups, where R 0 is D, and V1 has the definition given above or as a preferred definition.

[0085] In one embodiment of the present invention, Rx in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is of formula (1-2) and the linking group L has the definition given above or as a preferred definition. This is a particularly preferred embodiment.

[0086] In one embodiment of the present invention, Rx in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is one of formula (1-3), formula (1-4) and formula (1-5), and the linking group L has the definition given above or as a preferred definition. In formula (1-3) to formula (1-5), R 1 is preferably H, D, CN or F, more preferably H or D.

[0087] In one embodiment of the present invention, Rx in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is one of formula (1-6), formula (1-7), formula (1-8), formula (1-9), formula (1-10) and formula (1-11), and the linking group L has the definition given above or as a preferred definition.

[0088] In one embodiment of the present invention, Rx in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is one of formula (1-6), formula (1-7), formula (1-8) and formula (1-9), and the linking group L has the definition given above or as a preferred definition. This is a preferred embodiment.

[0089] In one embodiment of the present invention, Rx in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is one of formula (1-12), formula (1-13), formula (1-14), formula (1-15) and formula (1-16), and the linking group L has the definition given above or as a preferred definition.

[0090] In one embodiment of the present invention, Rx in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is one of formula (1-2), formula (1-6), formula (1-7), formula (1-8) and formula (1-9), and the linking group L has the definition given above or as a preferred definition. This is a preferred embodiment.

[0091] The symbol V in formula (1-6) to formula (1-11) is O, S or N-Ar4, where Ar4 is preferably an aromatic ring system having 6 to 20 ring atoms and may be substituted by one or more R 2 groups. R in N-Ar4 2 is preferably D, F or CN, more preferably D. In formula (1-6) to formula (1-11), Ar4 is more preferably selected from non-deuterated, partially deuterated or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl when it appears.

[0092] In formula (1-6) to formula (1-11), Ar4 is most preferably selected from phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl, which are partially deuterated or fully deuterated, when it appears.

[0093] The symbol V in formula (1-6) to formula (1-11) is preferably O or S, particularly preferably O.

[0094] In the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) or preferably the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), R a 、R b and R c represent mono-substituted, di-substituted, tri-substituted, maximally allowable substitution or unsubstituted, and R a 、R b and R c are each independently D in each case.

[0095] In the case of mono-substitution, R a 、R b and R c are each independently D in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) or preferably the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), that is, each of the compounds bears three substituents R a 、R b and R c .

[0096] In one embodiment of the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), one substituent R a 、R b or R c represents unsubstituted, and two substituents R a 、R b or R c are D.

[0097] In a preferred embodiment of the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), two substituents R a 、R b or R c represent unsubstituted, and one substituent R a 、R b or R c is D.

[0098] In a preferred embodiment of the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), R a , R b or R c represents unsubstituted.

[0099] In the case of maximum allowable substitution, R a , R b and R c are D in formula (1-6), formula (1-7), formula (1-8), formula (1-9), formula (1-10), formula (1-11), formula (1-12), formula (1-13), formula (1-14), formula (1-15) and formula (1-16).

[0100] For formula (1-6), formula (1-7), formula (1-8), formula (1-9), formula (1-10), formula (1-11), formula (1-12), formula (1-13), formula (1-14), formula (1-15) and formula (1-16), preferably R a , R b and R c represent maximum substitution or unsubstituted.

[0101] The compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) or the preferred compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) are partially deuterated, and in one embodiment, the substituents R a , R b and R c are D and each independently represents mono-substitution, di-substitution or tri-substitution.

[0102] In the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) or the preferred compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), Ar2 and Ar3 are the same or different in each case and are H, D, CN, F, an undeuterated or partially or fully deuterated alkyl group having 1 to 10 carbon atoms, a cyclic group having 5 to 40 ring atoms and optionally substituted by one or more R 2Group-substituted aromatic or heteroaromatic ring systems, where R 2 has the definition given above. R in Ar2 and Ar3 2 is preferably D, F or CN, more preferably D.

[0103] In the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) or preferably the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), where Rx conforms to one of formula (1-2), formula (1-3), formula (1-4) or formula (1-5), Ar2 and Ar3 are the same or different in each case and are preferably aromatic or heteroaromatic ring systems having 5 to 40 ring atoms and which may be substituted by one or more R 2 Group-substituted aromatic or heteroaromatic ring systems, where R 2 has the definition given above or as a particularly preferred definition.

[0104] Ar2 and Ar3 in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) are aromatic or heteroaromatic ring systems having 5 to 40 ring atoms and which may be substituted by one or more R 2 Group are preferably independently selected from the group of Ar-1 to Ar-24:

[0105]

[0106]

[0107]

[0108] where Y 3 is the same or different in each case and is O, S, NAr4 or C(R # )2, where R 3 is H, R 2 or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may be substituted by one or more R 2 groups, where the dashed bond represents the attachment to the remainder of formula (1-2) to formula (1-15), and where R 2 and Ar4 have the definition given above or as a preferred definition above.

[0109] R #The groups are the same or different in each case and are H, D, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, each of which may be substituted by one or more R 2 groups, where one or more hydrogen atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may in each case be substituted by one or more R 2 groups, an aryloxy or heteroaryloxy group having 5 to 40 ring atoms and which may be substituted by one or more R 2 groups, or an aralkyl or heteroaralkyl group having 5 to 40 ring atoms and which may be substituted by one or more R 2 groups.

[0110] Y 3 is preferably O, S, NAr4 or C(CH3)2. Y 3 is very particularly preferably O. Y 3 Most preferably it is NAr4, where Ar4 has the definition given above or as a preferred definition.

[0111] In structures Ar-1 to Ar-24, the substituent R 3 is preferably the same or different in each case and is selected from: H, D, F, CN or an aromatic ring system having 6 to 30 ring atoms and which may in each case be substituted by one or more R 2 groups. In structures Ar-1 to Ar-24, the substituent R 3 is more preferably the same or different in each case and is selected from: H, D, phenyl which is undehydrogenated or partially or fully deuterated, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl.

[0112] In structures Ar-1 to Ar-24, the substituent R 3 is more preferably the same or different in each case and is selected from: H, D, and phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl which are partially deuterated or fully deuterated. R 3 is more preferably D.

[0113] In structures Ar-1 to Ar-24, preferably at least one substituent R 3 is D.

[0114] In structures Ar-1 to Ar-24, particularly preferably all substituents R 3 are D.

[0115] More preferably, in the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), each of Ar2 or Ar3 is independently Ar-1, Ar-2, Ar-3, Ar-12 to Ar-15, wherein R 3 has the definition given above or as a preferred definition.

[0116] In the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) or the preferred compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), Ar1 is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may be substituted by one or more R 2 groups; wherein R 2 has the definition given above. R in Ar1 2 is preferably D, F, CN or Si(aryl)3, wherein the aryl is the same or different in each case and is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may be substituted by one or more substituents selected from D, F, CN, straight-chain alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups in the alkyl group may be replaced by O or S, and wherein one or more hydrogen atoms in the alkyl group may be replaced by D, F or CN.

[0117] R in Ar1 2 is more preferably D, F or CN, and most preferably D.

[0118] In the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) or the preferred compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), Ar1 is preferably selected from Ar-1 to Ar-24 as described above or as a preferred description, or Ar1 conforms to one of formula (1-2) to formula (1-16), and R 3 has the definition as described above or as a preferred description.

[0119] In the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) or the preferred compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), Ar1 is more preferably selected from Ar-1 to Ar-24 as described above or preferably described, especially when the linking group L represents an aromatic or heteroaromatic ring system of formula L-1 to formula L-41 as described above or preferably described as above.

[0120] In the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) or the preferred compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), Ar1 is more preferably selected from one of formula (1-2) to formula (1-16), especially when the linking group L represents a single bond.

[0121] In the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) or the preferred compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), when the linking group L represents a single bond, Ar1 is more preferably formula (1-2), wherein Ar2 and Ar3 have the definitions given above or given as preferred definitions.

[0122] Examples of suitable compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) as described above or preferably described are the structures shown in Table 1 below.

[0123] Table 1:

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136] Particularly suitable compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) as described above or preferably described are compounds E1 to E39 in Table 2.

[0137] Table 2:

[0138]

[0139]

[0140]

[0141]

[0142]

[0143] The compounds of the present invention can be prepared by synthetic steps known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc.

[0144] In the following synthetic schemes, the compounds are shown with a small number of substituents to simplify the structure. This does not exclude the presence of some other desired substituents in the process. The methods shown for synthesizing the compounds of the present invention should be regarded as illustrative. Those skilled in the art will be able to develop alternative synthetic routes within the scope of common general knowledge in the art.

[0145] Scheme 1:

[0146]

[0147] Scheme 2:

[0148]

[0149] Scheme 3:

[0150]

[0151] Scheme 4: Ar' corresponds to L-Rx

[0152]

[0153] The detailed reaction conditions are known from the prior art or are described in the Examples section.

[0154] By these methods, optionally followed by purification, such as recrystallization or sublimation, highly pure compounds as described above or preferably described can be obtained, preferably more than 99% (determined by 1 1H NMR and / or HPLC) of the compound of formula (1). As described above, starting from a partially or fully deuterated starting compound, a partially deuterated or fully deuterated product is formed. The compound of formula (1) can also be prepared according to Schemes 1 to 4 and subsequently deuterated as described in the context.

[0155] Processing the materials of the present invention for organic electronic devices from the liquid phase, for example by spin coating or by printing methods, requires a formulation comprising at least one compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) or a mixture with other functional materials such as matrix materials, fluorescent emitters, phosphorescent emitters and / or emitters exhibiting TADF. These formulations can be, for example, solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents can preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, di Alkanes, phenoxytoluenes (especially 3-phenoxytoluene), (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenyl ethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol monobutyl methyl ether, triethylene glycol monobutyl 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 a mixture of these solvents.

[0156] The compounds of the invention of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) as described above or preferably described are suitable for use in organic electroluminescent devices, especially as electron transport materials, as hole blocking materials or as matrix materials.

[0157] When a compound of the invention of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) is used as a matrix material or synonymously a host material in a light-emitting layer, it is preferably used in combination with other compounds.

[0158] The present invention therefore also provides a mixture comprising at least one compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) or at least one preferred compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), or at least one compound of Table 1, or at least one of Compounds E1 to E39, and at least one other compound selected from the group consisting of: matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence). Suitable matrix materials and emitters for such mixtures of the present invention are described below.

[0159] The present invention also provides a preparation, which comprises at least one compound of the present invention as described above, or a mixture of the present invention as described above, and at least one solvent. The solvent may be the above solvents or a mixture of these solvents.

[0160] The present invention also provides an organic electronic device, which comprises an anode, a cathode and at least one organic layer, and the organic layer comprises at least one compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j), or at least one preferred compound of one of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), or at least one compound in Table 1, or at least one of Compounds E1 to E39. The description related to the deuterated materials also applies accordingly.

[0161] The organic electronic device may be selected, for example, from an organic integrated circuit (OIC), an organic field effect transistor (OFET), an organic thin film transistor (OTFT), an organic electroluminescent device, an organic solar cell (OSC), an organic optical detector, and an organic photoreceptor.

[0162] The organic electronic device is preferably an organic electroluminescent device.

[0163] The organic electroluminescent device of the present invention (synonymous with the organic electroluminescent device) is, for example, an organic light emitting transistor (OLET), an organic field quenching device (OFQD), an organic light emitting electrochemical cell (OLEC, LEC, LEEC), an organic laser diode (O-laser), or an organic light emitting diode (OLED). The organic electroluminescent device of the present invention is especially an organic light emitting diode or an organic light emitting electrochemical cell. The device of the present invention is more preferably an OLED.

[0164] In addition to comprising a light emitting layer (EML), the organic layer of the device of the present invention preferably further comprises 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 comprise two or more layers selected from this group, preferably selected from EML, HIL, HTL, ETL, EIL and HBL. Similarly, an intermediate layer having an exciton blocking function, for example, may be introduced between two light emitting layers.

[0165] If there are multiple light-emitting layers, these light-emitting layers preferably have several emission maxima between 380 nm and 750 nm in general, such that the overall result is white light emission; in other words, various fluorescent or phosphorescent light-emitting compounds are used in the light-emitting layer. Two or more fluorescent and / or phosphorescent compounds may also be present in the light-emitting layer. A system with three light-emitting layers is particularly preferred, wherein the three layers exhibit blue, green, and orange or red light emission. As an alternative to the above combination, the light-emitting layer may also exhibit yellow light emission. Such combinations are known to those skilled in the art. The organic electroluminescent device of the present invention may also be a tandem electroluminescent device, particularly a white light-emitting OLED.

[0166] The device may also comprise an inorganic material or a layer formed entirely of an inorganic material.

[0167] It is not at all difficult for those skilled in the art to select materials suitable for the above layers of the organic electroluminescent device considering the various materials known in the prior art. Here, those skilled in the art will think about the chemical and physical properties of the materials in a conventional manner, as he knows how the materials interact with each other in the organic electroluminescent device. This is related to, for example, the energy levels of the orbitals (HOMO, LUMO) or the triplet and singlet energy levels, and also related to other material properties.

[0168] The compounds of the present invention of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i), or formula (1j) as described above or preferably described can be used in different layers herein. Preferably, the organic electroluminescent device comprises at least one compound of formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), or (1j) or the above preferred embodiments as a fluorescent emitter, a phosphorescent emitter, or an emitter exhibiting TADF (thermally activated delayed fluorescence), particularly as a host material for a phosphorescent emitter in the light-emitting layer. In addition, the at least one compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i), or formula (1j) can also be used in the electron transport layer or the hole blocking layer. It is particularly preferred to use the compounds of the present invention of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i), or formula (1j) as the host material in the light-emitting layer.

[0169] The present invention also provides an organic electronic device as described above, wherein the organic layer comprises at least one light-emitting layer, and the light-emitting layer comprises at least one compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j), or at least one preferred compound of one of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), or at least one compound of Table 1 or at least one of Compounds E1 to E39.

[0170] In one embodiment of the present invention, for the device of the present invention, at least one other host material is selected in the light-emitting layer and this host material is used together with a compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) as described above or preferably described, or with a compound of Table 1 or Compounds E1 to E39.

[0171] The present invention thus also provides an organic electronic device as described above, wherein the organic layer comprises at least one light-emitting layer, and the light-emitting layer comprises at least one compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j), or at least one preferred compound of one of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j), or at least one compound of Table 1 or at least one of Compounds E1 to E39, and at least one other host material.

[0172] Suitable host materials that can be used in combination with the compounds of the present invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or aromatic sulfones, triarylamines, carbazole derivatives, dicarbazoles, indolocarbazole derivatives, indacarbazole derivatives, azacarbazole derivatives, bipolar host materials, borazines or borate esters, triazine derivatives, zinc complexes, silyldiazoles or silyltetrazole derivatives, phosphadiazole derivatives, bridged carbazole derivatives, terphenyl derivatives or dibenzofuran derivatives. Similarly, other phosphorescent emitters having a shorter emission wavelength than the actual emitter can be present in the mixture as co-hosts, or compounds that do not contribute significantly even when participating in charge transport, such as wide-bandgap compounds, can be present.

[0173] A wide bandgap material, as used herein, refers to a material within the scope of the disclosure of US 7,294,849, characterized by a bandgap of at least 3.5 eV, where the bandgap refers to the gap between the HOMO and LUMO energies of the material.

[0174] Advantageously, particularly suitable host materials in a hybrid matrix system in combination with the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i), and formula (1j) as described above or preferably described can be selected from the compounds of formula (6), formula (7), formula (8), formula (9), formula (10), or formula (11) as described below.

[0175] The present invention thus also provides an organic electronic device comprising an anode, a cathode, and at least one organic layer, wherein the at least one organic layer comprises at least one light-emitting layer, and wherein the at least one light-emitting layer comprises at least one compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i), or formula (1j) as described above or preferably described as host material 1, and at least one compound of formula (6), formula (7), formula (8), formula (9), formula (10), or formula (11) as host material 2.

[0176]

[0177]

[0178] wherein the symbols and notations used are as follows:

[0179] A 1 is C(R 7 )2, NR 7 , O, or S;

[0180] L1 is a bond, O, S, C(R 7 )2, or NR 7 ;

[0181] A is independently in each case a group of formula (3) or formula (4).

[0182]

[0183] X2 is the same or different in each case and is CH, CR 6 , or N, where no more than 2 symbols X2 can be N;

[0184] * represents the binding site to formula (9);

[0185] U 1 , U2 When they occur, for the key, O, S, C(R 7 )2 or NR 7 ;

[0186] R 6 In each case the same or different and is D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group in each case may be substituted by one or more R 7 groups, and where one or more non-adjacent CH2 groups may be replaced by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7 , or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms and in each case may be substituted by one or more R 7 groups, where two R 6 groups may also together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;

[0187] Ar5 is in each case the same or different and independently is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and may be substituted by one or more R 7 groups;

[0188] R 7 In each case the same or different and is 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 alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group in each case may be substituted by one or more R 8 groups, where one or more non-adjacent CH2 groups may 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 may be substituted by one or more R 8Group-substituted aromatic or heteroaromatic ring systems; simultaneously, two or more R 7 groups together can form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; preferably, said R 7 groups do not form any such ring system;

[0189] R 8 is in each case the same or different and is H, D, F, or an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 carbon atoms, especially a hydrocarbon group, where one or more hydrogen atoms may also be replaced by F;

[0190] c, c1, c2 are each independently 0 or 1 in each case, where the sum of the marked c + c1 + c2 = 1 in each case;

[0191] d, d1, d2 are each independently 0 or 1 in each case, where the sum of the marked d + d1 + d2 = 1 in each case;

[0192] q, q1, q2 are each independently 0 or 1 in each case;

[0193] s is in each case the same or different and is 0, 1, 2, 3 or 4;

[0194] t is in each case the same or different and is 0, 1, 2 or 3;

[0195] u is in each case the same or different and is 0, 1 or 2;

[0196] u1, u2 are each independently 0 or 1 in each case, where the sum u1 + u2 = 1; and

[0197] v is 0 or 1.

[0198] In the compounds of formula (6), formula (7), formula (8), formula (10) or formula (11), when the R 6 group is not D, s is preferably 0 or 1, or more preferably 0.

[0199] In the compounds of formula (6), formula (7) or formula (8), when the R 6 group is not D, t is preferably 0 or 1, or more preferably 0.

[0200] In the compounds of formula (6), formula (7), formula (8) or formula (10), when the R 6 group is not D, u is preferably 0 or 1, or more preferably 0.

[0201] In the compounds of formula (6), formula (7), formula (8), formula (10) and formula (11), the sum of the labels s, t and u is preferably not more than 6, more preferably not more than 4, and even more preferably not more than 2. When R 6 is not D, this is the preferred case.

[0202] In the compound of formula (9), c, c1, and c2 are each independently 0 or 1 in each case, where the sum of the labels c + c1 + c2 is 1 in each case. c2 is preferably defined as 1.

[0203] In the compound of formula (9), L1 is preferably a single bond or C(R 7 )2, where R 7 has the definition given above; more preferably, L1 is a single bond.

[0204] In formula (4), U 1 or U 2 is preferably a single bond or C(R 7 )2 when it appears, where R 7 has the definition given above; more preferably, U 1 or U 2 is a single bond when it appears.

[0205] In a preferred embodiment of the compounds of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11) which can be combined with the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) according to the invention, R 6 is the same or different in each case and is selected from: D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl group can be substituted by one or more R 7 groups in each case, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, preferably having 5 to 40 ring atoms and which can be substituted by one or more R 7 groups in each case.

[0206] In a preferred embodiment of the compounds of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11) which can be combined with the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) according to the invention, R 6 is the same or different in each case and is selected from: D or an aromatic ring system having 6 to 30 ring atoms and which can be substituted by one or more R7 Group-substituted aromatic or heteroaromatic ring systems.

[0207] Preferably, in the compounds of formula (6), formula (7), formula (8), formula (10) and formula (11), Ar5 is selected from phenyl, biphenyl, especially o-biphenyl, m-biphenyl or p-biphenyl, terphenyl, especially o-terphenyl, m-terphenyl or p-terphenyl or branched terphenyl, quaterphenyl, especially o-quaterphenyl, m-quaterphenyl or p-quaterphenyl or branched quaterphenyl, fluorenyl which can be linked via the 1, 2, 3 or 4 positions, spirobifluorenyl which can be linked via the 1, 2, 3 or 4 positions, naphthyl, especially naphthyl bonded at the 1 or 2 position, or a group derived from the following: indole, benzofuran, benzothiophene, carbazole which can be linked via the 1, 2, 3 or 4 positions, dibenzofuran which can be linked via the 1, 2, 3 or 4 positions, dibenzothiophene which can be linked via the 1, 2, 3 or 4 positions, indeno[1,2-b]carbazole, indolo[1,2-b]carbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or terphenylidene, each of which can be substituted by one or more R 7 Group substitution. Ar5 is preferably unsubstituted.

[0208] When A in formula (7) or formula (8) or formula (11) 1 is NR 7 , the substituent R bonded to the nitrogen atom 7 is preferably an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms and which can also be substituted by one or more R 8 groups. In a particularly preferred embodiment, the substituent R 7 is in each case the same or different and is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, especially having 6 to 18 aromatic ring atoms. Preferred embodiments of R 7 are preferably unsubstituted phenyl, biphenyl, terphenyl and quaterphenyl and groups derived from triazine, pyrimidine and quinazoline which can be substituted by one or more R 8 groups.

[0209] When A in formula (7) or formula (8) or formula (11) 1 is C(R 7 )2, the substituent R bonded to this carbon atom 7 is in each case preferably the same or different and is a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms and which can also be substituted by one or more R 8 groups. Most preferably, R 7 is a methyl group or a phenyl group. In this case, R 7The groups together may also form a ring system, thereby obtaining a spiro ring system.

[0210] In a preferred embodiment of the compounds of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11), these compounds are partially or fully deuterated, more preferably fully deuterated.

[0211] The preparation of the compounds of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11) is generally known, and some compounds are commercially available.

[0212] The compounds of formula (9) are disclosed as examples on pages 110 to 119, especially on pages 120 to 127 in WO2021 / 180614. Their preparation is disclosed in the synthesis examples on pages 128 and 214 to 218 of WO2021 / 180614.

[0213] The preparation of the triarylamines of formula (11) is known to those skilled in the art, and some compounds are commercially available.

[0214] If the other matrix material is a deuterated compound, the other matrix material may be a mixture of deuterated compounds of the same chemical basic structure, which differ only in the deuteration level and / or deuteration pattern.

[0215] In a preferred embodiment of the other matrix material, this is a mixture of deuterated compounds of formula (6), formula (7), formula (8), formula (9), formula (10) or formula (11) as described above, wherein the average deuteration level of these compounds is at least 50% to 90%, preferably 70% to 100%. The corresponding deuteration methods are known to those skilled in the art and are described, for example, in KR2016041014, WO2017 / 122988, KR202005282, KR101978651 and WO2018 / 110887, or in Bulletin of the Chemical Society of Japan, 2021, 94(2), 600 - 605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063 - 1071.

[0216] 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 catalyst or a palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound containing one or more deuterium atoms and capable of releasing them under suitable conditions.

[0217] The platinum catalyst is preferably dry platinum on carbon, preferably 5% dry platinum on carbon. The palladium catalyst is preferably dry palladium on carbon, preferably 5% dry palladium on carbon. 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, where the fully deuterated solvents are not limited herein. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. A particularly preferred deuterium source is a combination of D2O and toluene-d8. The reaction is preferably carried out under heating, more preferably at a temperature heated to between 100 °C and 200 °C. In addition, the reaction is preferably carried out under pressure.

[0218] Examples of suitable other matrix materials for combination with the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) as described above or preferably described are the compounds described in Table 3 on pages 137 to 203 of WO2019 / 229011, which may also be partially or fully deuterated.

[0219] Examples of suitable other matrix materials for combination with the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) as described above or preferably described are the compounds described by Compounds 1 to 166 in the table on page 30 of WO2011 / 088877, which may also be partially or fully deuterated.

[0220] Examples of suitable other matrix materials for combination with the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) as described above or preferably described are the compounds described by Compounds 1 to 151 in the table on page 23 of WO2011 / 128017, which may also be partially or fully deuterated.

[0221] For combination with the compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) as described above or preferably described, particularly suitable compounds are the compounds of formula (6) and / or formula (9) and / or formula (10) as described above or preferably described.

[0222] For combinations with compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) as described above or preferably described, particularly suitable compounds are compounds of formula (6), wherein at least one Ar5 group is a heteroaromatic ring system having 5 to 40 ring atoms and which may be substituted by one or more R 7 groups, and / or compounds of formula (9) and / or compounds of formula (10).

[0223] For combinations with compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) as described above or preferably described, compounds of formula (9) or formula (10) are very particularly preferably suitable.

[0224] For combinations with compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) as described above or preferably described, compounds of formula (10) are very particularly preferably suitable.

[0225] Other examples of suitable host materials of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11) for combinations with compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) as described above or preferably described are the structures in Tables 3 and 4 given below.

[0226] Table 3:

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235] Particularly suitable compounds of formula (6), formula (7), formula (8), formula (9), formula (10) or formula (11) which are selected according to the present invention and are preferably combined with at least one compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) for use in the electroluminescent devices of the present invention are the compounds in Table 4.

[0236] Table 4:

[0237]

[0238]

[0239]

[0240]

[0241]

[0242] The host materials of the above formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) and their preferably described embodiments or the compounds in Table 1 or compounds E1 to E39 can be combined with the above matrix materials / host materials, matrix materials / host materials of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11) and their preferably described embodiments or compounds H1 to H33 in the devices of the present invention as needed.

[0243] A very particularly preferred mixture of compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) and host materials of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11) for use in the devices of the present invention is obtained by combining compounds E1 to E39 and compounds H1 to H33 as shown in Table 5 below. For example, the first mixture M1 is the combination of compound E1 and H1.

[0244] Table 5:

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262] In the mixture of the present invention or in the light-emitting layer of the device of the present invention, with respect to the total mixture or with respect to the total composition of the light-emitting layer, the total concentration of all host materials of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) as described above or preferably described is generally in the range of 5 wt% to 90 wt%, 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%.

[0263] In the mixture of the present invention or in the light-emitting layer of the device of the present invention, the total concentration of all host materials of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11) as described above or preferably described is generally in the range of 10% to 95% by weight, preferably in the range of 15% to 90% by weight, more preferably in the range of 15% to 80% by weight, even more preferably in the range of 20% to 70% by weight, very particularly preferably in the range of 40% to 80% by weight, and most preferably in the range of 50% to 70% by weight, relative to the total mixture or relative to the total composition of the light-emitting layer.

[0264] The present invention also relates to a mixture which, in addition to containing the host materials of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) described above (hereinafter referred to as host material 1) and at least one host material of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11) as described above or preferably described (hereinafter referred to as host material 2), further contains at least one phosphorescent emitter.

[0265] The present invention also relates to a mixture selected from M1 to M1287, which further contains at least one phosphorescent emitter.

[0266] The term "phosphorescent emitter" generally encompasses compounds that emit light through spin-forbidden transitions from excited states with a higher spin multiplicity, i.e., spin state > 1, such as transitions from triplet states or states with even higher spin quantum numbers (such as quintet states). This preferably refers to transitions from triplet states.

[0267] Suitable phosphorescent emitters (= triplet emitters) are especially those that emit light when appropriately excited, preferably in the visible region and 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 compounds of metals having such atomic numbers. Preferred phosphorescent emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium or platinum. In the context of the present invention, all luminescent compounds containing the above metals are regarded as phosphorescent emitters.

[0268] Generally, all phosphorescent complexes according to the prior art and known to those skilled in the art in the field of organic electroluminescent devices for phosphorescent OLEDs are suitable.

[0269] Preferred phosphorescent emitters according to the present invention conform to formula (IIIa):

[0270]

[0271] The symbols and notations used in formula (IIIa) are defined as follows:

[0272] n + m is 3, n is 1 or 2, and m is 2 or 1.

[0273] X is the same or different in each case and is N or CR.

[0274] R is the same or different in each case and 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 7 carbon atoms, which may be partially or fully deuterium-substituted, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms and may be partially or fully deuterium-substituted.

[0275] The present invention thus also provides an organic electroluminescent device as described above or preferably described, characterized in that in addition to comprising the host material 1 and the host material 2, the light-emitting layer further comprises at least one phosphorescent emitter conforming to formula (IIIa) as described above.

[0276] In the emitter of formula (IIIa), n is preferably 1 and m is preferably 2.

[0277] In the emitter of formula (IIIa), preferably, one X is selected from N and the other X is CR, or all X are the same or different in each case and are CR.

[0278] In the emitter of formula (IIIa), at least one R is preferably different from H. In the emitter of formula (IIIa), preferably two Rs are different from H and have one of the other definitions given above for the emitter of formula (IIIa).

[0279] The preferred phosphorescent emitters according to the present invention conform to formula (I), formula (II), formula (III), formula (IV), or formula (V):

[0280]

[0281]

[0282] The symbols and notations of these formula (I), formula (II), formula (III), formula (IV), and formula (V) are defined as follows:

[0283] 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 and may be partially or fully deuterium-substituted.

[0284] Preferred phosphorescent emitters according to the present invention conform to formula (VI), (VII) or (VIII):

[0285]

[0286] wherein the symbols and notations in these formulas (VI), (VII) and (VIII) are defined as follows:

[0287] 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 may be partially or fully deuterium-substituted.

[0288] Preferred examples of the phosphorescent emitters are described in Table 5 on pages 120 to 126 and Table 6 on pages 127 to 129 of WO2019 / 007867. The emitters are incorporated herein by reference into the specification of the present invention.

[0289] Particularly preferred examples of the phosphorescent emitters are listed in Table 6 below.

[0290] Table 6:

[0291]

[0292]

[0293]

[0294]

[0295]

[0296] In the mixture of the present invention or in the light-emitting layer of the device of the present invention, any mixture selected from the sum of mixtures M1 to M1287 is preferably combined with a compound of formula (IIIa) or a compound of formula (I) to formula (VIII) or a compound of Table 6.

[0297] The light-emitting layer containing at least one phosphorescent emitter in the organic electroluminescent device of the present invention is preferably an infrared light-emitting layer or a yellow, orange, red, green, blue or ultraviolet light-emitting layer, more preferably a yellow or green light-emitting layer, and most preferably a green light-emitting layer.

[0298] The yellow light-emitting layer herein refers to a layer with a photoluminescence maximum in the range of 540 nm to 570 nm. The orange light-emitting layer refers to a layer with a photoluminescence maximum in the range of 570 nm to 600 nm. The red light-emitting layer refers to a layer with a photoluminescence maximum in the range of 600 nm to 750 nm. The green light-emitting layer refers to a layer with a photoluminescence maximum in the range of 490 nm to 540 nm. The blue light-emitting layer refers to a layer with a photoluminescence maximum in the range of 440 nm to 490 nm. The photoluminescence maximum of the layer is measured herein by measuring the photoluminescence spectrum of a layer with a thickness of 50 nm at room temperature, and the layer has a creative combination of host material 1 of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) and host material 2 of at least one of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11) and a suitable luminescent body.

[0299] For example, the photoluminescence spectrum of the layer is recorded using a commercially available photoluminescence spectrometer.

[0300] Typically at room temperature in an oxygen-free solution of 10 -5 The photoluminescence spectrum of the selected luminescent body is measured, and a suitable solvent is any solvent in which the selected luminescent body is dissolved at the mentioned concentration. Particularly suitable solvents are usually toluene or 2-methyl-THF, and also dichloromethane. The measurement is carried out using a commercially available photoluminescence spectrometer. The triplet energy T1 is determined from the photoluminescence spectrum of the luminescent body, in eV. First, the peak maximum Plmax. (in nm) of the photoluminescence spectrum is determined. Then the peak maximum Plmax. (in nm) is converted to eV by the following formula: E(T1, in eV) = 1240 / E(T1, in nm) = 1240 / Plmax. (in nm).

[0301] Therefore, the preferred phosphorescent luminescent body is a yellow luminescent body, preferably the yellow luminescent body of formula (IIIa), formula (I) to formula (VIII) or Table 6, and its triplet energy T1 is preferably about 2.3 eV to about 2.1 eV.

[0302] Therefore, the preferred phosphorescent luminescent body is a green luminescent body, preferably the green luminescent body of formula (IIIa), formula (I) to formula (VIII) or Table 6, and its triplet energy T1 is preferably about 2.5 eV to about 2.3 eV.

[0303] Therefore, the particularly preferred phosphorescent luminescent body is a green luminescent body, preferably the green luminescent body of formula (IIIa), formula (I) to formula (VIII) or Table 6 as described above, and its triplet energy T1 is preferably about 2.5 eV to about 2.3 eV.

[0304] Most preferably, the green emitters as described above, preferably the green emitters of formula (IIIa), formulas (I) to (VIII) or Table 6, are selected for use in the mixtures or the light-emitting layers of the present invention.

[0305] Fluorescent emitters may also be present in the light-emitting layer of the device of the present invention or in the mixtures of the present invention.

[0306] Preferred fluorescent emitting compounds are selected from arylamines, wherein at least one of the aromatic or heteroaromatic ring systems of the arylamine is preferably a fused ring system, more preferably having at least 14 ring atoms. Preferred examples of these ring systems are aromatic anthrylamines, aromatic anthryldiamines, aromatic pyrylamines, aromatic pyryldiamines, aromatic perylamines or aromatic peryldiamines. Aromatic anthrylamines refer to compounds in which the diarylamino group is preferably directly bonded to the anthracene group at the 9-position. Aromatic anthryldiamines refer to compounds in which two diarylamino groups are preferably directly bonded to the anthracene group at the 9,10-positions. Aromatic pyrylamines, pyryldiamines, perylamines and peryldiamines are defined similarly, wherein the diarylamino group is preferably bonded to the pyrene at the 1-position or 1,6-positions. Other preferred emitting compounds are indeno[1,2-b]fluoreneamines or indeno[1,2-b]fluorenediamines, benzoindeno[1,2-b]fluoreneamines or benzoindeno[1,2-b]fluorenediamines and dibenzoindeno[1,2-b]fluoreneamines or dibenzoindeno[1,2-b]fluorenediamines and indeno[1,2-b]fluorene derivatives having fused aryl groups. Pyrylphenylamines are also preferred. Benzoindeno[1,2-b]fluoreneamines, benzo[1,2-b]fluoreneamines, extended benzoindeno[1,2-b]fluorenes, phen azine and fluorene derivatives linked to a furan unit or to a thiophene unit are also preferred. The light-emitting device or mixture of the present invention may also additionally contain materials exhibiting TADF (thermally activated delayed fluorescence).

[0307] In another preferred embodiment of the present invention, at least one light-emitting layer of the organic electroluminescent device may comprise three or four different host materials, preferably three different host materials. These corresponding mixed host systems may be composed of the host materials described for host material 1 and host material 2, but for example, in addition to containing host material 1 or host material 2, they may also contain a wide-bandgap material, a bipolar host material, an electron transport material (ETM) or a hole transport material (HTM) as the third or fourth host material.

[0308] Preferably, the mixed host system is optimized for the emitters of formula (IIIa), formulas (I) to (VIII) or Table 5.

[0309] According to one embodiment of the present invention, in addition to comprising the host material 1 of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) as described above and the component of host material 2 selected from one or more compounds of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11), the mixture does not contain any other components, i.e., functional materials. These are material mixtures used as such for manufacturing the light-emitting layer. These mixtures are also referred to as premix systems, which are used as the sole material source in the vapor deposition of the host material of the light-emitting layer and have a constant mixing ratio in the vapor deposition. In this way, the vapor deposition of a layer with a uniform distribution of components can be achieved in a simple and rapid manner without the need to precisely drive multiple material sources.

[0310] In an alternative embodiment of the present invention, as a mixture of the premix system, in addition to comprising the components of the host material 1 and the host material 2 as described above, it further comprises the phosphorescent emitter as described above. As described above, when the mixing ratio in the vapor deposition is appropriate, this mixture can also be used as the sole material source. Preferably, the premix system consists of two host materials, i.e., a compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) and a compound of one of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11).

[0311] Preferably, the premix system consists of three host materials, i.e., a compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) and two compounds of one of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11).

[0312] The components or ingredients of the light-emitting layer of the device of the present invention can be processed by vapor deposition or from a solution. For this purpose, the host material 1 and the host material 2 as described above or preferably described can be provided in a formulation containing at least one solvent, optionally in combination with the material of the phosphorescent emitter as described above or preferably described. Suitable formulations are described above.

[0313] According to the preferred embodiments and the luminescent compounds, relative to the overall composition of the light emitter and the matrix material, the light-emitting layer in the device of the present invention preferably contains a matrix material between 99.9 vol% and 1 vol%, more preferably between 99 vol% and 10 vol%, more preferably between 98 vol% and 60 vol%, and most preferably between 97 vol% and 80 vol%. According to the preferred embodiments, the matrix material comprises at least one compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) and at least one compound of formula (6), formula (7), formula (8), formula (9), formula (10) or formula (11). Accordingly, relative to the overall composition of the light-emitting layer composed of the light emitter and the matrix material, the light-emitting layer in the device of the present invention preferably contains a light emitter between 0.1 vol% and 99 vol%, more preferably between 1 vol% and 90 vol%, more preferably between 2 vol% and 40 vol%, and most preferably between 3 vol% and 20 vol%. If the compound is processed from a solution, the corresponding amounts in weight% are preferably used instead of the amounts in vol% described above.

[0314] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the organic layer comprises a hole injection layer (HIL) and / or a hole transport layer (HTL), and the hole injection material and the hole transport material belong to arylamine compounds.

[0315] The order of the layers in the organic electroluminescent device of the present invention is preferably as follows:

[0316] Anode / hole injection layer / hole transport layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0317] This layer order is the preferred order.

[0318] At the same time, it should be pointed out again that not all of the mentioned layers need to be present and / or other layers may also be present.

[0319] The material for the electron transport layer can be any material used as an electron transport material in the electron transport layer according to the prior art. 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, phosphadiazole derivatives, and phosphine oxide derivatives.

[0320] Suitable cathodes for the devices of the present invention are metals with a low work function, metal alloys or multi-layer structures composed of various metals such as alkaline earth metals, alkali metals, main group metals or lanthanide elements (such as Ca, Ba, Mg, Al, In, Yb, Sm, etc.). In addition, alloys containing alkali metals or alkaline earth metals and silver are suitable, such as alloys containing magnesium and silver. In the case of multi-layer structures, in addition to the metals mentioned, other metals with a relatively high work function, such as Ag or Al, can also be used. In this case, combinations of metals, such as Ca / Ag, Mg / Ag or Ba / Ag, are usually used. It is also preferably to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. For this purpose, examples of available materials are alkali metal or alkaline earth metal fluorides, and can also be the corresponding oxides or carbonates (such as LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). For this purpose, lithium quinolate (LiQ) can also be used. The layer thickness of this layer is preferably between 0.5 nm and 5 nm.

[0321] Preferred anodes are materials with a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. First, metals with a high redox potential are suitable for this purpose, such as Ag, Pt or Au. Second, metal / metal oxide electrodes (such as Al / Ni / NiO x , Al / PtO x ) can also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to be able to irradiate the organic material (organic solar cell) or couple out light (OLED, O-laser). Here, the preferred anode material is a conductive mixed metal oxide. Particularly preferred is indium tin oxide (ITO) or indium zinc oxide (IZO). In addition, conductive doped organic materials are preferred, especially conductive doped polymers. In addition, the anode can also consist of two or more layers, such as an inner layer of ITO and an outer layer of metal oxide, and the metal oxide is preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0322] Since the presence of water and / or air will shorten the lifespan of the devices of the present invention, the organic electroluminescent devices of the present invention are appropriately (depending on the application) structured during the manufacturing process, provided with contact connections, and finally sealed.

[0323] The manufacturing of the devices of the present invention is not limited herein. One or more organic layers, including the light-emitting layer, can be coated by sublimation. In this case, the materials are applied by vapor deposition at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6 mbar in a vacuum sublimation system. However, in this case, the initial pressure can even be lower, such as less than 10-7 mbar.

[0324] Preferably, the organic electroluminescent device according to the invention is characterized in that one or more layers are coated by means of OVPD (organic vapor phase deposition) or by means of sublimation with a carrier gas. In this case, the material is applied under a pressure between 10 -5 mbar and 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, in which the material is applied directly through a nozzle and thus structured (e.g., M.S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0325] More preferably, the organic electroluminescent device according to the invention is characterized in that one or more organic layers comprising the composition according to the invention are produced 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 LITI (light-induced thermal imaging, thermal transfer) or inkjet printing. For this purpose, soluble host material 1 and host material 2 and a phosphorescent emitter are required. The advantage of processing from a solution is that, for example, the light-emitting layer can be applied in a very simple and inexpensive manner. This technique is particularly suitable for mass-producing organic electroluminescent devices.

[0326] In addition, a hybrid method is feasible, in which, for example, one or more layers are applied from a solution and one or more other layers are applied by vapor deposition.

[0327] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices.

[0328] In the case of production by means of vapor deposition, in principle there are two ways to apply or vapor deposit the organic layer according to the invention, preferably the light-emitting layer, onto any substrate or previous layer. First, the materials used can each be initially loaded in a material source and finally evaporated from different material sources ("co-evaporation"). Second, the various materials can be premixed (premix system), the mixture can be initially loaded in a single material source and finally evaporated therefrom ("premix evaporation"). In this way, vapor deposition of a light-emitting layer with a uniform distribution of components can be achieved in a simple and rapid manner without the need to precisely drive multiple material sources.

[0329] The following methods are feasible:

[0330] A method for producing an organic electroluminescent device according to the invention as described above or preferably described, characterized in that the organic layer, preferably the light-emitting layer, the electron transport layer and / or the hole blocking layer are applied by vapor deposition, in particular by sublimation and / or by means of OVPD (organic vapor phase deposition) and / or by means of sublimation with a carrier gas, or from a solution, in particular by spin coating or by a printing method.

[0331] A method for producing a device of the present invention, characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein at least one compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is vapor-deposited from at least two material sources in sequence or simultaneously together with other materials for forming the light-emitting layer.

[0332] A method for producing a device of the present invention, characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein the at least one compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) and formula (1j) is vapor-deposited in sequence or simultaneously as a premix with at least one other material and a luminescent material, and the luminescent material is selected from: phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

[0333] Compared with the prior art, the electronic devices of the present invention, especially organic electroluminescent devices, are notable for one or more of the following surprising advantages:

[0334] 1. An electronic device, especially an organic electroluminescent device, containing a compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) or a preferred embodiment described in the context, especially as a matrix material, has a very good lifetime. In this case, these compounds especially bring about a low roll-off, that is, the power efficiency of the device has a small decrease at high luminous density.

[0335] 2. The compounds of the present invention of formula (1a) and / or formula (1b) or the preferred embodiments described in the context exhibit extremely high stability and lifetime.

[0336] 3. By using a compound of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j) or a preferred embodiment described in the context, the formation of light loss channels in electronic devices, especially organic electroluminescent devices, can be avoided. Therefore, these devices are characterized by high PL efficiency of the emitter and thus high EL efficiency, as well as excellent energy transfer from the matrix to the dopant.

[0337] 4. The compounds of formula (1), formula (1a), formula (1b), formula (1c), formula (1d), formula (1e), formula (1f), formula (1g), formula (1h), formula (1i) or formula (1j), or the low triplet energy level T1 of the preferred embodiments described in the context, can be, for example, in the range of 2.50 eV to -2.90 eV.

[0338] These above-mentioned advantages are not accompanied by excessive deterioration of other electronic properties.

[0339] It should be noted that the scope of the present invention covers variations of the embodiments described in the present invention. Unless this is explicitly excluded, any feature disclosed in the present invention can be exchanged for an alternative feature that provides the same purpose or an equivalent or similar purpose. Therefore, unless otherwise stated, any feature disclosed in the present invention should be regarded as an instance of a general series or an equivalent or similar feature.

[0340] Unless specific features and / or steps are mutually exclusive, all features of the present invention can be combined with each other in any manner. This is especially true for combinations of the preferred features of the present invention.

[0341] The technical teachings disclosed in the present invention can be extracted and combined with other embodiments.

[0342] The present invention is illustrated in detail by the following examples, and is not intended to limit the present invention thereby. Examples

[0343] General method:

[0344] In all quantum chemical calculations, the Gaussian16 (Rev. 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 of the B3LYP / 6-31G(d) optimized ground state energy were determined at the B3LYP / 6-31G(d) level. Then, TD-DFT singlet and triplet excitations (vertical excitations) were calculated by the same method (B3LYP / 6-31G(d)) with the optimized ground state geometry. Standard settings for SCF and gradient convergence were used.

[0345] According to the energy calculation, the obtained HOMO is the last occupied orbital (αocc. eigenvalue) occupied by two electrons, and the LUMO is the first unoccupied orbital (αvirt. eigenvalue), in Hartree, where HEh and LEh represent the HOMO energy in Hartree and the LUMO energy in Hartree, respectively. This is used to determine the HOMO and LUMO values in electron volts, calibrated by the values measured by cyclic voltammetry, as follows:

[0346] HOMO calibration value = 0.90603 * HOMO - 0.84836

[0347] LUMO calibration value = 0.99687 * LUMO - 0.72445

[0348] The triplet energy level T1 of the material is defined as the relative excitation energy (in eV) of the triplet with the lowest energy, which is obtained by quantum chemical energy calculation.

[0349] The singlet energy level S1 of the material is defined as the relative excitation energy (in eV) of the singlet with the second lowest energy, which is obtained by quantum chemical energy calculation.

[0350] The singlet with the lowest energy is called S0.

[0351] The method described herein is independent of the software package used and always gives the same result. Examples of common programs for this purpose are "Gaussian09" (Gaussian, Inc.) and Q-Chem 4.1 (Q-Chem, Inc.). In this case, the software package "Gaussian16 (Rev. B.01)" was used to calculate the energy.

[0352] Synthesis Example

[0353] Unless otherwise stated, the following syntheses are carried out in a dry solvent under a protective gas atmosphere. Solvents and reagents can be purchased from, for example, Sigma-ALDRICH or ABCR. For compounds known from the literature, the corresponding CAS numbers are also reported in each case.

[0354] 1) 1-bromo-4H-naphtho[1,2,3,4-def]carbazole)-d 10

[0355]

[0356] 3.7 g (15.5 mmol, 1.00 equivalent) of 4H-naphtho[1,2,3,4-def]carbazole and 20.0 g of 5% Pt / activated carbon were suspended in 400 g (502 mmol, 1.00 equivalent) of deuterium oxide [CAS 7789-20-0] and 200 g (778 mmol, 1.55 equivalents) of toluene-d8 [CAS 2037-26-5]. The reaction mixture was stirred at 165 °C and elevated autogenous pressure for 5 hours. After cooling, it was extracted twice with tetrahydrofuran, the combined organic phases were washed with a saline solution, and dried over sodium sulfate. After filtration, the solvent was removed under reduced pressure. After further purification by extraction, recrystallization and sublimation, the above product was obtained in the form of a mixture of H / D isotopomers and H / D isotopologues fractions.

[0357] The yield was 1.7 g (6.9 mmol), corresponding to 47% of the theoretical value.

[0358] The following compounds were prepared in a similar manner:

[0359]

[0360]

[0361] 2) 1-Bromo-4H-naphtho[1,2,3,4-def]carbazole

[0362]

[0363] 43 g (180.0 mmol) of 4H-naphtho[1,2,3,4-def]carbazole was suspended in 1500 ml of DMF. To this suspension was added portionwise 32 g (180 mmol) of NBS (N-bromosuccinimide) at 0 °C, and the mixture was stirred in the dark for 5 hours, during which the temperature gradually rose to 30 °C. Thereafter, water / ice was added, the solid was taken out and washed with ethanol. The residue was recrystallized from toluene / ethanol (1:1). The yield was 39 g (123 mmol), corresponding to 69% of the theoretical value.

[0364] The following compounds were prepared in a similar manner:

[0365]

[0366]

[0367] 3) 1-Bromo-4-phenylnaphtho[1,2,3,4-def]carbazole

[0368]

[0369] The initial charge of 7.9 g (24.8 mmol, 1.00 equiv) of 1-bromo-4H-naphtho[1,2,3,4-def]carbazole, 26.1 g (128 mmol, 5.2 equiv) of iodobenzene, and 7.1 g (74.4 mmol, 3 equiv) of NaOtBu in 220 ml of dry DMF was inerted with argon. Subsequently, 0.62 g (2.7 mmol, 0.11 equiv) of 1,3-bis(2-pyridyl)propane-1,3-dione and 0.52 g (2.7 mmol, 0.11 equiv) of copper(I) iodide were added, and the mixture was heated at 140 °C for three days. After the reaction was completed, the mixture was carefully concentrated on a rotary evaporator, the precipitated solid was suction filtered, and washed with water and ethanol. The crude product was purified twice with a hot extractant (toluene / heptane 1:1), and the resulting solid was recrystallized from toluene. The yield after sublimation was 8.3 g (20.9 mmol), 85% of the theoretical value.

[0370] The following compounds were prepared in a similar manner:

[0371]

[0372]

[0373] 4) 4-Phenyl-(4,4,5,5-tetramethyl-[1,3,2]-dioxaborolan-1-yl)naphtho[1,2,3,4-def]carbazole

[0374]

[0375] 8.7 g (22 mmol) of 1-bromo-4-phenylnaphtho[1,2,3,4-def]carbazole, 6.2 g (24 mmol) of bis(pinacolato)diboron, and 6.3 g (64 mmol) of potassium acetate were suspended in 75 ml of di ane. To this suspension was added a complex of 0.53 g (0.66 mmol) of 1,1-bis(diphenylphosphino)ferrocene dichloropalladium(II) with DCM (dichloromethane). The reaction mixture was heated under reflux for 16 hours. After cooling, the organic phase was taken out, washed three times with 50 ml of water, and then concentrated to dryness. The residue was recrystallized from toluene. The yield after sublimation was 7.2 g (16.2 mmol), 74% of the theoretical value.

[0376] The following compounds were prepared in a similar manner:

[0377]

[0378]

[0379]

[0380] 5) 1-[9-(4,6-diphenyl-[1,3,5]triazin-2-yl)dibenzofuran-2-yl]-9-phenyl-4H-naphtho[1,2,3,4-def]carbazole

[0381]

[0382] 75 g (157 mmol) of 2-(8-bromodibenzofuran-1-yl)-4,6-diphenyl-[1,3,5]-triazine, 76 g (172 mmol) of N-phenylcarbazole-3-boronic acid and 36 g (340 mmol) of sodium carbonate were suspended in 1000 ml of ethylene glycol diamine ether and 280 ml of water. 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)palladium(0) was added to this suspension, and the reaction mixture was heated under reflux for 16 hours. After cooling, the organic phase was taken out, 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 / heptane (1:2), and finally sublimated under high vacuum (p = 5×10 -7 mbar) (99.9% purity).

[0383] The yield was 75 g (105 mmol), corresponding to 67% of the theoretical value.

[0384] The following compounds were prepared in a similar manner:

[0385]

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392]

[0393]

[0394]

[0395]

[0396]

[0397]

[0398]

[0399]

[0400]

[0401]

[0402]

[0403]

[0404] 6) 1-[3'-(4-[1,1'-Biphenyl]-4-yl-6-phenyl-1,3,5-triazin-2-yl)[1,1'-biphenyl]-3-yl]-4-phenylnaphtho[1,2,3,4-def]carbazole-d 36

[0405]

[0406] 38.8 g (50.0 mmol, 1.00 equivalent) of 1-[3'-(4-[1,1'-biphenyl]-4-yl-6-phenyl-1,3,5-triazin-2-yl)[1,1'-biphenyl]-3-yl]-4-phenylnaphtho[1,2,3,4-def]carbazole was suspended in 640 ml (120 equivalents) of toluene-d8 [CAS 2037-26-5]. While cooling, 16.6 ml (6.00 equivalents) of trifluoromethanesulfonic acid was added to this mixture. The reaction mixture was stirred at room temperature for 6 hours. Thereafter, 120 ml (130 equivalents) of deuterium oxide [CAS 7789-20-0] was added dropwise at 0 °C. It was neutralized with a potassium sulfate solution, then extracted with toluene, the combined organic phases were washed with a physiological saline solution, and dried over sodium sulfate. After filtration, the solvent was removed under reduced pressure. After purification by chromatography, 32.5 g (39 mmol, 80% of theory) of the above product in the form of a mixture of H / D isotope isomers and H / D isotope configurational isomer fractions was obtained, and finally sublimated (99.9% purity) under high vacuum (p = 5 × 10 -7 mbar).

[0407] The following compounds were prepared in a similar manner:

[0408]

[0409] Manufacture of OLED

[0410] In the following examples (see Tables 7 and 8), data for various OLEDs are provided.

[0411] Examples B1 to B15 show data for the OLEDs of the present invention. The substrate for the OLEDs in Table 7 is a glass plate coated with structured ITO (indium tin oxide) having a thickness of 50 nm.

[0412] The exact structure of the OLEDs can be found in Table 7. The materials required for fabricating the OLEDs are shown in Table 9 if not described above.

[0413] All materials are applied by hot vapor deposition in a vacuum chamber. In this case, the light-emitting layer always consists of at least one matrix material (also referred to as the host material) and a light-emitting dopant (lumophore), and the light-emitting dopant is added to one or more matrix materials by co-evaporation in a specific volume ratio. The details reported in the form of EE1:H1:TEG2 (32%:60%:8%) 40 nm mean that in a 40-nm-thick layer, the material EE1 as host material 1 is present in a volume ratio of 32%, the compound H1 as host material 2 is present in a ratio of 60%, and TEG2 is present in a ratio of 8%. Similarly, the electron transport layer can also consist of a mixture of two materials.

[0414] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectrum and the current-voltage-luminance density characteristic line (IUL characteristic line) are measured; these are used to calculate the EQE. The calculation is carried out assuming Lambertian emission characteristics. The electroluminescence spectrum is measured at a luminance density of 1000 cd / m 2 and these are used to calculate the CIE 1931 x and y color coordinates. The parameter U1000 in Table 8 here refers to the voltage required for a luminance density of 1000 cd / m 2 The EQE1000 refers to the external quantum efficiency at a working luminance density of 1000 cd / m 2 .

[0415] The lifetime LT is defined as the time during which the luminance density drops from an initial luminance density L0 (in cd / m 2 2) to a certain ratio L1 (in cd / m 2 2) while operating at a constant current density j0 (in mA / cm 2 2). The number L1 / L0 = 80% in Table 8 means that the lifetime reported in the LT column corresponds to the time (in h) after the luminance density has dropped to 80% of its initial value (L0).

[0416] Use of the compounds and mixtures of the present invention in OLEDs

[0417] The compound or material combination of the present invention can be used in the light-emitting layer of a phosphorescent green OLED.

[0418] The data of various OLEDs are collated in Table 8. Examples V1 to V4, V5 to V10, V12, V13, and V15 are comparative examples; Examples B1 to B4 and B6 to B15 show the data of the OLEDs of the present invention. The inventive examples show a distinct benefit in terms of device lifetime.

[0419] Table 7: Structure of OLED

[0420]

[0421]

[0422] Table 8:

[0423]

[0424] Table 9: Materials used not described above

[0425]

[0426]

Claims

1. A material for an organic electronic device, the material comprising at least one compound of formula (1): wherein the symbols and notations used are as follows: L is the same or different in each case and is a single bond, or an aromatic ring system having 5 to 20 ring atoms or a heteroaromatic ring system having 5 to 30 ring atoms, and the aromatic ring system or heteroaromatic ring system may be substituted by one or more R 0 groups; R 0 the same or different in each case and selected from: D, F, Cl, Br, I, CN, NO2, C(=O)R 2 , P(=O)(Ar)2, P(Ar)2, B(Ar)2, Si(Ar)3, Si(R 2 )3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, each of said groups being optionally substituted by one or more R 2 groups; wherein one or more non-adjacent CH2 groups may be replaced by R 2 C=CR 2 , Si(R 2 )2, C=O, C=S, C=NR 2 , P(=O)(R 2 ), SO, SO2, NR 2 , O, S or CONR 2 ; and wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and optionally substituted by one or more R 2 groups, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms and optionally substituted by one or more R 2 groups, or an aralkyl or heteroaralkyl group having 5 to 40 ring atoms and optionally substituted by one or more R 2 groups; Rx conforms to one of formula (1-2) to formula (1-16): * represents a bond connected to L; R a , R b and R c represent mono-substitution, di-substitution, tri-substitution, maximum allowable substitution or no substitution, R a 、R b and R c is D in each case; V is O, S or N-Ar4; R 1 Independently in each case H, D, CN, F or phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl which is either undehydrogenated or partially or fully deuterated; Ar is the same or different in each case and is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may be substituted by one or more R 2 groups; aryl is the same or different in each case and is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and may be substituted by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups in the alkyl group may be replaced by O or S, and wherein one or more hydrogen atoms in the alkyl group may be replaced by D, F or CN; Ar1 is an aromatic or heteroaromatic ring system having from 5 to 40 ring atoms and which may be substituted by one or more R 2 groups Ar2 and Ar3 are the same or different in each case and are H, D, CN, F, an undehydrogenated or partially or fully deuterated alkyl group having 1 to 10 carbon atoms, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may be substituted by one or more R 2 groups; R 2 identical or different in each case and selected from: D, F, CN, Si(aryl)3, a straight-chain alkyl group having from 1 to 20 carbon atoms or a branched or cyclic alkyl group having from 3 to 20 carbon atoms, where one or more non-adjacent CH2 groups may be replaced by O or S and where one or more hydrogen atoms may be replaced by D, F or CN, wherein the compound of formula (1) is partially or completely deuterated.

2. The material for an organic electronic device according to claim 1, wherein L conforms to one of Formula L-1 to Formula L-41 which can be substituted by one or more R 0 groups and R 0 is D: wherein the dashed line represents a bond connected to Rx or to the remainder of formula (1); V1 and V2 are each independently O, S, Se or N-Ar4; and Ar4 is the same or different in each case and is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may be substituted by one or more R 2 groups.

3. The material for an organic electronic device according to claim 1 or 2, wherein R a , R b and R c each independently refer to mono-substitution, di-substitution or tri-substitution.

4. The material for an organic electronic device according to one or more of claims 1 to 3, wherein Rx conforms to formula (1-2).

5. The material for an organic electronic device according to one or more of claims 1 to 4, the material comprising at least one compound selected from Compound 1 to Compound 39:

6. A mixture, the mixture comprising at least one compound according to one or more of claims 1 to 5 and at least one other compound, the other compound being selected from: a matrix material, a phosphorescent emitter, a fluorescent emitter and / or an emitter exhibiting TADF (thermally activated delayed fluorescence).

7. A formulation, the formulation comprising at least one compound according to one or more of claims 1 to 5 or the mixture according to claim 6 and at least one solvent.

8. An organic electronic device, the organic electronic device comprising an anode, a cathode and at least one organic layer, the organic layer comprising at least one compound according to one or more of claims 1 to 5.

9. The organic electronic device according to claim 8, wherein the electronic device is an electroluminescent device.

10. The organic electronic device according to claim 8 or 9, wherein the organic layer comprises at least one light-emitting layer, an electron transport layer or a hole-blocking layer, the light-emitting layer, the electron transport layer or the hole-blocking layer comprising at least one compound according to any one of claims 1 to 5.

11. The organic electronic device according to one or more of claims 8 to 10, characterized in that, The light-emitting layer comprises the at least one compound according to any one of claims 1 to 5.

12. The organic electronic device according to one or more of claims 8 to 11, characterized in that, In addition to comprising the compound according to any one of claims 1 to 5, the light-emitting layer further comprises at least one other matrix material.

13. The organic electroluminescent device according to claim 12, wherein The other matrix material corresponds to one or more compounds of formula (6), formula (7), formula (8), formula (9), formula (10) and formula (11): wherein the symbols and notations used are as follows: A 1 is C(R 7 )2, NR 7 , O or S; L1 is a key, O, S, C(R 7 )2 or NR 7 ; A is independently in each case a group of formula (3) or formula (4), X2 is the same or different in each case and is CH, CR 6 or N, where no more than two of the symbols X2 can be N; * represents the binding site to formula (9); U 1 , U 2 When they appear, for keys, O, S, C(R 7 )2 or NR 7 ; R 6 Identical or different in each case and being D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R 7 groups, and where one or more non-adjacent CH2 groups may be replaced by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7 , or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms and which may in each case be substituted by one or more R 7 groups; here two R 6 groups may also together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar5 is the same or different in each case and independently is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may be substituted by one or more R 7 groups; R 7 identical or different in each case and being 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 alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R 8 groups, where one or more non-adjacent CH2 groups may be replaced by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 , or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms and which may in each case be substituted by one or more R 8 groups; simultaneously, two or more R 7 groups together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; preferably, the R 7 groups do not form any such ring system; R 8 which are the same or different in each case and are H, D, F or an aliphatic, aromatic or heteroaromatic organic group having from 1 to 20 carbon atoms, in particular a hydrocarbon radical, where one or more hydrogen atoms may also be replaced by F; c, c1, and c2 are each independently 0 or 1 in each case, where the sum of the labels c + c1 + c2 = 1 in each case; d, d1, and d2 are each independently 0 or 1 in each case, where the sum of the labels d + d1 + d2 = 1 in each case; q, q1, and q2 are each independently 0 or 1 in each case; s is the same or different in each case and is 0, 1, 2, 3, or 4; t is the same or different in each case and is 0, 1, 2, or 3; u is the same or different in each case and is 0, 1, or 2; u1 and u2 are each independently 0 or 1 in each case, where the sum u1 + u2 = 1; and v is 0 or 1.

14. The organic electronic device according to one or more of claims 8 to 13, characterized in that, The light-emitting layer contains a phosphorescent emitter.

15. The organic electronic device according to one or more of claims 8 to 14, characterized in that, The organic electronic device is an electroluminescent device selected from an organic light-emitting transistor (OLET), an organic field quenching device (OFQD), an organic light-emitting electrochemical cell (OLEC, LEC, LEEC), an organic laser diode (O-laser), and an organic light-emitting diode (OLED).

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