Materials for organic electroluminescent devices

Abstract

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

Description

[0001] Materials for organic electroluminescent devices

[0002] Technical area

[0003] The present invention relates to 4 / 7-naphtho[1,2,3,4-ctef]carbazoles, mixtures and formulations containing them and electronic devices containing these compounds, in particular organic electroluminescent devices containing these compounds as matrix materials, electron transport materials or hole blocking materials.

[0004] State of the art

[0005] Phosphorescent organometallic complexes are frequently used in organic electroluminescent devices (OLEDs). In general, there is still room for improvement in OLEDs, for example, with regard to efficiency, operating voltage, and lifetime. The properties of phosphorescent OLEDs are determined not only by the triplet emitters used. The other materials used, such as matrix materials, are also particularly important. Improvements to these materials can therefore also lead to significant improvements in OLED properties.

[0006] According to the state of the art, carbazole derivatives, dibenzofuran derivatives, indenocarbazole derivatives, indolocarbazole derivatives, benzofurocarbazole derivatives and benzothienocarbazole derivatives are used as matrix materials for phosphorescent emitters.

[0007] In WO2012048781 A1 , CN115626914 A and US2021119134 A1, special 4H-naphtho[1,2,3,4-ctef]carbazole derivatives are described, among other things, as matrix materials.

[0008] In CN 113248477 A, US2019315759 A1 , WO22038065 A1 , US2022263031 A1, complex carbazole derivatives are described, among other things, as matrix materials.

[0009] In CN111978355 A and US20190051844 A1, 4H-naphtho[1,2,3,4-def]carbazole derivatives are described as ligands for emitters.

[0010] In general, these materials still require improvement, particularly for use as matrix materials. The object of the present invention is to provide compounds that are particularly suitable for use as matrix materials, electron-transport materials, or hole-blocking materials in a phosphorescent OLED. In particular, the object of the present invention is to provide matrix materials that lead to an improved lifetime. This applies in particular to the use of a low to medium emitter concentration, i.e., emitter concentrations in the range of 3 to 20%, in particular 3 to 15%, since the device lifetime is particularly limited in this case.

[0011] It has now been found that electroluminescent devices containing compounds according to the following formula (1) exhibit improvements over the prior art, in particular when using the compounds as matrix material for phosphorescent dopants.

[0012] It has further been found that the combination of at least one compound of formula (1) as first host material and at least one hole-transporting compound, for example in combination with one or more compounds of formulas (6), (7), (8), (9), (10) or (11), as further host material / further host materials in a light-emitting layer of an organic electronic device, in particular an organic electroluminescent device, solves this problem and eliminates the disadvantages of the prior art.

[0013] Summary of the invention

[0014] A first subject of the present invention is a material for an organic electronic device comprising at least one compound according to formula (1), Formula (1), where the symbols and indices used are:

[0015] L is, identically or differently at each occurrence, a single bond or an aromatic or heteroaromatic ring system having 5 to 20 ring atoms, which may be substituted by one or more radicals R°; R° is, identically or differently at each occurrence, selected from the group consisting of D, F, CI, Br, I, CN, NO2, C(=O)R 2 , P(=O)(Ar)2, P(Ar)2, B(Ar)2, Si(Ar)3, Si(R 2 )s, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl group having 2 to 20 C atoms, each of which is substituted by one or more radicals R 2may be substituted, with one or more non-adjacent CH2 groups being substituted 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 Fl atoms may be replaced by D, F, CI, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, which may be substituted with one or more radicals R 2 may be substituted, or an aralkyl or heteroaralkyl group having 5 to 40 ring atoms which may be substituted by one or more radicals R 2 can be substituted;

[0016] Rx corresponds to one of the formulas (1-2) to (1-16)

[0017] Formula (1-8) Formula (1-9)

[0018] * denotes the connection to L,

[0019] Ra, Rb and Rc represent a monosubstitution, a disubstitution, a trisubstitution, the maximum permissible substitution or no substitution,

[0020] Ra, Rb and Rc are D at each occurrence independently of each other;

[0021] V is O, S or N-Au;

[0022] R 1 is at each occurrence independently H, D, CN, F or non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl;

[0023] Ar is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by one or more radicals R;

[0024] Aryl is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more non-adjacent CH2 groups of the alkyl group may be replaced by O or S and where one or more H atoms of the alkyl group may be replaced by D, F, or CN;

[0025] An is an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be substituted by one or more radicals R,

[0026] Ar2, Ars are, identically or differently at each occurrence, H, D, CN, F, a non-deuterated or partially or fully deuterated alkyl group having 1 to 10 C atoms, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R; and

[0027] R is, at each occurrence, identically or differently selected from the group consisting of D, F, CN, Si(aryl)s, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more non-adjacent CH2 groups may be replaced by O or S and where one or more H atoms may be replaced by D, F or CN, where the compound of formula (1) is partially or fully deuterated.

[0028] The invention further relates to a mixture comprising at least one compound of formula (1) as described above or preferably described later and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters which exhibit TADF (thermally activated delayed fluorescence).

[0029] The invention further provides a formulation comprising at least one compound of formula (1) as described above or preferably described later, or a mixture as described above, and at least one solvent.

[0030] The invention further provides an organic electronic, preferably electroluminescent, device comprising an anode, a cathode, and at least one organic layer containing at least one compound of formula (1) as described above or preferably described later. Description of the invention

[0031] In this patent application, “D” or “D atom” refers to deuterium.

[0032] An aryl group within the meaning of this invention contains 6 to 40 ring atoms, preferably C atoms. A heteroaryl group within the meaning of this invention contains 5 to 40 ring atoms, where the ring atoms comprise C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e. phenyl, derived from benzene, or a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene, or a fused aryl or heteroaryl group, for example derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline. An aryl group with 6 to 18 C atoms is therefore preferably phenyl, naphthyl, phenanthryl or triphenylenyl, whereby the attachment of the aryl group as a substituent is not restricted.The aryl or heteroaryl group within the meaning of this invention may carry one or more radicals, with the appropriate radical being described below. If no such radical is described, the aryl or heteroaryl group is unsubstituted.

[0033] An aromatic ring system within the meaning of this invention contains 6 to 40 carbon atoms in the ring system. The aromatic ring system also includes aryl groups, as described above.

[0034] An aromatic ring system with 6 to 18 C atoms is preferably selected from phenyl, fully deuterated phenyl, biphenyl, naphthyl, phenanthryl and triphenylenyl.

[0035] A heteroaromatic ring system within the meaning of this invention contains 5 to 40 ring atoms and at least one heteroatom. A preferred heteroaromatic ring system has 9 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system also includes heteroaryl groups, as described above. The heteroatoms in the heteroaromatic ring system are preferably selected from N, O, and / or S.

[0036] An aromatic or heteroaromatic ring system within the meaning of this invention is understood to mean a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be interrupted by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as a C or O atom or a carbonyl group. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diaryl ethers, stilbene, etc. are also to be understood as aromatic or heteroaromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group. Furthermore, systems in which two or more aryl or heteroaryl groups are directly bonded to one another, such asBiphenyl, terphenyl, quaterphenyl or bipyridine, are also included in the definition of the aromatic or heteroaromatic ring system.

[0037] An aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which can be linked to the aromatic or heteroaromatic ring via any position, is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, Isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine,Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1 ,2-Thiazol, 1 ,3- Thiazol, Benzothiazol, Pyridazin, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin,

[0038] 1.5-Diazaanthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1 ,6-Diazapyren, 1 ,8-Diazapyren,

[0039] 4.5-Diazapyren, 4,5,9, 10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Pheno- thiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1 ,2,3- Triazol, 1 ,2,4-Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1 ,2,4-Oxadiazol, 1 ,2,5-Oxadiazol,

[0040] 1.3.4-Oxadiazol, 1 ,2,3-Thiadiazol, 1 ,2,4-Thiadiazol, 1 ,2,5-Thiadiazol, 1 ,3,4-Thiadiazol,

[0041] 1.3.5-Triazin, 1 ,2,4-Triazin, 1 ,2,3-Triazin, Tetrazol, 1 ,2,4,5-Tetrazin, 1 ,2,3,4-Tetrazin,

[0042] 1.2.3.5-Tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0043] The abbreviations Ar, An, and Au, identically or differently at each occurrence, mean an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R, where the radical R or the substituents R have a meaning as described above or below. A preferred meaning of Ar and An and An is described below.

[0044] The abbreviation “aryl” means, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more non-adjacent CH2 groups of the alkyl group may be replaced by O or S and where one or more H atoms of the alkyl group may be replaced by D, F or CN.

[0045] The abbreviations Ar2 and Ars mean, identically or differently, on each occurrence H, D, CN, F, a non-deuterated or partially or fully deuterated alkyl group having 1 to 10 C atoms, an aromatic ring system having 6 to 40 ring atoms or a heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R, where the radical R or the substituents

[0046] R has / have a meaning as described above or below. A preferred meaning of Ar2 and Ars is described below.

[0047] The abbreviation Ars stands, the same or different at each occurrence, for an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which is substituted with one or more radicals R 7 may be substituted, where the radical R 7 or the substituents R 7 has / have a meaning as described above or below.

[0048] A preferred meaning of Ars is described below.

[0049] A cyclic alkyl, alkoxy or thioalkyl group in the sense of this invention is understood to mean a monocyclic, a bicyclic or a polycyclic group.

[0050] Im Rahmen der vorliegenden Erfindung werden unter einer geradkettigen, verzweigten oder cyclischen Ci- bis C2o-Alkylgruppe beispielsweise die Reste Methyl, Ethyl, n-Propyl, i-Propyl, Cyclopropyl, n-Butyl, i-Butyl, s-Butyl, t-Butyl, Cyclobutyl, 2-Methyl- butyl, n-Pentyl, s-Pentyl, t-Pentyl, 2-Pentyl, neo-Pentyl, Cyclopentyl, n-Hexyl, s-Hexyl, t-Hexyl, 2-Hexyl, 3-Hexyl, neo-Hexyl, Cyclohexyl, 1 -Methylcyclopentyl, 2-Methylpentyl, n-Heptyl, 2-Heptyl, 3-Heptyl, 4-Heptyl, Cycloheptyl, 1 -Methylcyclohexyl, n-Octyl, 2-Ethylhexyl, Cyclooctyl, 1-Bicyclo[2,2,2]octyl, 2-Bicyclo[2,2,2]octyl, 2-(2,6-Dimethyl)- octyl, 3-(3,7-Dimethyl)octyl, Adamantyl, Trifluormethyl, Pentafluorethyl, 2,2,2-Tri- fluorethyl, 1,1-Dimethyl-n-hex-1-yl-, 1 ,1-Dimethyl-n-hept-1-yl-, 1,1-Dimethyl-n-oct-1-yl-,

[0051] 1.1-Dimethyl-n-dec-1-yl-, 1,1-Dimethyl-n-dodec-1-yl-, 1,1-Dimethyl-n-tetradec-1-yl-,

[0052] 1.1-Dimethyl-n-hexadec-1-yl-, 1,1-Dimethyl-n-octadec-1-yl-, 1,1-Diethyl-n-hex-1-yl-,

[0053] 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-Diethyln-n-hexadec-1-yl-, 1, 1-Diethyl-n-octadec-1-yl-, 1-(n-propyl)-cyclohex-1-yl-, 1-(n-butyl)-cyclohex-1-yl-, l-(n-hexyl)-cyclohex-1-yl-, 1-(n-Octyl)-cyclohex-1-yl- and 1-(n-Decyl)-cyclohex-1-yl- understood.

[0054] The following describes the material for an organic electronic device comprising one or more compounds of formula (1) and preferred embodiments of the compounds of formula (1). The preferred embodiments also apply to the mixture according to the invention, the formulation according to the invention, and the organic electronic or electroluminescent device according to the invention.

[0055] In compounds of formula (1) the substituent L-Rx can be bonded at any position.

[0056] Preferred compounds of formula (1) are compounds of formulas (1a) to (1j),

[0057] Formula (1a) Formula (1b),

[0058]

[0059] Formula (1i) Formula (1j), wherein Rx, L, Ra, Rb, Rc and An have a meaning mentioned above or mentioned below with preference and wherein the compounds of the formulas (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) are partially or completely deuterated.

[0060] Since the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) are deuterated compounds, it is possible during their preparation if the preparation is chosen by reacting a non-deuterated compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) with a deuteration source or if deuterated starting compounds are chosen during the preparation which are a mixture of deuterated starting compounds, that a mixture of deuterated products of the same basic chemical structure is formed which only differ in the degree of deuteration and / or the deuteration patterns.

[0061] Therefore, the present invention is directed to a material for an organic electronic device comprising at least one compound according to formula (1), wherein the at least one compound according to formula (1) may comprise a mixture of deuterated products of the same basic chemical structure, wherein the deuterated compounds differ only in the degree of deuteration and / or the deuteration pattern.

[0062] Therefore, the present invention is preferably directed to a material for an organic electronic device consisting of a compound of formula (1) with a specific deuteration pattern or consisting of two or more compounds of formula (1) with the same basic chemical structure of formula (1), which differ only in the degree of deuteration and / or the deuteration pattern.

[0063] In a preferred embodiment of the material according to the 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%, particularly preferably 40 mol% to 80 mol%, most particularly preferably 50 mol% to 70 mol%.

[0064] Corresponding deuteration methods are known to the person skilled in the art and are described, for example, in KR2016041014, WO2017 / 122988, KR202005282, KR101978651 and W02018 / 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.

[0065] Particularly preferred compounds of formula (1) are the compounds of formulas (1a) and (1b), where Rx, L, Ra, Rb, Rc and An have a meaning mentioned above or mentioned below as preferred, which are partially or completely deuterated.

[0066] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) represents an aromatic or heteroaromatic ring system of formulas L-1 to L-41, which may be substituted by one or more radicals R°, where R° D is:

[0067] L-13 L-14 L-15 L-16

[0068]

[0069] L-37 L-38

[0070]

[0071] L-41 wherein the dashed lines indicate the attachment to Rx or to the residue of formula (1) or the residue of formulas (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j);

[0072] Vi and V2 are each independently O, S, Se or N-Au; and

[0073] Ar4 is, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by one or more radicals R, where the radical R or the substituents R has / have a meaning as described above or below.

[0074] In a preferred embodiment of the invention, L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is a single bond.

[0075] In a preferred embodiment of the invention, the linker L in compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the group of linkers L-1 to L-7 and L-14 to L-41, which may be substituted by one or more radicals R°, where R° is D. In the linkers L-18 to L-30 and L-35 to L-41, Vi is preferably O, S or N-Au and Au is preferably an aromatic ring system having 6 to 20 ring atoms, which may be substituted by one or more radicals R. R in N-Au is preferably D, F or CN, particularly preferably D. In the linkers L-18 to L-30 and L-35 to L-41, Au, when occurring, is particularly preferably selected from non-deuterated, partially deuterated or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl.In linkers L-18 to L-30 and L-35 to L-41, Au, when occurring, is most preferably selected from partially deuterated or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl.

[0076] In linkers L-18 to L-30 and L-35 to L-41, Vi is particularly preferably O or S. In linkers L-18 to L-30 and L-35 to L-41, Vi is most preferably O.

[0077] In linkers L-35 to L-38, V2 is preferably O or S, particularly preferably O.

[0078] The substituent R°, when identical or different, is preferably selected from the group consisting of

[0079] Group D, F, CN, Si(Ar)s or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, where Ar has a meaning mentioned above. The substituent R°, when occurring, is preferably D. Ar in Si(Ar)3 is preferably the same and is an aromatic ring system having 6 to 20 ring atoms, which may be substituted by one or more radicals R. R in Ar is preferably D, F or CN, particularly preferably D. In Si(Ar)3, Ar is particularly preferably selected from non-deuterated, partially deuterated or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl.

[0080] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-1 to L-3, which may be substituted by one or more radicals R°, where R° is D.

[0081] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-1 to L-3 which are substituted by one or more radicals R°, where R° is D.

[0082] In one embodiment of the invention, the linker L in compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-4 to L-7, which may be substituted by one or more radicals R°, where R° is D. In one embodiment of the invention, the linker L in compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-4 to L-7, which are substituted by one or more radicals R°, where R° is D.

[0083] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-14 to L-17, which may be substituted by one or more radicals R°, where R° is D.

[0084] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-14 to L-17 which are substituted by one or more radicals R°, where R° is D.

[0085] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-18 to L-30, which may be substituted by one or more radicals R°, where R° is D and Vi has a meaning given previously or preferably.

[0086] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-18 to L-30 which are substituted with one or more radicals R°, where R° is D and Vi has a meaning given previously or preferably.

[0087] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-31 to L-34, which may be substituted by one or more radicals R°, where R° is D.

[0088] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-31 to L-34 which are substituted by one or more radicals R°, where R° is D.

[0089] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-35 to L-38, which may be substituted by one or more radicals R°, where R° is D and Vi and V2 have a meaning given previously or preferably.

[0090] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-35 to L-38 which are substituted with one or more radicals R°, where R° is D and V1 and V2 have a meaning given previously or preferably.

[0091] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-39 to L-41, which may be substituted by one or more radicals R°, where R° is D and V1 has a meaning given previously or preferably.

[0092] In one embodiment of the invention, the linker L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) is selected from the linkers L-39 to L-41 which are substituted with one or more radicals R°, where R° is D and V1 has a meaning given previously or preferably.

[0093] In one embodiment of the invention, Rx in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), and (1j) represents formula (1-2), and the linker L has a meaning previously indicated or preferably indicated. This is a particularly preferred embodiment.

[0094] In one embodiment of the invention, Rx in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) represents one of formulas (1-3), (1-4) or (1-5) and the linker L has a meaning given previously or preferably. In formulas (1-3) to (1-5), R 1 preferably H, D, CN or F, particularly preferably H or D.

[0095] In one embodiment of the invention, Rx in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) represents one of formulas (1-6), (1-7), (1-8), (1-9), (1-10) or (1-11) and the linker L has a meaning given above or given as preferred.

[0096] In one embodiment of the invention, Rx in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), and (1j) represents one of formulas (1-6), (1-7), (1-8), or (1-9), and the linker L has a meaning previously indicated or preferably indicated. This is a preferred embodiment.

[0097] In one embodiment of the invention, Rx in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) represents one of formulas (1-12), (1-13), (1-14), (1-15) or (1-16) and the linker L has a meaning given above or preferably given.

[0098] In one embodiment of the invention, Rx in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), and (1j) represents one of formulas (1-2), (1-6), (1-7), (1-8), or (1-9), and the linker L has a meaning previously indicated or preferably indicated. This is a preferred embodiment.

[0099] The symbol V in the formulas (1-6) to (1-11) denotes O, S or N-Au, where Au preferably denotes an aromatic ring system having 6 to 20 ring atoms, which may be substituted by one or more radicals R. R in N-Au is preferably D, F or CN, particularly preferably D. In the formulas (1-6) to (1-11), Au, when it occurs, is particularly preferably selected from non-deuterated, partially deuterated or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl.

[0100] In formulas (1-6) to (1-11), Au, when occurring, is most preferably selected from phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl, which are partially deuterated or fully deuterated.

[0101] The symbol V in formulas (1-6) to (1-11) preferably represents O or S, particularly preferably O.

[0102] In compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), Ra, Rb and Rc represent a monosubstitution, a disubstitution, a trisubstitution, the maximum permissible substitution or no substitution and Ra, Rb and Rc are independently D at each occurrence.

[0103] In the case of monosubstitution, Ra, Rb and Rc each independently of one another in compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) represent D, ie the compounds each carry three substituents Ra, Rb and Rc.

[0104] In one embodiment of the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), one substituent Ra, Rb or Rc does not represent a substitution and two substituents Ra, Rb or Rc represent D.

[0105] In a preferred embodiment of the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), two substituents Ra, Rb or Rc do not represent a substitution and one substituent Ra, Rb or Rc represents D.

[0106] In a preferred embodiment of the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), Ra, Rb or Rc do not represent a substitution.

[0107] With maximum permissible substitution, Ra, Rb and Rc in formulas (1-6), (1-7), (1-8), (1-9), (1-10), (1-11), (1-12), (1-13), (1-14), (1-15) and (1-16) represent D.

[0108] For formulas (1-6), (1-7), (1-8), (1-9), (1-10), (1-11), (1-12), (1-13), (1-14), (1-15) and (1-16) it is preferred if Ra, Rb and Rc represent maximum substitution or no substitution.

[0109] The compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) or preferred compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) are partially deuterated and in one embodiment the substituents Ra, Rb and Rc are D and each independently represent monosubstitution, disubstitution or trisubstitution.

[0110] In compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), Ar2 and Ars are, on each occurrence, identical or different, H, D, CN, F, a non-deuterated or partially or fully deuterated alkyl group having 1 to 10 C atoms, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more R radicals; where R has a meaning as defined above. R in Ar2 and Ars is preferably D, F or CN, particularly preferably D.

[0111] In compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), in which Rx corresponds to one of the formulas (1-2), (1-3), (1-4) or (1-5), Ar2 and Ars, identical or different at each occurrence, preferably represent an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R; where R has a meaning mentioned above or particularly preferred.

[0112] The aromatic or heteroaromatic ring system with 5 to 40 ring atoms in Ar2 and Ars of the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), which may be substituted by one or more radicals R, is preferably selected independently from the group Ar-1 to Ar-24:

[0113]

[0114] Ar-23 Ar-24 where Y 3 at each occurrence, the same or different, O, S, NAu or C(R # )2 means, o 2 where R is H, R or an aromatic or heteroaromatic ring system with 5 to

[0115] 2

[0116] 40 ring atoms, which may be substituted by one or more radicals R, where the dashed bond represents the bond to the radical of the formulas (1-2) to (1-2

[0117] 15) and wherein R and Ar4 have a previously mentioned or a previously preferred meaning.

[0118] The rest R # is at each occurrence, identically or differently, H, D, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl group having 2 to 20 C atoms, each of which is substituted by one or more radicals R 2may be substituted, where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, which may be substituted with one or more radicals R 2 may be substituted, or an aralkyl or heteroaralkyl group having 5 to 40 ring atoms which may be substituted with one or more radicals R 2 can be substituted.

[0119] Y 3 is preferably O, S, NAu or C(CHs)2. Y 3 is especially preferred O. Y 3 is very particularly preferably NAu, where Au has a meaning mentioned above or preferably mentioned.

[0120] In the structures Ar-1 to Ar-24, the substituent R is preferably selected, identically or differently at each occurrence, from the group consisting of H, D, F, CN or an aromatic ring system having 6 to 30 ring atoms, each of which is substituted by one or more radicals R 2 can be substituted. In the structures Ar-1 to Ar-24, the

[0121] Substituent R is particularly preferably selected, identically or differently at each occurrence, from the group consisting of H, D, non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl.

[0122] In the structures Ar-1 to Ar-24, the substituent R is particularly preferably selected, identically or differently at each occurrence, from the group consisting of H, D or phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl, which are partially deuterated or fully deuterated. R particularly preferably denotes D. o In the structures Ar-1 to Ar-24, it is preferred if at least one substituent denotes RD.

[0123] In the structures Ar-1 to Ar-24 it is particularly preferred if all substituents R 3 D means.

[0124] Particularly preferably, Ar2 or Ars in compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) each independently represent Ar-1, Ar-2, Ar-3, Ar-12 to Ar-15, where R has a meaning given above or preferably given.

[0125] In compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), An is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R; where R has a meaning as previously mentioned.R in An preferably denotes D, F, CN or Si(aryl)s, where aryl on each occurrence, identically or differently, denotes an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more non-adjacent CH2 groups of the alkyl group may be replaced by O or S and where one or more H atoms of the alkyl group may be replaced by D, F or CN.

[0126] R in An particularly preferably represents D, F, or CN, most preferably D.

[0127] In compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), An is preferably selected from the group Ar-1 to Ar-24, as previously described or preferably described, or An corresponds to one of the formulas (1-2) to (1-16) and R has a meaning as previously described or preferably described

[0128] In compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), An is particularly preferably selected from the group Ar-1 to Ar-24, as described above or preferably described, in particular when the linker L is an aromatic or heteroaromatic ring system of the formulas L-1 to L-41, as described above or preferably described above.

[0129] In compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), An is particularly preferably selected from one of the formulas (1-2) to (1-16), in particular when the linker L represents a single bond.

[0130] In compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), An very particularly preferably represents the formula (1-2) when the linker L represents a single bond, where Ar2 and Ars have a meaning given above or given preferably.

[0131] Examples of suitable compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f),

[0132] (Ig), (1h), (1i) and (1j), as previously described or preferably described, are the structures shown below in Table 1.

[0133] Table 1 :

[0134] Particularly suitable compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j), as described above or preferably described, are compounds E1 to E39 of Table 2.

[0135] Table 2:

[0136]

[0137] The compounds according to the invention can be prepared by synthesis steps known to the person skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc.

[0138] In the following synthesis schemes, the compounds are shown with a small number of substituents to simplify the structures. This does not exclude the presence of any additional substituents in the processes. The processes shown for the synthesis of the compounds of the invention are to be understood as examples. The skilled person can develop alternative synthesis routes within the scope of their general technical knowledge. Scheme 1:

[0139] Scheme 4: Ar' corresponds to L-Rx

[0140] Detailed reaction conditions are known from the state of the art or are described in the examples section.

[0141] By these processes, optionally followed by purification, such as

[0142] Recrystallization or sublimation, the compounds of formula (1), as described above or preferably described, can be obtained in high purity, preferably more than 99% (determined by 1H-NMR and / or HPLC). Starting from partially or fully deuterated starting compounds, partially deuterated or fully deuterated products are formed, as described above. It is also possible to prepare the compounds of formula (1) according to Schemes 1 to 4 and subsequently deuterate them, as described above and below.

[0143] For processing the material according to the invention for organic electronic devices from the liquid phase, for example by spin coating or by printing processes, formulations comprising at least one compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) or mixtures with further functional materials, such as matrix materials, fluorescent emitters, phosphorescent emitters and / or emitters exhibiting TADF, are required. These formulations can be, for example, solutions, dispersions or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene,1- Methylnaphthalin, 2-Methylbenzothiazol, 2-Phenoxyethanol, 2-Pyrrolidinon, 3- Methylanisol, 4-Methylanisol, 3,4-Dimethylanisol, 3,5-Dimethylanisol, Acetophenon, a- Terpineol, Benzothiazol, Butylbenzoat, Cumol, Cyclohexanol, Cyclohexanon, Cyclohexylbenzol, Decalin, Dodecylbenzol, Ethylbenzoat, Indan, NMP, p-Cymol, Phenetol, 1,4-Diisopropylbenzol, Dibenzylether, Diethylenglycolbutylmethylether, Tri- ethylenglycolbutylmethylether, Diethylenglycoldibutylether, T riethylenglycol- dimethylether, Diethylenglycolmonobutylether, Tripropyleneglycoldimethylether, Tetra- ethylenglycoldimethylether, 2-lsopropylnaphthalin, Pentylbenzol, Hexylbenzol, Heptylbenzol, Octylbenzol, 1,1-Bis(3,4-dimethylphenyl)ethan, 2-Methylbiphenyl, 3-Methylbi- phenyl, 1-Methylnaphthalin, 1-Ethylnaphthalin, Ethyloctanoat, Sebacinsäure- diethylester, Octyloctanoat, Heptylbenzol, Menthyl-isovalerat, Cyclohexylhexanoat oder Mischungen dieser Lösemittel.,

[0144] The compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) and (1j) according to the invention, as described above or preferably described, are suitable for use in an organic electroluminescent device, in particular as an electron transport material, as a hole blocking material or as a matrix material.

[0145] If the compound according to the invention of one of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) is used as matrix material or synonymously host material in an emitting layer, it is preferably used in combination with another compound.

[0146] The invention therefore further provides a mixture comprising at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) or at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) or at least one compound of Table 1 or at least one of the compounds E1 to E39 and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence). Suitable matrix materials and emitters that can be used in this mixture according to the invention are described below.

[0147] The present invention also further provides a formulation comprising at least one compound according to the invention, as described above, or a mixture according to the invention, as described above, and at least one solvent. The solvent can be one of the solvents mentioned above or a mixture of these solvents.

[0148] The present invention further provides an organic electronic device comprising an anode, a cathode and at least one organic layer containing at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) or at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) or at least one compound of Table 1 or at least one of the compounds E1 to E39. The statements regarding deuterated materials apply accordingly.

[0149] The organic electronic device can be selected, for example, from organic integrated circuits (OLCs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors, organic photoreceptors.

[0150] The organic electronic device is preferably an organic electroluminescent device. The organic electroluminescent device according to the invention (synonymously with organic electroluminescent device) is, for example, an organic light-emitting transistor (OLET), an organic field quench device (OFQD), an organic light-emitting electrochemical cell (OLEC, LEG, LEEC), an organic laser diode (O-laser), or an organic light-emitting diode (OLED). The organic electroluminescent device according to the invention is in particular an organic light-emitting diode or an organic light-emitting electrochemical cell. The device according to the invention is particularly preferably an OLED.

[0151] The organic layer of the device according to the invention preferably contains, in addition to a light-emitting layer (EML), a hole-injection layer (HIL), a hole-transport layer (HTL), a hole-blocking layer (HBL), an electron-transport layer (ETL), an electron-injection layer (EIL), an exciton-blocking layer, an electron-blocking layer, and / or charge-generation layers. The device according to the invention can also contain several layers from this group, preferably selected from EML, HIL, HTL, ETL, EIL, and HBL. Interlayers, which, for example, have an exciton-blocking function, can also be introduced between two emitting layers.

[0152] If a plurality of emission layers are present, these preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, resulting in an overall white emission, i.e. different emitting compounds which can fluoresce or phosphoresce are used in the emitting layers. A plurality of fluorescent and / or phosphorescent compounds can also be present in one emitting layer. Systems with three emitting layers are particularly preferred, wherein the three layers exhibit blue, green and orange or red emission. As an alternative to the combination as described above, an emitting layer can also exhibit yellow emission. Such combinations are known to the person skilled in the art. The organic electroluminescent device according to the invention can also be a tandem electroluminescent device, in particular for white-emitting OLEDs.

[0153] The device may also contain inorganic materials or layers made entirely of inorganic materials.

[0154] It is not difficult for a person skilled in the art to draw on a multitude of materials known in the prior art to select suitable materials for use in the layers of the organic electroluminescent device described above. In doing so, the person skilled in the art will consider common considerations regarding the chemical and physical properties of the materials, as they are aware that the materials in an organic electroluminescent device are interrelated. This applies, for example, to the energy positions of the orbitals (HOMO, LIIMO) or the position of triplet and singlet energies, as well as other material properties.

[0155] The compound according to the invention of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as described above or preferably described, can be used in different layers. Preference is given to an organic electroluminescent device comprising at least one compound of the formula (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) or the preferred embodiments described above in a light-emitting layer as a matrix material for fluorescent emitters, phosphorescent emitters or for emitters that exhibit TADF (thermally activated delayed fluorescence), in particular for phosphorescent emitters. Furthermore, the at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) can also be used in an electron-transporting layer or in a hole-blocking layer.The compound according to the invention of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) is particularly preferably used as matrix material in a light-emitting layer.

[0156] The present invention further provides an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer which contains at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) or which contains at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) or at least one compound of Table 1 or at least one of the compounds E1 to E39.

[0157] In one embodiment of the invention, at least one further matrix material is selected for the device according to the invention in the light-emitting layer, which is used with compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as described above or preferably described, or with the compounds of Table 1 or the compounds E1 to E39.The present invention accordingly further provides an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer which contains at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) or which contains at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) or at least one compound of Table 1 or at least one of the compounds E1 to E39 and at least one further matrix material.

[0158] Suitable matrix materials that can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, biscarbazoles, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasilole or tetraazasilole derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or dibenzofuran derivatives. Likewise, another phosphorescent emitter that emits at a shorter wavelength than the actual emitter can be present in the mixture as a co-host, or a compound that does not participate, or only participates to a limited extent, in charge transport, such as a wide-band-gap compound.

[0159] A wide-band-gap material is understood herein to mean a material within the meaning of the disclosure of US 7,294,849, which is characterized by a band gap of at least 3.5 eV, where the band gap is understood to be the distance between the HOMO and LUMO energy of a material.

[0160] Particularly suitable matrix materials which are advantageously combined with compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as previously described or preferably described, in a mixed matrix system can be selected from the compounds of formulas (6), (7), (8), (9), (10) or (11), as described below.

[0161] A further subject matter of the invention is accordingly an organic electronic device comprising an anode, a cathode and at least one organic layer containing at least one light-emitting layer, wherein the at least one light-emitting layer contains at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) as matrix material 1, as described above or described as preferred, and at least one compound of the formulas (6), (7), (8), (9), (10) or (11) as matrix material 2,

[0162] Formula (9)

[0163] ), where the symbols and indices used are:

[0164] A 1 is C(R 7 )2, NR 7 , O or S;

[0165] Li is a bond, O, S, C(R 7 )2 or NR 7 ;

[0166] A is at each occurrence independently a group of formula (3) or (4),

[0167] X2 is the same or different at each occurrence CH, CR 6 or N, where a maximum of 2 symbols X2 can mean N;

[0168] * indicates the binding site to formula (9);

[0169] U 1 , U 2 are a bond, O, S, C(R 7 )2 or NR 7 ;

[0170] R 6 is, identically or differently at each occurrence, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; two radicals R 6 also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with each other;

[0171] Ars, identically or differently at each occurrence, independently represents an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is substituted by one or more radicals R 7 can be substituted;

[0172] R 7 is the same or different at each occurrence D, F, CI, Br, I, N(R 8 )2, CN, NO2, OR 8 , SR 8 , Si(R 8 )3, B(OR 8 )2, C(=O)R 8 , P(=O)(R 8 )2, S(=O)R 8 , S(=O)2R 8 , OSO2R 8, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 8 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted; two or more radicals R 7 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R 7 no such ring system;

[0173] R 8is, on each occurrence, the same or different, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical having 1 to 20 C atoms, in which one or more H atoms may also be replaced by F; c, c1, c2 each independently denote on each occurrence 0 or 1, where the sum of the indices on each occurrence is c+c1+c2 = 1; d, d1, d2 each independently denote on each occurrence 0 or 1, where the sum of the indices on each occurrence is d+d1+d2 = 1; q, q1, q2 each independently denote 0 or 1 on each occurrence; s is, on each occurrence, the same or different, 0, 1, 2, 3 or 4; t is, on each occurrence, the same or different, 0, 1, 2 or 3; u is the same or different at each occurrence: 0, 1, or 2; u1, u2 each independently mean 0 or 1 at each occurrence, where the sum u1 + u2 = 1; and v is 0 or 1.

[0174] In compounds of formulas (6), (7), (8), (10) or (11), s is preferably 0 or 1 when the radical R 6 is different from D, or more preferably 0.

[0175] In compounds of formulas (6), (7) or (8), t is preferably 0 or 1 when the radical R 6 is different from D, or more preferably 0.

[0176] In compounds of formulas (6), (7), (8) or (10), u is preferably 0 or 1 when the radical R 6 is different from D, or more preferably 0.

[0177] The sum of the indices s, t and u in compounds of the formulas (6), (7), (8), (10) or (11) is preferably at most 6, particularly preferably at most 4 and particularly preferably at most 2. This preferably applies when R 6 is different from D.

[0178] In compounds of formula (9), c, c1, c2 each independently represent 0 or 1 at each occurrence, where the sum of the indices c+c1+c2 represents 1 at each occurrence. Preferably, c2 represents 1.

[0179] In compounds of formula (9), Li is preferably a single bond or C(R 7 )2, where R 7 has a meaning mentioned above, particularly preferably Li is a single bond.

[0180] In formula (4), U or U when occurring are preferably a single bond or C(R 7 )2, where R 7 has a meaning mentioned above, particularly preferred are U 1 or U 2 when a single bond occurs.

[0181] In a preferred embodiment of the compounds of formulas (6), (7), (8), (9), (10) or (11), which can be combined according to the invention with compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as described above, R 6 identically or differently on each occurrence selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl group is in each case substituted with one or more radicals R 7 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, preferably having 5 to 40 ring atoms, each substituted by one or more radicals R 7may be substituted. In a preferred embodiment of the compounds of formulas (6), (7), (8), (9), (10) or (11), which can be combined according to the invention with compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as described above, R 6 identically or differently on each occurrence selected from the group consisting of D or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which is reacted with one or more radicals R 7 can be substituted.

[0182] Preferably, Ars in compounds of formulas (6), (7), (8), (10) or (11) is selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorenyl, which may be linked via the 1-, 2-, 3- or 4-position, spirobifluorenyl, which may be linked via the 1-, 2-, 3- or 4-position, naphthyl, in particular 1- or 2-linked naphthyl, or residues derived from indole, benzofuran, benzothiophene, carbazole, which may be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which may be linked via the 1-, 2-, 3- or 4-position, dibenzo- thiophene, which can be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene,which are each substituted with one or more radicals R, 7 may be substituted. Preferably, Ars is unsubstituted.

[0183] If A 1 in formula (7) or (8) or (11) for NR 7 the substituent R 7 which is bonded to the nitrogen atom, preferably represents an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 8 In a particularly preferred embodiment, this substituent R 7 identical or different on each occurrence, represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 18 aromatic ring atoms. Preferred embodiments for R 7 are phenyl, biphenyl, terphenyl and quaterphenyl, which are preferably unsubstituted, as well as radicals derived from triazine, pyrimidine and quinazoline, which are substituted by one or more radicals R8 can be substituted. If A 1 in formula (7) or (8) or (11) for C(R 7 )2, the substituents R 7 which are bonded to this carbon atom, preferably identically or differently on each occurrence, represent a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 8 R is particularly preferably 7 represents a methyl group or a phenyl group. The radicals R 7 also form a ring system with each other, resulting in a spiro system. In a preferred embodiment of the compounds of formulas (6), (7), (8), (9), (10), and (11), these compounds are partially or fully deuterated, particularly preferably fully deuterated.

[0184] The preparation of the compounds of formulas (6), (7), (8), (9), (10) and (11) are generally known and some of the compounds are commercially available.

[0185] Compounds of formula (9) are disclosed, for example, in WO2021 / 180614, pages 110 to 119, in particular as examples on pages 120 to 127. Their preparation is disclosed in WO2021 / 180614 on page 128 and in the synthesis examples on pages 214 to 218.

[0186] The preparation of the triarylamines of formula (11) is known to the person skilled in the art and some of the compounds are commercially available.

[0187] If the additional matrix material is a deuterated compound, it is possible that the additional matrix material is a mixture of deuterated compounds with the same basic chemical structure, which differ only in the degree of deuteration and / or the deuteration pattern.

[0188] In a preferred embodiment of the further matrix material, this is a mixture of deuterated compounds of the formulas (6), (7), (8), (9), (10), or (11), as described above, wherein the average degree of deuteration of these compounds is at least 50% to 90%, preferably 70% to 100%. Corresponding deuteration methods are known to the person 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.

[0189] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for diatoms is to treat the compound to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound containing one or more diatoms and capable of releasing them under suitable conditions.

[0190] The platinum catalyst is preferably dry platinum on carbon, preferably 5% dry platinum on carbon. The palladium catalyst is preferably dry palladium on carbon, preferably 5% dry palladium on carbon. A suitable deuterium source is D2O, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid-d4, methanol-d4, or toluene-d8. A preferred deuterium source is D2O or a combination of D2O and a fully deuterated organic solvent. A particularly preferred deuterium source is the combination of D2O with a fully deuterated organic solvent, whereby the fully deuterated solvent is not limited here. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. A particularly preferred deuterium source is a combination of D2O and toluene-d8.The reaction is preferably carried out with heating, more preferably with heating to temperatures between 100 °C and 200 °C. Furthermore, the reaction is preferably carried out under pressure.

[0191] Examples of suitable further matrix materials for combination with compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as previously described or preferably described, are the compounds described in W02019 / 229011 , Table 3, pages 137 to 203, which may also be partially or completely deuterated.

[0192] Examples of suitable further matrix materials for a combination with compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as previously described or preferably described, are the compounds described in WO2011 / 088877, table page 30, compounds 1 to 166, which may also be partially or completely deuterated.

[0193] Examples of suitable further matrix materials for a combination with compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as described above or preferably described, are the compounds described in WO2011 / 128017, table page 23, compounds 1 to 151, which may also be partially or fully deuterated. For a combination with compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as described above or preferably described, compounds of the formula (6) and / or the formula (9) and / or the formula (10) are particularly suitable, as described above or preferably described.

[0194] For a combination with compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as described above or preferably described, compounds of the formula (6) are particularly suitable in which at least one group Ars represents a heteroaromatic ring system having 5 to 40 ring atoms, which with one or more radicals R 7 may be substituted and / or compounds of formula (9) and / or compounds of formula (10).

[0195] For a combination with a compound of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as described above or preferably described, compounds of formula (9) or (10) are very particularly preferably suitable.

[0196] For a combination with a compound of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as described above or preferably described, compounds of formula (10) are very particularly preferably suitable.

[0197] Further examples of suitable host materials of formulas (6), (7), (8), (9), (10) and (11) for combination with compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as previously described or preferably described, are the structures of Table 3 and Table 4 mentioned below.

[0198] Table 3: 9S

[0199] 93

[0200] 03

[0201] 91.

[0202] -179 -

[0203]

[0204] Particularly suitable compounds of formulas (6), (7), (8), (9), (10) or (11), which are selected according to the invention and are preferably used in combination with at least one compound of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) in the electroluminescent device according to the invention, are the compounds of Table 4.

[0205] The above-mentioned host materials of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) and their preferably described embodiments or the compounds of Table 1 or the compounds E1 to E39 can be combined in the device according to the invention as desired with the above-mentioned matrix materials / host materials, the matrix materials / host materials of the formulas (6), (7), (8), (9), (10) or (11) and their preferably described

[0206] Embodiments of Table 3 or compounds H1 to H33.

[0207] Very particularly preferred mixtures of the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) with the host materials of formulas (6), (7), (8), (9), (10) or (11) for the device according to the invention are obtained by combining the compounds E1 to E39 with the compounds H1 to H33 as shown below in Table 5. The first mixture M1, for example, is a combination of the compound E1 with H1.

[0208] Table 5:

[0209] The concentration of the sum of all host materials of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), as described above or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 5 wt.% to 90 wt.%, preferably in the range from 10 wt.% to 85 wt.%, more preferably in the range from 20 wt.% to 85 wt.%, even more preferably in the range from 30 wt.% to 80 wt.%, very particularly preferably in the range from 20 wt.% to 60 wt.% and most preferably in the range from 30 wt.% to 50 wt.%, based on the entire mixture or based on the entire composition of the light-emitting layer.

[0210] The concentration of the sum of all host materials of the formulas (6), (7), (8), (9), (10) or (11), as described above or described as preferred, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 10 wt.% to 95 wt.%, preferably in the range from 15 wt.% to 90 wt.%, more preferably in the range from 15 wt.% to 80 wt.%, even more preferably in the range from 20 wt.% to 70 wt.%, very particularly preferably in the range from 40 wt.% to 80 wt.% and most preferably in the range from 50 wt.% to 70 wt.%, based on the total mixture or based on the total composition of the light-emitting layer.

[0211] The present invention also relates to a mixture which, in addition to the above-mentioned host materials of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), hereinafter referred to as host material 1, and the host material of at least one of the formulas (6), (7), (8), (9), (10) or (11), hereinafter referred to as host material 2, as described above or preferably described, contains at least one phosphorescent emitter.

[0212] The present invention also relates to a mixture selected from M1 to M1287, which contains at least one phosphorescent emitter.

[0213] The term "phosphorescent emitters" typically encompasses compounds in which light emission occurs through a spin-forbidden transition from an excited state with higher spin multiplicity, i.e., a spin state > 1, for example, through a transition from a triplet state or a state with an even higher spin quantum number, such as a quintet state. Preferably, this refers to a transition from a triplet state.

[0214] Particularly suitable phosphorescent emitters (= triplet emitters) are compounds that emit light upon suitable excitation, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are used as phosphorescent emitters, in particular compounds containing iridium or platinum. For the purposes of the present invention, all luminescent compounds containing the above-mentioned metals are considered phosphorescent emitters.

[0215] In general, all phosphorescent complexes as used in the prior art for phosphorescent OLEDs and as known to the person skilled in the art in the field of organic electroluminescent devices are suitable.

[0216] Preferred phosphorescent emitters according to the present invention correspond to the formula (IIIa),

[0217] Formula (Illa), where the symbols and indices for this formula (Illa) have the meaning: n+m is 3, n is 1 or 2, m is 2 or 1 ,

[0218] X is the same or different at each occurrence, N or CR,

[0219] R is, on each occurrence, identically or differently, H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 7 C atoms which may be partially or fully substituted with deuterium or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms which may be partially or fully substituted with deuterium.

[0220] A further subject matter of the invention is accordingly an organic electroluminescent device as described above or preferably described, characterized in that the light-emitting layer contains, in addition to the host materials 1 and 2, at least one phosphorescent emitter which corresponds to the formula (IIIa), as described above.

[0221] In emitters of formula (IIIa), n is preferably 1 and m is preferably 2.

[0222] In emitters of formula (IIIa), one X is preferably selected from N and the other Xs are CR or all Xs, identically or differently on each occurrence, are CR. In emitters of formula (IIIa), at least one R is preferably different from H. In emitters of formula (IIIa), two Rs are preferably different from H and have one of the meanings otherwise previously given for the emitters of formula (IIIa).

[0223] Preferred phosphorescent emitters according to the present invention correspond to the formulas (I), (II), (III), (IV) or (V),

[0224]

[0225] Formula (IV)

[0226] formula where the symbols and indices for these formulas (I), (II), (III), (IV) and (V) are the

[0227] Meaning:

[0228] Ri is H or D, R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium.

[0229] Preferred phosphorescent emitters according to the present invention correspond to the formulas (VI), (VII) or (VIII),

[0230] formula

[0231] where the symbols and indices for these formulas (VI), (VII) and (VIII) have the meaning:

[0232] Ri is H or D, R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium.

[0233] Preferred examples of phosphorescent emitters are described in WO2019 / 007867 on pages 120 to 126 in Table 5 and on pages 127 to 129 in Table 6. The emitters are incorporated into the description by this reference.

[0234] Particularly preferred examples of phosphorescent emitters are listed in Table 6 below.

[0235] Table 6: 

[0236]

[0237] In the mixtures according to the invention or in the light-emitting layer of the device according to the invention, each mixture selected from the sum of the mixtures M1 to M1287 is preferably combined with a compound of the formula (IIIa) or a compound of the formulas (I) to (VIII) or a compound from Table 6.

[0238] The light-emitting layer in the organic electroluminescent device according to the invention containing at least one phosphorescent emitter is preferably an infrared-emitting, yellow, orange, red, green, blue or ultraviolet-emitting layer, particularly preferably a yellow or green-emitting layer and very particularly preferably a green-emitting layer.

[0239] A yellow-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 540 to 570 nm. An orange-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 570 to 600 nm. A red-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 600 to 750 nm. A green-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 490 to 540 nm. A blue-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 440 to 490 nm.The photoluminescence maximum of the layer is determined by measuring the photoluminescence spectrum of the layer with a layer thickness of 50 nm at room temperature, wherein the layer contains the inventive combination of the host material 1 of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) and the host material 2 of at least one of the formulas (6), (7), (8), (9), (10) or (11) and the corresponding emitter.

[0240] The photoluminescence spectrum of the layer is recorded, for example, using a commercially available photoluminescence spectrometer.

[0241] The photoluminescence spectrum of the selected emitter is usually measured in oxygen-free solution, 10' 5molar, measured at room temperature, and any solvent in which the selected emitter dissolves at the specified concentration is suitable. Particularly suitable solvents are usually toluene or 2-methyl-THF, but also dichloromethane. The measurement is carried out using a commercially available photoluminescence spectrometer. The triplet energy T1 in eV is determined from the photoluminescence spectra of the emitters. First, the peak maximum Plmax. (in nm) of the photoluminescence spectrum is determined. The peak maximum Plmax. (in nm) is then converted to eV according to: E(T1 in eV) = 1240 / E(T1 in nm) = 1240 / PLmax. (in nm).

[0242] Preferred phosphorescent emitters are therefore yellow emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 6, whose triplet energy T 1 is preferably between ~2.3 eV and ~2.1 eV. Preferred phosphorescent emitters are therefore green emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 6, whose triplet energy T is preferably between ~2.5 eV and ~2.3 eV.

[0243] Particularly preferred phosphorescent emitters are accordingly green emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 6, as previously described, whose triplet energy T-| is preferably between ~2.5 eV and ~2.3 eV.

[0244] Very particular preference is given to selecting green emitters, preferably of the formula (IIIa), the formulas (I) to (VIII) or from Table 6, as described above, for the mixture according to the invention or the emitting layer according to the invention.

[0245] Fluorescent emitters can also be present in the light-emitting layer of the device according to the invention or in the mixture according to the invention. Preferred fluorescent emitting compounds are selected from the class of arylamines, wherein preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, particularly preferably with at least 14 ring atoms. Preferred examples thereof are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to be a compound in which one diarylamino group is bonded directly to one anthracene group, preferably in the 9-position. An aromatic anthracenediamine is understood to be a compound in which two diarylamino groups are bonded directly to one anthracene group, preferably in the 9,10-position.Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, with the diarylamino groups on the pyrene preferably being bonded in the 1-position or 1,6-position. Further preferred emitting compounds are indenofluorenamines or diamines, benzoindenofluorenamines or diamines, and dibenzoindenofluorenamines or diamines, as well as indenofluorene derivatives with fused aryl groups. Pyrenearylamines are also preferred. Also preferred are benzoindenofluoreneamines, benzofluoreneamines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives linked to furan units or thiophene units. Furthermore, the light-emitting device or the mixture according to the invention can also contain materials that exhibit TADF (thermally activated delayed fluorescence).In a further preferred embodiment of the invention, the at least one light-emitting layer of the organic electroluminescent device can comprise three or four different matrix materials, preferably three different matrix materials. These corresponding mixed-matrix systems can consist of the matrix materials described for host material 1 and host material 2, but they can also contain, as a third or fourth matrix material, for example, in addition to host material 1 or host material 2, wide-band-gap materials, bipolar host materials, electron-transport materials (ETMs), or hole-transport materials (HTMs).

[0246] Preferably, the mixed matrix system is optimized for an emitter of formula (IIIa), formulas (I) to (VIII) or from Table 5.

[0247] According to one embodiment of the present invention, the mixture contains no further components, i.e., functional materials, in addition to the constituents of the host material of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), or (1j) as host material 1 and the host material 2, selected from one or more of the compounds of formulas (6), (7), (8), (9), (10), or (11), as described above. These are material mixtures that are used as such to produce the light-emitting layer. These mixtures are also referred to as premix systems, which are used as the sole material source during the vapor deposition of the host materials for the light-emitting layer and which have a constant mixing ratio during vapor deposition.This allows the vapor deposition of a layer with a uniform distribution of the components to be achieved in a simple and rapid manner, without the need for precise control of a large number of material sources.

[0248] According to an alternative embodiment of the present invention, the mixture contains, as a premix system, in addition to the constituents of host material 1 and 2, as described above, a phosphorescent emitter, as described above. With a suitable mixing ratio during vapor deposition, this mixture can also be used as the sole material source, as described above. Preferred premix systems are those consisting of two matrix materials, namely a compound of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) and a compound of one of formulas (6), (7), (8), (9), (10) or (11). Preferred are premix systems consisting of three matrix materials, namely a compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) and two compounds of one of the formulas (6), (7), (8), (9), (10) or (11).

[0249] The components or constituents of the light-emitting layer of the device according to the invention can be processed by vapor deposition or from solution. The material combination of host materials 1 and 2, as described above or preferably described, optionally with the phosphorescent emitter, as described above or preferably described, can be provided for this purpose in a formulation containing at least one solvent. Suitable formulations have been described previously.

[0250] The light-emitting layer in the device according to the invention according to the preferred embodiments and the emitting compound preferably contains between 99.9 and 1 vol.%, more preferably between 99 and 10 vol.%, particularly preferably between 98 and 60 vol.%, most preferably between 97 and 80 vol.% of matrix material made of at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) and at least one compound of the formulas (6), (7), (8), (9), (10) or (11) according to the preferred embodiments, based on the total composition of emitter and matrix material. Accordingly, the light-emitting layer in the device according to the invention preferably contains between 0.1 and 99 vol.%, more preferably between 1 and 90 vol.%, particularly preferably between 2 and 40 vol.%, most preferably between 3 and 20 vol.-% of the emitter based on the total composition of the light-emitting layer consisting of emitter and matrix material. If the compounds are processed from solution, the corresponding amounts in wt.% are preferred instead of the above-mentioned amounts in vol.%.

[0251] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the organic layer contains a hole injection layer (HIL) and / or a hole transport layer (HTL), whose hole injecting material and hole transporting material belong to the class of arylamines.

[0252] The sequence of layers in the organic electroluminescent device according to the invention is preferably the following: anode | hole injection layer | hole transport layer | emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0253] This sequence of layers is a preferred sequence.

[0254] It should be noted again that not all of the layers mentioned need to be present and / or that additional layers may be present.

[0255] All materials used in the prior art as electron-transport materials in the electron-transport layer can be used as materials for the electron-transport layer. Particularly suitable are aluminum complexes, for example Alqβ, zirconium complexes, for example Zrq4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives.

[0256] Suitable cathodes for the device according to the invention include metals with low work functions, metal alloys, or multilayer structures made of different metals, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys made of an alkali or alkaline earth metal and silver, for example, an alloy of magnesium and silver, are also suitable. In multilayer structures, in addition to the metals mentioned, other metals with a relatively high work function, such as Ag or Al, can also be used. Combinations of the metals, such as Ca / Ag, Mg / Ag, or Ba / Ag, are then generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor.Suitable materials for this purpose include alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Ü2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). Lithium quinolinate (LiQ) can also be used. The thickness of this layer is preferably between 0.5 and 5 nm.

[0257] Materials with a high work function are preferred as anodes. The anode preferably has a work function greater than 4.5 eV vs. vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Metal / metal oxide electrodes (e.g., Al / Ni / NiO) can also be used. x , AI / PtO x) may be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to enable either the irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive, doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of several layers, for example an inner layer made of ITO and an outer layer made of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0258] The organic electroluminescent device according to the invention is structured, contacted and finally sealed accordingly (depending on the application) during production, since the lifetime of the devices according to the invention is shortened in the presence of water and / or air.

[0259] The production of the device according to the invention is not restricted in this regard. It is possible for one or more organic layers, including the light-emitting layer, to be coated using a sublimation process. The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10'5 mbar, preferably less than 10'6 mbar. However, it is also possible for the initial pressure to be even lower, for example, less than 10'7 mbar.

[0260] The organic electroluminescent device according to the invention is preferably characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are applied at a pressure between 10 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (e.g., BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0261] Furthermore, the organic electroluminescent device according to the invention is preferably characterized in that one or more organic layers comprising the composition according to the invention are produced from solution, for example by spin coating, or by any printing process, such as screen printing, flexographic printing, nozzle printing, or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or inkjet printing. Soluble host materials 1 and 2 and phosphorescent emitters are required for this purpose. Processing from solution has the advantage that, for example, the light-emitting layer can be applied very easily and cost-effectively. This technique is particularly suitable for the mass production of organic electroluminescent devices.

[0262] Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are deposited by vapor deposition.

[0263] These methods are generally known to the person skilled in the art and can be applied to organic electroluminescent devices.

[0264] When manufactured by vapor deposition, there are basically two ways in which the organic layer according to the invention, preferably the light-emitting layer, can be applied or vapor-deposited onto any substrate or the previous layer. Firstly, the materials used can each be placed in a material source and then evaporated from the various material sources ("co-evaporation"). Secondly, the various materials can be premixed ("premixed" systems) and the mixture placed in a single material source, from which it is then vaporized ("premix evaporation"). This allows for the vapor deposition of the light-emitting layer with a uniform distribution of the components in a simple and rapid manner, without the need for precise control of a large number of material sources.

[0265] The following procedures are possible:

[0266] A method for producing the organic electroluminescent device according to the invention, as described above or preferably described, characterized in that the organic layer, preferably the light-emitting layer, the electron transport layer and / or hole blocking layer, is applied by vapor phase deposition, in particular with a sublimation process and / or with an OVPD (Organic Vapor Phase Deposition) process and / or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing process.

[0267] A method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein the at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) together with the further materials which form the light-emitting layer are deposited successively or simultaneously from at least two material sources from the vapor phase.

[0268] A method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein the at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) together with at least one further matrix material as a premix, are deposited from the vapor phase successively or simultaneously with the light-emitting materials selected from the group of phosphorescent emitters, fluorescent emitters and / or emitters which exhibit TADF (thermally activated delayed fluorescence).

[0269] The electronic devices according to the invention, in particular organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art:

[0270] 1. Electronic devices, in particular organic electroluminescent devices containing compounds according to formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), or the preferred embodiments described above and below, in particular as matrix material, exhibit a very good lifetime. These compounds, in particular, result in low roll-off, i.e., a low drop in the power efficiency of the device at high luminance levels.

[0271] 2. The compounds according to the invention according to formula (1a) or formula (1b), or the preferred embodiments described above and below, exhibit very high stability and longevity. 3. Using compounds according to formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j), or the preferred embodiments described above and below, the formation of optical loss channels can be avoided in electronic devices, particularly organic electroluminescent devices. As a result, these devices are characterized by high PL and thus high EL efficiency of emitters and excellent energy transfer from the matrices to dopants.

[0272] 4. The compounds according to formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i) or (1j) or the preferred embodiments described above and below have a deep triplet level Ti, which can be, for example, in the range of 2.50 eV - 2.90 eV.

[0273] These advantages mentioned above are not accompanied by an excessive deterioration of the other electronic properties.

[0274] It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Any feature disclosed in the present invention may, unless explicitly excluded, be replaced by alternative features serving the same, equivalent, or similar purpose. Thus, unless otherwise stated, any feature disclosed in the present invention is to be considered an example of a generic series or an equivalent or similar feature.

[0275] All features of the present invention can be combined with each other in any way, unless certain features and / or steps are mutually exclusive. This applies in particular to the combination of preferred features of the present invention.

[0276] The teaching of technical action disclosed in the present invention can be abstracted and combined with other examples.

[0277] The invention is explained in more detail by the following examples, without intending to limit it thereby.

[0278] Examples

[0279] General Methods: The Gaussian16 program package (Rev. B.01) is used for all quantum chemical calculations. The neutral singlet ground state is optimized at the B3LYP / 6-31G(d) level of theory. HOMO and LUMO values ​​are determined at the B3LYP / 6-31G(d) level for the ground-state energy optimized with B3LYP / 6-31G(d). TD-DFT singlet and triplet excitations (vertical excitations) are then calculated using the same method (B3LYP / 6-31G(d)) and the optimized ground-state geometry. The default settings for SCF and gradient convergence are used.

[0280] From the energy calculation, the HOMO is determined as the last orbital occupied by two electrons (alpha occupancy eigenvalues) and LIIMO as the first unoccupied orbital (alpha virtual eigenvalues) in Hartree units, where HEh and LEh represent the HOMO energy in Hartree units and the LUMO energy in Hartree units, respectively. From this, the HOMO and LUMO values ​​in electronvolts, calibrated using cyclic voltammetry measurements, are determined as follows:

[0281] HOMOcorr = 0.90603 * HOMO - 0.84836

[0282] LUMOcorr = 0.99687 * LUMO - 0.72445

[0283] The triplet level T1 of a material is defined as the relative excitation energy (in eV) of the lowest energy triplet state resulting from quantum chemical energy calculations.

[0284] The singlet level S1 of a material is defined as the relative excitation energy (in eV) of the singlet state with the second lowest energy, which results from the quantum chemical energy calculation.

[0285] The lowest energy singlet state is called SO.

[0286] The method described here is independent of the software package used and always produces the same results. Examples of commonly used programs for this purpose are "Gaussian09" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.). In this case, the program package "Gaussian16 (Rev. B.01)" is used to calculate the energies.

[0287] Synthesis examples

[0288] Unless otherwise stated, the following syntheses were carried out under a protective gas atmosphere in dried solvents. Solvents and reagents can be purchased from Sigma-ALDRICH or ABCR, for example. The corresponding CAS numbers are also given for the compounds known from the literature. 1) 1-Bromo-4H-Naphtho[1,2,3,4-otef]carbazole)-dio [ - - ]

[0289] 3.7 g (15.5 mmol; 1.00 eq) of 4 / 7-naphtho[1,2,3,4-de / ]carbazole and 20.0 g of 5% Pt on activated carbon were suspended in 400 g (502 mmol; 1.00 eq) of deuterium oxide [CAS 7789-20-0] and 200 g (778 mmol; 1.55 eq) of toluene-d8 [CAS 2037-26-5]. The reaction mixture was stirred for 5 days at 165°C under elevated autogenous pressure. After cooling, the mixture was extracted twice with tetrahydrofuran, and the combined organic phases were washed with brine and dried over sodium sulfate. After filtration, the solvent was removed under reduced pressure. The product shown above in a mixture with proportions of H / D isotopomers and H / D isotopologues is obtained after further purification by extraction, recrystallization and sublimation.

[0290] The yield is 1.7 g (6.9 mmol), corresponding to 47% of theory.

[0291] Analogously, the following connections are made:

[0292] ) 1-Bromo-4H-Naphtho[1,2,3,4-otef]carbazole

[0293] [109606-75-9] 43 g (180.0 mmol) of 4 / 7-naphtho[1,2,3,4-de / ]carbazole are suspended in 1500 mL of DMF. 32 g (180 mmol) of NBS (N-bromosuccinimide) are added portionwise to this suspension at 0°C and stirred for 5 hours in the dark, during which the temperature slowly increases to 30°C. Water / ice is then added, the solid is separated, and the residue is washed with ethanol. The residue is recrystallized from toluene / ethanol (1:1). The yield is 39 g (123 mmol), corresponding to 69% of theory.

[0294] Analogously, the following connections are made:

[0295] 3) 1-Bromo-4-phenyl-naphtho[1,2,3,4-otef]carbazole

[0296] 7.9 g (24.8 mmol, 1 000eq) of 1-bromo-4 / 7-naphtho[1,2,3,4-def]carbazole, 26.1 g (128 mmol, 5.2 eq) of iodobenzene, and 7.1 g (74.4 mmol, 3 eq) of NaOtBu were placed in 220 ml of dried DMF and inertized with argon. Subsequently, 0.62 g (2.7 mmol, 0.11 eq) of 1,3-di(2-pyridyl)-1,3-propanedione and 0.52 g (2.7 mmol, 0.11 eq) of copper(I) iodide were added, and the mixture was heated at 140°C for three days. After the reaction is complete, the reaction mixture is carefully concentrated on a rotary evaporator, the precipitated solid is filtered off with suction and washed with water and ethanol. The crude product is purified twice using a hot extractor (toluene / heptane 1:1), and the resulting solid is recrystallized from toluene. The yield after sublimation is 8.3 g (20.9 mmol), 85% of theory.

[0297] Analogously, the following connections are made:

[0298]

[0299] 4) 4-Phenyl-(4,4,5,5-tetramethyl-[1,3,2]-dioxaborolan-1-yl)Naphtho[1,2,3,4-

[0300] 8.7 g (22 mmol) of 1-bromo-4-phenyl-naphtho[1,2,3,4-cfef]carbazole, 6.2 g (24 mmol) of bis(pinacolato)diborane, and 6.3 g (64 mmol) of potassium acetate are suspended in 75 ml of dioxane. 0.53 g (0.66 mmol) of 1,1-bis(diphenylphosphino)ferrocene dichloropalladium(II) complex with DCM (dichloromethane) is added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated, washed three times with 50 mL of water, and then evaporated to dryness. The residue is recrystallized from toluene. The yield after sublimation is 7.2 g (16.2 mmol), 74% of theory. The following compounds are prepared analogously: 5) 1-[9-(4,6-Diphenyl-[1,3,5]triazin-2-yl)-dibenzofuran-2-yl]-9-phenyl-4H-naptho[1,2,3,4-def]carbazole

[0301] [1822310-63-3]

[0302] 75 g (157 mmol) of 2-(8-bromo-dibenzofuran-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) were added to this suspension, and the reaction mixture was heated under reflux for 16 h. After cooling, the organic phase was separated, filtered through silica gel, washed three times with 200 mL of water, and then evaporated to dryness. The product is purified by column chromatography on silica gel with toluene / heptane (1 :2) and finally evaporated in high vacuum (p = 5 x 10 -7 mbar) sublimated (purity 99.9%).

[0303] The yield is 75 g (105 mmol), corresponding to 67% of theory.

[0304] Analogously, the following connections are made:

[0305] 6) 1-[3'-(4-[1,1'-Biphenyl]-4-yl-6-phenyl-1,3,5-triazin-2-yl)[1,1'-biphenyl]-3-yl]- 4- phenyl-Naphtho[1,2,3,4-otef]carbazol-d36

[0306] 38.8 g (50.0 mmol; 1.00 eq) of 1-[3'-(4-[1,1'-biphenyl]-4-yl-6-phenyl-1,3,5-triazin-2-yl)[1,1-biphenyl]-3-yl]-4-phenyl-naphtho[1,2,3,4-def]carbazole is suspended in 640 mL (120 eq) of toluene-d8 [CAS 2037-26-5]. 16.6 mL (6.00 eq) of trifluoromethanesulfonic acid is added to this mixture while cooling. The reaction mixture is stirred at ambient temperature for 6 hours. Subsequently, 120 mL (130 eq) of deuterium oxide [CAS 7789-20-0] is added dropwise at 0°C. After neutralization with potassium sulfate solution, the mixture is extracted with toluene, and the combined organic phases are washed with brine and dried over sodium sulfate. After filtration, the solvent is removed under reduced pressure. 32.5 g (39 mmol, 80% of theory) of the product shown above, mixed with portions of H / D isotopomers and H / D isotopologues, are obtained after chromatographic purification and finally concentrated under high vacuum (p = 5 x 10 -7 mbar) sublimated (purity 99.9%).

[0307] Analogously, the following connection is established: Production of OLEDs

[0308] In the following examples (see Tables 7 and 8) the data of different OLEDs are presented.

[0309] Examples B1 to B15 show data from OLEDs according to the invention. The substrates used for the OLEDs in Table 7 are glass plates coated with a 50 nm thick patterned ITO (indium tin oxide).

[0310] The exact structure of the OLEDs can be found in Table 7. The materials required to manufacture the OLEDs are shown in Table 9, unless previously described.

[0311] All materials are thermally evaporated in a vacuum chamber. The emission layer always consists of at least one matrix material (also called host material) and an emitting dopant (dopant, emitter), which is mixed into the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as EE1:H1:TEG2 (32%:60%:8%) 40nm means that the material EE1 is present in a volume fraction of 32% as host material 1, the compound H1 as host material 2 in a volume fraction of 60%, and TEG2 in a volume fraction of 8% in a 40nm thick layer. Analogously, the electron transport layer can also consist of a mixture of two materials.

[0312] The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra and current-voltage-luminance characteristics (IUL characteristics) are measured, from which the EQE is calculated. The calculation is performed assuming a Lambertian radiation pattern. The electroluminescence spectra are measured at a luminance of 1000 cd / m². 2 and from this the CIE 1931 x and y color coordinates are calculated. The value U1000 in Table 8 refers to the voltage required for a luminance of 1000 cd / m 2 is required. EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd / m 2 .

[0313] The lifetime LT is defined as the time after which the luminance in mA / cm 2 from a starting luminance L0 (in cd / m 2 ) to a certain proportion L1 (in cd / m 2). A value of L1 / L0 = 80% in Table 8 means that the lifetime given in column LT corresponds to the time (in hours) after which the luminance drops to 80% of its initial value (L0).

[0314] Use of compounds and mixtures according to the invention in OLEDs The compounds or material combinations according to the invention can be used in the emission layer in phosphorescent green OLEDs.

[0315] The data for the various OLEDs are summarized in Table 8. Examples C1 to C4, C5 to C10, C12, C13, and C15 are comparative examples; examples B1 to B4 and B6 to B15 show data for OLEDs according to the invention. The inventive examples demonstrate a significant advantage in device lifetime.

[0316] Table 7: Structure of the OLEDs

[0317] Table 8:

[0318] Table 9: Materials used, unless previously described

Claims

Claims Material for an organic electronic device containing at least one compound according to formula (1), where the symbols and indices used are: L is, identically or differently at each occurrence, a single bond, an aromatic ring system with 5 to 20 ring atoms or a heteroaromatic ring system with 5 to 30 ring atoms which may be substituted by one or more radicals R°; R° is, at each occurrence, the same or different, selected from the group consisting of D, F, CI, Br, I, CN, NO2, C(=O)R 2 , P(=O)(Ar)2, P(Ar)2, B(Ar)2, Si(Ar)s, Si(R 2 )s, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl group having 2 to 20 C atoms, each of which is substituted by one or more radicals R 2may be substituted, with one or more non-adjacent CH2 groups being substituted 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 Fl atoms may be replaced by D, F, CI, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, which may be substituted with one or more radicals R 2 may be substituted, or an aralkyl or heteroaralkyl group having 5 to 40 ring atoms which may be substituted with one or more radicals R 2 can be substituted; Rx corresponds to one of the formulas (1-2) to (1-16) Formula (1-13) Formula (1-14) Formula (1-15) * denotes the connection to L, Ra, Rb and Rc represent a monosubstitution, a disubstitution, a trisubstitution, the maximum allowable substitution or no substitution, Ra, Rb and Rc are D at every occurrence; V is O, S or N-Au; R 1 is at each occurrence independently H, D, CN, F or non-deuterated or partially or fully deuterated phenyl, 1,4-biphenyl, 1,3-biphenyl or 1,2-biphenyl; Ar is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by one or more radicals R; Aryl is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more non-adjacent CH2 groups of the alkyl group may be replaced by O or S and where one or more H atoms of the alkyl group may be replaced by D, F, or CN; An is an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be substituted by one or more radicals R, Ar2, Ars are, identically or differently at each occurrence, H, D, CN, F, a non-deuterated or partially or fully deuterated alkyl group having 1 to 10 C atoms, an aromatic or heteroaromatic ring system 2 having 5 to 40 ring atoms, which may be substituted by one or more radicals R; R is, at each occurrence, identically or differently selected from the group consisting of D, F, CN, Si(aryl)s, a straight-chain alkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more non-adjacent CH2 groups may be replaced by O or S, and where one or more H atoms may be replaced by D, F, or CN, where the compound of formula (1) is partially or completely deuterated. Material for an organic electronic device according to claim 1, where L corresponds to one of the formulas L-1 to L-41, which may be substituted by one or more radicals R° and R° denotes D: L-13 L-14 L-15 L-16 L-36 L-37 where the dashed lines indicate the attachment to Rx or to the rest of formula (1); Vi and V2 are each independently O, S, Se or N-Ar4; and Ar4 is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R. Material for an organic electronic device according to claim 1 or 2, wherein Ra, Rb and Rc each independently of one another denote monosubstitution, disubstitution or trisubstitution. Material for an organic electronic device according to one or more of claims 1 to 3, wherein Rx corresponds to formula (1-2). Material for an organic electronic device according to one or more of claims 1 to 4, comprising at least one compound selected from the compounds 1 to 39.

6. A mixture comprising at least one compound according to one or more of claims 1 to 5 and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence).

7. Formulation comprising at least one compound according to one or more of claims 1 to 5 or a mixture according to claim 6 and at least one solvent.

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

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

10. Organic electronic device according to claim 8 or 9, wherein the organic layer comprises at least one light-emitting layer, a electron-transporting layer or a hole-blocking layer containing at least one compound according to one of claims 1 to 5. Organic electronic device according to one or more of claims 8 to 10, characterized in that the light-emitting layer contains the at least one compound according to one of claims 1 to 5. Organic electronic device according to one or more of claims 8 to 11, characterized in that the light-emitting layer contains at least one further matrix material in addition to the compound according to one of claims 1 to 5. Organic electroluminescent device according to claim 12, characterized in that the further matrix material corresponds to one or more of the compounds of formulas (6), (7), (8), (9), (10) or (11), Formula (10), where the symbols and indices used are: A 1 is C(R 7 )2, NR 7 , O or S; Li is a bond, O, S, C(R 7 )2 or NR 7 ; A is, at each occurrence independently, a group of the formula (3) or (4), X2 is the same or different at each occurrence CH, CR 6 or N, where a maximum of 2 symbols X2 can mean N; * indicates the binding site to formula (9); U 1 , U 2 are a bond, O, S, C(R 7 )2 or NR 7 ; R 6is, identically or differently at each occurrence, D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted; two radicals R 6 also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with each other; Ars, identically or differently at each occurrence, independently represents an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is substituted by one or more radicals R 7 can be substituted; R 7 is the same or different at each occurrence D, F, CI, Br, I, N(R 8 )2, CN, NO2, OR 8 , SR 8 , Si(R 8 )3, B(OR 8 )2, C(=O)R 8 , P(=O)(R 8 )2, S(=O)R 8 , S(=O)2R 8 , OSO2R 8 , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 8 may be substituted, with one or more non-adjacent CH2 groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted; two or more radicals R 7 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R 7 no such ring system; Q R is, identically or differently at each occurrence, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may be replaced by F; c, c1, c2 each independently at each occurrence denote 0 or 1, where the sum of the indices at each occurrence c+c1+c2 = 1; d, d1, d2 each independently at each occurrence mean 0 or 1, where the sum of the indices at each occurrence is d+d1+d2 = 1; q, q1, q2 each independently at each occurrence is 0 or 1; s is the same or different at each occurrence and is 0, 1, 2, 3 or 4; t is the same or different at each occurrence and is 0, 1, 2 or 3; u is the same or different at each occurrence and is 0, 1 or 2; u1, u2 each independently at each occurrence is 0 or 1, where the sum u1 + u2 = 1; and v is 0 or 1. Organic electronic device according to one or more of claims 8 to 13, characterized in that the light-emitting layer contains a phosphorescent emitter.Organic electronic device according to one or more of claims 8 to 14, characterized in that it is an electroluminescent device selected from the group consisting of organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers), and organic light-emitting diodes (OLEDs).

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