Materials for organic electroluminescent devices

Abstract

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

Description

[0001] Materials for organic electroluminescent devices Technical field 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. State of the art 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 of particular importance here.Improvements to these materials can therefore also lead to significant improvements in OLED properties. 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. WO2018060218 A1, KR20220135761 A, KR20220063428 A, and WO22207678 A1 describe, among other things, specific diazadibenzofuran-carbazole derivatives and diazadibenzothiophene-carbazole derivatives as matrix materials. WO2012048781 A1, CN110437241 A, and US2022263031 A1 describe, among other things, specific 4H-naphtho[1,2,3,4-def]carbazole derivatives as matrix materials. KR20210036304 A, KR20210034528 A, WO22038065 A1, CN115073356 A, CN112062753 A, and US2022263031 A1 describe, among other things, complex carbazole derivatives as matrix materials.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.

[0002] 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.

[0003] It has further been found that the combination of at least one compound of the formula (1) as the first host material and at least one hole-transporting compound, for example in combination with one or more compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), as a further host material or 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.

[0004] Summary of the invention

[0005] A first aspect of the present invention is a compound according to formula (1),

[0006] (D) b where the symbols and indices used are:

[0007] L is, identically or differently at each occurrence, a single bond or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which is linked to one or more radicals R 1 can be substituted;

[0008] R° is, at each occurrence, the same or different, selected from the group consisting of 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 )3, 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 H 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;

[0009] R 1 is selected at each occurrence, identically or differently, 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 )a, 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 2 may 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 H atoms may be replaced by D, F, CI, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 40 aromatic 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 2may 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; * indicates the connection to L-Rx,

[0010] V is O or S;

[0011] R# is at each occurrence independently D, F, CN or phenyl which may be substituted with one or more radicals R 2 can be substituted;

[0012] [R#]a2 represents a monosubstitution, a disubstitution, the maximum allowed substitution or no substitution with R#;

[0013] 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;

[0014] An, Ar2 are independently an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be substituted by one or more radicals R;

[0015] Ars is an aromatic ring system with 6 to 40 ring atoms, which may be substituted with one or more radicals R, or a heteroaromatic

[0016] 9 ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R and wherein the heteroaromatic ring system contains one or more heteroatoms selected from O, S, Se or Si;

[0017] AM is, at each occurrence, the same or different, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by one or more radicals R;

[0018] R is, at each occurrence, identically or differently 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 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;

[0019] (D) a ,(D)b, (D)c represent a monosubstitution, a disubstitution, a trisubstitution, the maximum allowed substitution or no substitution with deuterium; a1 is 0, 1 or 2.

[0020] 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).

[0021] 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. The invention further provides the use of a compound of formula (1) in an organic electronic device.

[0022] A further subject matter of the invention is 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.

[0023] A further subject of the invention is a process for producing an organic electronic, preferably electroluminescent, device, as described above or preferably described below, characterized in that the organic layer is applied by vapor deposition or from solution.

[0024] Description of the invention

[0025] In this patent application, “D” or “D atom” refers to deuterium.

[0026] 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.

[0027] 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.

[0028] An aromatic ring system with 6 to 18 carbon atoms is preferably selected from phenyl, fully deuterated phenyl, biphenyl, naphthyl, phenanthryl, and triphenylenyl. 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.

[0029] 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.

[0030] 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, 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, Phenan- thrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1,2-Thiazol, 1,3-Thiazol, Benzo- thiazol, Pyridazin, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1,5-Diaza- anthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1 ,6-Diazapyren, 1,8-Diazapyren, 4,5-Diaza- pyren, 4,5,9, 10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1 ,2,3-Triazol, 1,2,4- Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1,2,4-Oxadiazol, 1 ,2,5-Oxadiazol, 1,3,4-Oxadiazol, 1,2,3-Thiadiazol, 1 ,2,4-Thiadiazol, 1,2,5-Thiadiazol, 1,3,4-Thiadiazol, 1 ,3,5-Triazin, 1,2,4- Triazin, 1 ,2,3-Triazin, Tetrazol, 1,2,4,5-Tetrazin, 1,2,3,4-Tetrazin, 1,2,3,5-Tetrazin, Purin, Pteridin, Indolizin und Benzothiadiazol.,

[0031] The abbreviations Ar, An, Ar2, and An, identically or differently, denote 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 have a meaning as described above or below. A preferred meaning of Ar and An and Ar2 and An is described below.

[0032] The abbreviation Ars, identically or differently on each occurrence, stands for an aromatic ring system having 6 to 40 ring atoms, which may be substituted by one or more radicals R, or a heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R, where the heteroaromatic ring system contains one or more heteroatoms selected from O, S, Se, or Si, where the radical R or the substituents R has / have a meaning as described above or below. A preferred meaning of Ars is described below.

[0033] 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 7has / have a meaning as described above or below. A preferred meaning of Ars is described below.

[0034] For the purposes of this description, the phrase "two or more residues can form a ring" means, among other things, that the two residues are linked by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme: Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring. This is illustrated by the following scheme:

[0035] 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.

[0036] In the context of the present invention, a straight-chain, branched or cyclic Ci- to C2o-alkyl group is understood to mean, for example, the radicals methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-Octyl, 2-Ethylhexyl, Cyclooctyl, 1-Bicyclo[2,2,2]octyl, 2-Bicyclo[2,2,2]octyl, 2-(2,6-Dimethyl)octyl, 3-(3,7-Dimethyl)octyl, Adamantyl, Trifluoromethyl, Pentafluoroethyl, 2,2,2-Trifluoroethyl, 1 ,1-Dimethyl-n-hex-1-yl-,

[0037] 1.1-Dimethyl-n-hept-1-yl-, 1,1-Dimethyl-n-oct-1-yl-, 1,1-Dimethyl-n-dec-1-yl-, 1,1-Dimethyl-n-dodec-1-yl-, 1,1-Dimethyl-n-tetradec-1-yl-, 1 ,1-Dimethyl-n-hexadec-1-yl-, 1,1-Dimethyl-n-octadec-1-yl-, 1, 1-Diethyl-n-hex-1-yl-, 1, 1-Diethyl-n-hept-1 -yl-, 1, 1-Diethyl-n-oct-1 -yl-,

[0038] 1.1-Diethyl-n-dec-1-yl-, 1,1-Diethyl-n-dodec-1-yl-, 1,1-Diethyl-n-tetradec-1-yl-, 1,1-Diethyln-n-hexadec-1-yl-, 1,1-Diethyl-n-octadec-1-yl-, 1-(n-propyl)-cyclohex-1-yl-, 1-(n-butyl)-cyclohex-1-yl-, 1-(n-hexyl)-cyclohex-1-yl-, 1-(n-octyl)-cyclohex-1-yl- and 1-(n-decyl)-cyclohex-1-yl- understood.

[0039] The compounds of formula (1) and their preferred embodiments are described below. 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.

[0040] The index a1 represents 0, 1, or 2, whereby the position of the substituents R° is not restricted. Preferred compounds of formula (1) are compounds of formula (1a) where a1 = 0, compounds of formula (1b) where a1 = 1, and compounds of formula (1c) where a1 = 2.

[0041] where R°, (D) a , (D)b, (D) c , L and Rx have a meaning mentioned above or preferred below.

[0042] The radical R° is, identically or differently at each occurrence, preferably 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 or an alkenyl group having 2 to 20 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, an aromatic ring system with 6 to 40 ring atoms, each of which is substituted by one or more radicals R 2may be substituted, dibenzofuranyl or dibenzothiophenyl, each substituted with one or more radicals R 2 may be substituted or corresponds to one of the formulas (1-1), (1-2), (1-3) or (1-4), where An, Ar2, Ars, AR, a1, V, R# and [R#]a2 have a meaning mentioned above or mentioned below with preference. The radical R° is, identically or differently at each occurrence, particularly preferably F, CN, phenyl, 1,2-biphenyl, 1,3-biphenyl or 1,4-biphenyl, where phenyl, 1,2-biphenyl, 1,3-biphenyl or 1,4-biphenyl can be substituted with one or more radicals R 2 can be substituted.

[0043] Particularly preferred compounds of formula (1) are the compounds of formulas (1a), (1b) and (1c) in which Rx corresponds to a formula (1-1) or (1-2), where R°, a1 , (D) a , (D)b, (D)c, L, [R#]a2, R#, V, An, Ar2, Ars and An have a meaning mentioned above or preferred below.

[0044] Preferred compounds of formula (1) are further compounds of formula (1 d),

[0045] (1e), (1f) and (1g),

[0046] where R 0 , a1, (D) a , (D) b , (D) c , L, [R#] a2 , R#, V, Ar1, Ar2, Ar3 and Ar4 have a meaning mentioned above or mentioned below with preference. Particularly preferred compounds of formula (1) are the compounds of formulas (1d) and (1e), ie compounds of formula (1) in which Rx corresponds to a formula (1-1) or (1-2), where R 0 , a1, (D) a , (D) b , (D) c , L, [R#] a2 , R#, V, Ar1, Ar2, Ar3 and Ar4 have a meaning mentioned above or mentioned below as preferred. Particularly preferred compounds of formulas (1d) and (1e) are compounds of formulas (1h) to (1m),

[0047] ( ) where R 0, (D)a, (D)b, (D)c, L, [R#]a2, R#, V, Ar1, Ar2, Ar3 and Ar4 have a meaning mentioned above or mentioned with preference below. In one embodiment of the invention, the linker L in compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (1l) and (1m) represents a bond or an aromatic or heteroaromatic ring system of the formulas L-1 to L-34, which are substituted by one or more radicals R 1 can be substituted: where the dashed lines represent the connection to the rest of the formula

[0048] (1) or the remainder of formulas (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) or (1m);

[0049] Vi is O, S or Se and where R 1 has a meaning previously specified or subsequently specified.

[0050] In a preferred embodiment of the invention, L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (1l) and (1m) is a single bond.

[0051] 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), (1j), (1k), (11) and (1m) is a single bond or it is selected from the group of linkers L-1 to L-30, which are linked to one or more radicals R 1 may be substituted, where R 1 has a meaning given previously or below. In linkers L-18 to L-30, Vi is preferably O or S, particularly preferably O.

[0052] From the group of linkers L-1 to L-30, which are terminated with one or more residues R 1may be substituted, the following linkers are preferred: L-2, L-3, L-4, L-7, L-8, L-12, L-15, L-20, L-22, L-26, which are substituted with one or more residues R 1 may be substituted, where R 1 has a meaning previously specified or subsequently specified.

[0053] In a preferred embodiment of the invention, L in compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) is the linker L-15 which is substituted with one or more radicals R 1 may be substituted, where R 1 has a meaning previously specified or subsequently specified.

[0054] The substituent R 1 is, when identical or different, preferably selected from the group D, F, CN, Si(Ar)3 or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, where Ar has a meaning mentioned above. The substituent R 1is preferably D, phenyl or dibenzofuranyl. 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. The substituent R 1 is particularly preferred when occurring D.

[0055] The symbol V in formulas (1-1) to (1-4) or in compounds of formulas (1d) to (1m) as described above preferably represents O.

[0056] The invention accordingly further relates to compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f) or (1g), as described above with linkers L, as described above or preferably described, in which VO is.

[0057] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) or preferred compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) represent (D) a , (D)b and (D) c a monosubstitution, a disubstitution, a trisubstitution, the maximum permissible substitution or no substitution with deuterium.

[0058] If the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) are deuterated compounds, it is possible during their preparation, provided that the preparation is chosen by reacting a non-deuterated compound of one of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) with a deuteration source or provided that 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.

[0059] Such mixtures of deuterated compounds having the same basic chemical structure of formula (1) or the basic structure of the preferred embodiments, which differ only in the degree of deuteration and / or the deuteration patterns, are understood by the terms “compound of formula (1)” or “at least one compound of formula (1)” in the sense of the invention.

[0060] In a preferred embodiment of the invention, the compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) are deuterated, wherein the (average) degree of deuteration of the compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) is preferably at least 10 mol% to 100 mol%, particularly preferably 50 mol% to 95 mol% and very particularly preferably 70 mol% to 90 mol%. 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.

[0061] 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.

[0062] 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.

[0063] In one embodiment of the invention, (D) a , (D)b and (D) c for no substitution. In one embodiment of the invention, (D) a , (D)b and (D) c for maximum substitution.

[0064] In compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), R# is preferably at each occurrence independently of one another D, F, CN or a non-deuterated, a partially deuterated or a fully deuterated phenyl, particularly preferably D. If R# is D, then [R#] a2 preferably represents the maximum permissible substitution. If R# stands for F or CN, then [R#] a 2 preferably represents monosubstitution or disubstitution.

[0065] If R# represents a non-deuterated, a partially deuterated or a fully deuterated phenyl, then [R#] a 2 preferably represents monosubstitution. In one embodiment of the invention, [R#]a2 in compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) or in preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) does not represent substitution.

[0066] In one embodiment of the invention, [R#]a2 in compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) or in preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) does not represent a substitution or represents a monosubstitution, a disubstitution or the maximum permissible substitution with R#=D.

[0067] In compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), Ar, An, Ar2 and AM are, identically or differently, on each occurrence, preferably 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 mentioned with preference.

[0068] In compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (11), (1j), (1k), (11) and (1m) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), An, Ar2 and AM are, on each occurrence, identical or different, preferably an aromatic or heteroaromatic ring system having 5 to 40 ring atoms from the group Ar-1 to Ar-35,

[0069] where o

[0070] Y at each occurrence, identically or differently, represents O, S, NAr or C(R)2,

[0071] R is methyl or phenyl, o 9

[0072] R denotes H, R or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R; the dashed bond represents the bond to the radical of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (1l) and (1m); m is 0 or 1, where m=0 means that the group ar is not present and R and Ar have a previously mentioned or a preferred meaning. oo

[0073] Y is preferably O, S, NAr or C(CH3)2. Y is most preferably O.

[0074] Ar is preferably phenyl, 1,2-biphenyl, 1,3-biphenyl, 1,4-biphenyl, triphenylenyl, dibenzofuranyl or dibenzothiophenyl, which may be substituted by one or more radicals R, where R has a meaning mentioned above or mentioned with preference. Ar is particularly preferably phenyl, 1,2-biphenyl, 1,3-biphenyl or 1,4-biphenyl.

[0075] The substituent R, when identical or different, is preferably selected from the group D, F, CN or a straight-chain or branched alkyl group having 1 to 10 C atoms, where one or more H atoms of the alkyl group may be replaced by D, F, or CN. The substituent R, when occurring, is preferably D or F, especially

[0076] 9 preferably D. R in Ar is preferably D, F or CN, particularly preferably D. o

[0077] In the structures Ar-1 to Ar-35, 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-35 the o

[0078] 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.

[0079] In compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k),

[0080] In the compounds of formulas (1), (11) and (1m) or in the preferred compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), An, Ar2 and AM are, identically or differently, on each occurrence, preferably a group selected from Ar-1 to Ar-28 and Ar-33 to Ar-35, as described above, or particularly preferably a group selected from Ar-1 to Ar-4, Ar-12 to Ar-16, Ar-21 to Ar-27 and Ar-33 to Ar-35, as described above.

[0081] In one embodiment of the invention, it is preferred if Ar2 in the formula (1-1) or in compounds of the formulas (1d), (1h), (1i) and (1j) represents the group Ar-2, where o

[0082] R has a meaning previously specified or preferred.

[0083] In one embodiment of the invention, it is preferred if at least An or at least Ar2 in the formula (1-2) or in compounds of the formulas (1 e), (1k), (11) and o

[0084] (lm) represents the group Ar-2, where R has a meaning given above or preferably given. In one embodiment of the invention, it is preferred if AM in the formula (1-3), the formula (1-4) or in compounds of the formulas (1f) and (1g) represents the group Ar-1 or o

[0085] Ar-2, where R has a meaning given previously or preferably and a1 stands for 1.

[0086] In compounds of the formulas (1), (1a), (1b), (1c), (1f) and (1g) or preferred compounds of the formulas (1), (1a), (1b), (1c), (1f) and (1g), Ars preferably represents a group selected from Ar-1 to Ar-15, Ar-17 to Ar-28 and Ar-33 to Ar-35, as described above, with the proviso that Y represents O, S or C(R)2 or particularly preferably represents a group selected from Ar-1 to Ar-4, Ar-12 to Ar-15, Ar-21 to Ar-27 and Ar-33 to Ar-35, as described above with the proviso that Y represents O, S or C(R)2.

[0087] In one embodiment of the invention, it is preferred if Ars in formula (1-3), formula (1-4) or in compounds of formulas (1f) and (1g) represents the group Ar-2 o, where R has a meaning given above or given preferably.

[0088] Examples of suitable compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) are the structures listed below in Table 1.

[0089] Table 1 : P23-091 Sc

[0090] -22- ro

[0091] P23-091 Sc

[0092] -28-

[0093] 5

[0094] 15

[0095] 20

[0096] 25

[0097] 35

[0098] Particularly suitable compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) are the compounds E1 to E45 of Table 2.

[0099] Table 2:

[0100]

[0101] The compounds of the invention can be prepared by known synthetic steps, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc. 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 other substituents in the processes. The processes shown for the synthesis of the compounds of the invention are to be understood as examples. Alternative synthetic routes can be developed within the scope of general expert knowledge. Detailed reaction conditions are known from the state of the art or are described in the examples section.

[0102] By these processes, optionally followed by purification, such as recrystallization or sublimation, the compounds of formula (1) can be obtained in high purity, preferably more than 99% (determined by 1 H-NMR and / or HPLC).

[0103] For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention or mixtures of compounds of the invention with other 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-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 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 riethylenglycoldimethylether, Diethylenglycolmonobutylether, Tripropyleneglycoldimethylether, Tetraethylenglycoldi- methylether, 2-lsopropylnaphthalin, Pentylbenzol, Hexylbenzol, Heptylbenzol, Octylbenzol, 1 ,1-Bis(3,4-dimethylphenyl)ethan, 2-Methylbiphenyl, 3-Methylbiphenyl, 1- Methylnaphthalin, 1-Ethylnaphthalin, Ethyloctanoat, Sebacinsäure-diethylester, Octyloctanoat, Heptylbenzol, Menthyl-isovalerat, Cyclohexylhexanoat oder Mischungen dieser Lösemittel.,

[0104] A suitable formulation is a formulation comprising at least one compound according to the invention, as described above, or a mixture according to the invention, as described below, and at least one solvent. The solvent can be one of the solvents mentioned above or a mixture of these solvents.

[0105] The compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) according to the invention, as described above or preferably described, are suitable for use in an organic electroluminescent device, in particular as matrix material.

[0106] If the compound according to the invention is used as matrix material or synonymously host material in an emitting layer, it is preferably used in combination with another compound.

[0107] The invention therefore further provides a mixture comprising at least one compound of the formula (1) or at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), or a compound of Table 1 or one of the compounds E1 to E45 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). Suitable matrix materials and emitters which can be used in this mixture according to the invention are described below.

[0108] 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 formula (1) or at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), or a compound of Table 1 or one of the compounds E1 to E45.

[0109] 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.

[0110] Preferably, the organic electronic device is an organic electroluminescent device.

[0111] The organic electroluminescent device according to the invention (synonymously referred to as 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.

[0112] 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.

[0113] 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.

[0114] The device may also contain inorganic materials or layers made entirely of inorganic materials.

[0115] A large number of materials known in the art are suitable for use in the layers of the organic electroluminescent device described above. When making the selection, common considerations regarding the chemical and physical properties of the materials must be taken into account, since the materials in an organic electroluminescent device are interrelated. This applies, for example, to the energy positions of the orbitals (HOMO, LUMO) or the position of triplet and singlet energies, but also other material properties. The compound of the formula (1) according to the invention, as described above or preferably described, can be used in different layers, depending on the precise structure. Preference is given to an organic electroluminescent device comprising a compound according to formula (1) orThe preferred embodiments described above in an emitting layer as a matrix material for fluorescent emitters, phosphorescent emitters, or for emitters exhibiting TADF (thermally activated delayed fluorescence), in particular for phosphorescent emitters. Furthermore, the compound according to the invention can also be used in an electron-transport layer and / or in a hole-transport layer and / or in an exciton-blocking layer and / or in a hole-blocking layer. The compound according to the invention is particularly preferably used as a matrix material in an emitting layer or as an electron-transport or hole-blocking material in an electron-transport or hole-blocking layer.

[0116] 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 formula (1) or at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), or a compound of Table 1 or one of the compounds E1 to E45.

[0117] 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 formula (1), as described above or preferably described, or with the compounds of Table 1 or the compounds E1 to E45.

[0118] A further subject matter of the present invention is accordingly 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 formula (1) or the at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), or a compound of Table 1 or one of the compounds E1 to E45 and at least one further matrix material.

[0119] A further subject matter of the present invention is accordingly 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 formula (1) or the at least one preferred compound of one of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), or a compound of Table 1 or one of the compounds E1 to E45 and two further matrix materials.

[0120] 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 does not participate to a significant extent, in charge transport, such as a wide-band-gap compound.

[0121] 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.

[0122] Particularly suitable hole-transporting matrix materials which are advantageously combined with compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), as previously described or preferably described, in a mixed matrix system, can be selected from the compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), as described below.

[0123] A further subject 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 formula (1) as matrix material 1, as described above or described as preferred, and at least one compound of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) as matrix material 2, Formula (HH-6), where the symbols and indices used are:

[0124] A 1 is C(R 7 )2, NR 7 , O or S;

[0125] L is a bond, O, S, C(R 7 )2 or NR 7 ;

[0126] A is, at each occurrence, independently a group of the formula (HH-4-

[0127] 1) or (HH-4-2),

[0128] Formula (HH-4-1) Formula (HH-4-2);

[0129] X2 is the same or different at each occurrence CH, CR 6 or N, where a maximum of 2 symbols X2 can mean N;

[0130] * indicates the binding site to the formula (HH-4); U 1 , U 2 are a bond, O, S, C(R 7 )2or NR 7 ;

[0131] 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;

[0132] 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 may 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 CFh groups being substituted by Si(R 8 )2, C=O, NR 8 , O, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 may be substituted, where R 8 does not denote H; 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;

[0133] 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 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 d+d1+d2 = 1; q, q1, q2 each independently denote 0, 1, 2, 3 or 4; 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, 1, 2, or 3.

[0134] Preferred compounds of formula (HH-5) are compounds of formulas (HH-5-A) to (HH-5-E),

[0135] where Ars, R 6 , s and u have a previously specified or preferred meaning.

[0136] In compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) or (HH-6), s is preferably 0 or 1 when the radical R 6 is different from D, or more preferably 0.

[0137] In compounds of the formulas (HH-1), (HH-2) or (HH-3), t is preferably 0 or 1 when the radical R 6 is different from D, or more preferably 0.

[0138] In compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D) or (HH-5-E), u is preferably 0 or 1 when the radical R 6is different from D, or particularly preferably 0. The sum of the indices s, t and u in compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) or (HH-6) 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.

[0139] In compounds of formula (HH-4), 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.

[0140] In compounds of formula (HH-4), L is preferably a single bond or C(R 7 )2, where R 7 has a meaning mentioned above, particularly preferably L is a single bond.

[0141] In formula (HH-4-1) v is preferably 0 or 1 when the radical R 6 is different from D.

[0142] In formula (HH-4-2), 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.

[0143] In formula (HH-4-2), q, q1 , q2 are preferably 0 or 1 when the radical R 6 is different from D.

[0144] In a preferred embodiment of the compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) or (HH-6), which can be combined according to the invention with compounds of formula (1) or preferred compounds of formula (1), as described above, R 6identically 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 7 can be substituted.

[0145] In a preferred embodiment of the compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) or (HH-6), which can be combined according to the invention with compounds of formula (1) or preferred compounds of formula (1), as described above, R 6identically 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.

[0146] Preferably, Ars in compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) or (HH-6) 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 radicals derived from indole, benzofuran, benzothiophene, carbazole, which may be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which can be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, 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, each of which is substituted with one or more radicals R, 7 may be substituted. Preferably, Ars is unsubstituted.

[0147] If A 1 in formula (HH-2) or (HH-3) or (HH-6) 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 ring atoms, which may also be substituted by one or more radicals R 8 In a particularly preferred embodiment, this substituent R 7 identically or differently on each occurrence represents an aromatic or heteroaromatic ring system having 6 to 24 ring atoms, in particular having 6 to 18 ring atoms. Preferred embodiments for R 7are 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 R 8 may be substituted, where R 8 does not mean H.

[0148] If A 1 in formula (HH-2) or (HH-3) or (HH-6) 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 ring atoms, which can also be substituted by one or more radicals R 8 may be substituted, where R 8 does not represent H. Most preferably, R 7 represents a methyl group or a phenyl group. The radicals R 7also form a ring system with each other, which leads to a spiro system.

[0149] In a preferred embodiment of the compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E), and (HH-6), these compounds are partially or fully deuterated, particularly preferably fully deuterated. The preparation of the compounds of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E), and (HH-6) is generally known, and some of the compounds are commercially available.

[0150] Compounds of formula (HH-4) 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 A1 on page 128 and in the synthesis examples on pages 214 to 218.

[0151] The preparation of the triarylamines of formula (HH-6) is known to the person skilled in the art and some of the compounds are commercially available.

[0152] If the at least one further matrix material is a deuterated compound, it is possible that this at least one matrix material is a mixture of deuterated compounds with the same basic chemical structure, differing only in the degree of deuteration and / or the deuteration pattern. The statements regarding deuterated mixtures and the preparation of deuterated materials, as previously described for compounds of formula (1), apply here accordingly.

[0153] In a preferred embodiment of the at least one further matrix material, this is a mixture of deuterated compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) or (HH-6), as described above, wherein the average degree of deuteration of these compounds is at least 50 mol% to 90 mol%, preferably 70 mol% to 100 mol%.

[0154] Examples of suitable further matrix materials for a combination with compounds of formula (1), as previously described or preferably described, are the compounds described in WO2019 / 229011 A1, Table 3, pages 137 to 203, which may also be partially or completely deuterated.

[0155] Examples of suitable further matrix materials for combination with compounds of formula (1) or preferred compounds of formula (1) as previously described or preferably described are the compounds described in WO2021 / 180625 A1, Table 3, pages 131 to 137 and in Table 4, pages 137 to 139, which may also be partially or completely deuterated.

[0156] Examples of suitable further matrix materials for combination with compounds of formula (1) or preferred compounds of formula (1) as previously described or preferably described are the compounds described in KR20230034896 A, on pages 42 to 47, compounds [2-1] to [2-110], or on pages 49 to 51, compounds [3-1] to [3-26],

[0157] Examples of suitable further matrix materials for combination with compounds of formula (1) or preferred compounds of formula (1), as previously described or preferably described, are the compounds described in KR20230154750 A, on pages 39 to 49, compounds [B-1] to [B-243], or on pages 49 to 53, compounds [C-1] to [C-102] or on pages 54 to 57, compounds [D-1] to [D-120],

[0158] For a combination with compounds of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), as described above or preferably described, compounds of the formula (HH-1) and / or the formula (HH-4) and / or the formula (HH-5) are particularly suitable, as described above or preferably described.

[0159] For a combination with compounds of the formulas ((1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), as described above or preferably described, compounds of the formula (HH-1) are particularly suitable in which at least one group Ars denotes 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 (HH-4) and / or compounds of formula (HH-5).

[0160] In the subgroup of compounds of formula (HH-5), selected from compounds of formulas (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E), compounds of formulas (HH-5A, (HH-5-B) and (HH-5-D) are preferred, with compounds of formula (HH-5-A) being particularly preferred.

[0161] For a combination with a compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), as previously described or preferably described, compounds of the formula (HH-4) or (HH-5) or (HH-5-A) are very particularly suitable.]

[0162] Further examples of suitable host materials of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) and (HH-6) for combination with compounds of the formula (1) or preferred compounds of the formula (1), as previously described or preferably described, are the structures of Table 3 and Table 4 mentioned below. P23-091 Sc P23-091 Sc

[0163] 5

[0164] 15

[0165] 20

[0166] 25

[0167] 35 P23-091 Sc

[0168] - 65 -

[0169] Particularly suitable compounds of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) or (HH-6), which are selected according to the invention and preferably used in combination with at least one compound of the formula (1) in the electroluminescent device according to the invention

[0170] 5 are the compounds in Table 4.

[0171] Table 4:

[0172] 15

[0173] 20

[0174] 25

[0175] 35 P23-091 Sc P23-091 Sc

[0176]

[0177] The above-mentioned host materials of formula (1) and their preferred embodiments or the compounds of Table 1 and the compounds E1 to E45 can be combined as desired in the device according to the invention with the above-mentioned matrix materials / host materials, the matrix materials / host materials of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) or (HH-6) and their preferred embodiments of Table 3 or the compounds H1 to H33.

[0178] Very particularly preferred mixtures of the compounds of formula (1) with the host materials of formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) or (HH-6) for the device according to the invention are obtained by combining the compounds E1 to E45 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. Table 5:

[0179] The concentration of the host material of formula (1), as described above or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 5 wt.% to 90 wt.%, preferably in the range from 10 wt.% to 85 wt.%, more preferably in the range from 20 wt.% to 85 wt.%, even more preferably in the range from 30 wt.% to 80 wt.%, very particularly preferably in the range from 20 wt.% to 60 wt.% and most preferably in the range from 30 wt.% to 50 wt.%, based on the total mixture or based on the total composition of the light-emitting layer.

[0180] The concentration of the sum of all host materials of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) and (HH-6), 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 entire mixture or based on the entire composition of the light-emitting layer.

[0181] The present invention also relates to a mixture which, in addition to the above-mentioned host materials of the formula (1), hereinafter referred to as host material 1, and the host material of at least one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) and (HH-6), hereinafter referred to as host material 2, as described above or preferably described, contains at least one phosphorescent emitter.

[0182] The present invention also relates to a mixture selected from M1 to M1485, which contains at least one phosphorescent emitter.

[0183] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the light-emitting layer contains at least one phosphorescent emitter in addition to the above-mentioned host materials of the formula (1) and at least one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) and (HH-6), as described above or preferably described, in particular the material combinations M1 to M1485.

[0184] 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.

[0185] 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.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.

[0186] Preferred phosphorescent emitters according to the present invention correspond to the formula (IIIa), 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 ,

[0187] X is the same or different at each occurrence, N or CR,

[0188] 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.

[0189] 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.

[0190] In emitters of formula (IIIa), n is preferably 1 and m is preferably 2.

[0191] 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). Preferred phosphorescent emitters according to the present invention correspond to formulas (I), (II), (III), (IV) or (V),

[0192] where the symbols and indices for these formulas (I), (II), (III), (IV) and (V) have the meaning:

[0193] 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.

[0194] Preferred phosphorescent emitters according to the present invention correspond to the formulas (VI), (VII) or (VIII),

[0195] R

[0196] where the symbols and indices for these formulas (VI), (VII) and (VIII) have the meaning:

[0197] 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

[0198] Alkyl group with 1 to 10 C atoms or a cycloalkyl group with 4 to 10 C atoms, which may be partially or fully substituted with deuterium.

[0199] 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.

[0200] Particularly preferred examples of phosphorescent emitters are listed in Table 6 below.

[0201] Table 6:

[0202]

[0203] 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 M1485 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.

[0204] 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.

[0205] A yellow-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 540 to 570 nm. An orange-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 570 to 600 nm. A red-emitting layer is defined as a layer whose photoluminescence maximum lies in the range from 600 to 750 nm.

[0206] A green-emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 490 to 540 nm. A blue-emitting layer is defined as a layer whose photoluminescence maximum lies in the range of 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), (1j), (1k), (11) or (1m) and the host material 2, consisting of at least one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) and (HH-6), and the corresponding emitter.

[0207] The photoluminescence spectrum of the layer is recorded, for example, using a commercially available photoluminescence spectrometer. The photoluminescence spectrum of the selected emitter is usually measured in an 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). Preferred phosphorescent emitters are therefore yellow emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 6, whose triplet energy T1 is preferably at ~2.3 eV to ~2.1 eV Preferred phosphorescent emitters are accordingly green emitters, preferably of the formula (IIIa), of the formulas (I) to (VIII) or from Table 6, whose triplet energy T1 is preferably between ~2.5 eV and ~2.3 eV. Particularly preferred phosphorescent emitters are accordingly green emitters, preferably of the formula (IIIa), of the formulas (I) to (VIII) or from Table 6, as described above, whose triplet energy T1 is preferably between ~2.5 eV and ~2.3 eV. Very particular preference is given to selecting green emitters, preferably of the formula (IIIa), of the formulas (I) to (VIII) or from Table 6, as described above, for the mixture according to the invention or emitting layer according to the invention. 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, where preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, particularly preferably having at least 14 ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to be a compound in which 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. Pyrene-arylamines are also preferred. Also preferred are benzoindenofluorene amines, benzofluorene amines, 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).

[0208] In a further preferred embodiment of the invention, the at least one light-emitting layer of the organic electroluminescent device can have three or four different matrix materials, preferably three different matrix materials. These corresponding mixed-matrix systems can consist of the matrix materials described for host material 1 and host material 2, but they can also contain, as a third or fourth matrix material, for example, in addition to a host material 1 or host material 2, w / de-öand-gap materials, bipolar host materials, electron-transport materials (ETM), or hole-transport materials (HTM). The mixed-matrix system is preferably optimized for an emitter of formula (IIIa), formulas (I) to (VIII), or an emitter of Table 6.

[0209] According to one embodiment of the present invention, the mixture contains no further components, i.e., functional materials, apart from the components of host material 1 and host material 2, as previously described or preferably described. These are material mixtures that are used as such to produce the light-emitting layer. These mixtures are also referred to as premix systems, which are used as the sole material source during the vapor deposition of the host materials for the light-emitting layer and which have a constant mixing ratio during vapor deposition. This allows for the simple and rapid vapor deposition of a layer with a uniform distribution of the components, without the need for precise control of a large number of material sources.

[0210] According to an alternative embodiment of the present invention, the mixture contains, in addition to the components of the host material of formula (1) and the host material 2, as described above or preferably described, a phosphorescent emitter as described above. With a suitable mixing ratio during vapor deposition, this mixture can also be used as the sole material source.

[0211] Preferred are premix systems consisting of two matrix materials, namely a compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) or (1m) and a compound of one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) or (HH-6).

[0212] 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), (1j), (1k), (11) or (1m) and two compounds of one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) or (HH-6).

[0213] The components or constituents of the light-emitting layer of the device according to the invention can thus 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, is provided for this purpose in a formulation containing at least one solvent. Suitable formulations have been described previously.

[0214] 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.%, further preferably between 99 and 10 vol.%, particularly preferably between 98 and 60 vol.%, very particularly preferably between 97 and 80 vol.% of matrix material made of at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) or (1m) and at least one compound of one of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5), (HH-5-A), (HH-5-B), (HH-5-C), (HH-5-D), (HH-5-E) or (HH-6) according to the preferred embodiments, based on the total composition of emitter and matrix material. Accordingly, the light-emitting layer in the device according to the invention preferably contains between 0.1 and 99 vol.%, more preferably between 1 and 90 vol.%, particularly preferably between 2 and 40 vol.-%, very particularly preferably between 3 and 20 vol.% of the emitter, based on the total composition of the light-emitting layer consisting of emitter and matrix material. If the compounds are processed from solution, the corresponding amounts in wt.% are preferably used instead of the above-specified amounts in vol.%.

[0215] 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.

[0216] The sequence of layers in the organic electroluminescent device according to the invention is preferably as follows:

[0217] Anode / hole injection layer / hole transport layer / emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0218] This sequence of layers is a preferred sequence.

[0219] It should be noted again that not all of the layers mentioned need to be present and / or that additional layers may be present.

[0220] 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 Alqs, 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.

[0221] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the organic layer contains an electron injection layer (EIL) and / or an electron transport layer (ETL) and / or a hole blocking layer, whose electron injecting material and electron transporting material are selected from the compounds of formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (1l) or (1m), as described above or preferably described.

[0222] 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, 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, U2O, 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.

[0223] Materials with a high work function are preferred as the anode. 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 / NiOx, Al / PtOx) may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent 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. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. 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 of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0224] 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.

[0225] The manufacture of the device according to the invention is not restricted in this respect. It is possible for one or more organic layers, including the light-emitting layer, to be coated using a sublimation process. The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10'5 mbar, preferably less than 10'6 mbar. However, it is also possible for the initial pressure to be even lower, for example, less than 10'7 mbar.

[0226] 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).

[0227] 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.

[0228] Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are vapor-deposited.

[0229] These methods are generally known to the person skilled in the art and can be applied to organic electroluminescent devices.

[0230] A further subject of the invention is therefore 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 hole injection layer and / or hole transport 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.

[0231] 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.

[0232] The following procedures are possible:

[0233] 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.

[0234] A method for producing the organic electroluminescent device according to the invention, as described above or preferably described, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (1l) or (1m) together with the further materials which form the light-emitting layer are deposited successively or simultaneously from at least two material sources from the gas phase.

[0235] 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), (1j), (1k), (11) or (1m) is deposited from the vapor phase together with at least one further matrix material as a premix, sequentially 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).

[0236] 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:

[0237] 1. Electronic devices, in particular organic

[0238] Electroluminescent devices containing compounds according to formula (1) or the preferred embodiments described above and below, particularly as matrix material or as electron-conducting materials, exhibit a very long lifetime. These compounds, in particular, result in low roll-off, i.e., a low drop in the device's power efficiency at high luminance levels.

[0239] 2. Electronic devices, in particular organic electroluminescent devices containing compounds of formula (1) or the preferred embodiments described above and below as electron-conducting materials and / or matrix materials, exhibit excellent efficiency. Compounds of the invention according to formula (1) or the preferred embodiments described above and below result in a low operating voltage when used in electronic devices.

[0240] 3. The compounds according to the invention according to formula (1) or the preferred embodiments described above and below show a very high stability and lifetime.

[0241] 4. Using compounds according to formula (1) 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.

[0242] 5. The use of compounds according to formula (1) or the preferred embodiments described above and below in layers of electronic devices, in particular organic electroluminescent devices, leads to a high mobility of the electron conductor structures.

[0243] 6. Compounds according to formula (1) or the preferred embodiments described above and below have excellent glass film formation.

[0244] 7. Compounds according to formula (1) and the preferred embodiments described above and below form very good films from solutions. 8. The compounds according to formula (1) and the preferred embodiments described above and below have a deep triplet Ti level, which can be in the range of 2.50 eV - 2.90 eV.

[0245] These advantages mentioned above are not accompanied by an excessive deterioration of the other electronic properties.

[0246] 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.

[0247] All features of the present invention may be combined with each other in any way, unless certain features and / or steps are mutually exclusive. This applies in particular to preferred features of the present invention. Likewise, features of non-essential combinations may be used separately (and not in combination).

[0248] The teaching of technical action disclosed in the present invention can be abstracted and combined with other examples.

[0249] The invention is explained in more detail by the following examples, without intending to limit it thereby.

[0250] Examples

[0251] General methods:

[0252] The Gaussian16 program package (Rev. B.01) is used for all quantum chemical calculations. The neutral singlet ground state is optimized at the B3LYP / 6-31G(d) level. HOMO and LUMO values ​​are determined at the B3LYP / 6-31G(d) level for the ground-state energy optimized with B3LYP / 6-31G(d). TD-DFT singlet and triplet excitations (vertical excitations) are then calculated using the same method (B3LYP / 6-31G(d)) and the optimized ground-state geometry. The default settings for SCF and gradient convergence are used.

[0253] From the energy calculation, the HOMO is determined as the last orbital occupied by two electrons (alpha occupancy eigenvalues) and the LUMO 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:

[0254] HOMOcorr = 0.90603 * HOMO - 0.84836

[0255] LUMOcorr = 0.99687 * LUMO - 0.72445

[0256] 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.

[0257] 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.

[0258] The lowest energy singlet state is called SO.

[0259] 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.

[0260] Synthesis examples

[0261] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The compounds of the invention can be prepared using synthesis methods known to those skilled in the art.

[0262] To a solution of 99 g (489 mmol) of 2-bromo-6-hydroxy-benzonitrile and 99.5 g (489 mmol) of bromoacetophenone in 790 ml of acetone, 319 g (979 mmol) of cesium carbonate are added portionwise under argon at room temperature.

[0263] The reaction mixture is heated to 60°C for 2 hours. The mixture is then cooled to room temperature, filtered, and then concentrated to dryness under reduced pressure and recrystallized from heptane.

[0264] The yield is 107 g (316 mmol), corresponding to 69% of theory. The following brominated compounds are prepared analogously: a) 6-Bromo-2-cyanophenyl benzoate

[0265] [73289-85-7]

[0266] A solution of 10 g (50 mmol) of 2-bromo-6-hydroxybenzonitrile, 10.4 ml (75 mmol) of triethylamine, and 61 mg (0.5 mmol) of 4-N,N-dimethylaminopyridine in 200 ml of CH2Cl2 is initially charged, cooled to 0°C, and then 10.5 g (75 mmol) of benzoyl chloride is added. The mixture is stirred at room temperature for 3 h. The reaction mixture is poured into 20 ml of sodium chloride solution and extracted three times with Et2O. The combined organic phase is dried over MgSO4. The organic solvent

[0267] 15 is removed under reduced pressure and the residue is subjected to flash column chromatography on silica gel (hexane / AcOEt = 20 / 1-7 / 1).

[0268] Yield: 10.4 g (33 mmol), 70% of theory. b) S-(2-cyano-3-bromophenyl)-benzenecarbothionate

[0269] 20

[0270] [1245648-93-4]

[0271] In a baked-out flask under argon, 8 g (25 mmol) of 2-bromo-6-iodobenzonitrile, 0.47 g (10 mol%, 2.5 mmol) of Cul, 0.9 g (20 mol%, 5 mmol) of 1,10-phenanthroline, and 5.1 g (37.5 mmol) of thiobenzoic acid were added to 20 ml of degassed toluene under nitrogen and stirred at 100 °C for 24 h. The reaction mixture was cooled to room temperature. Diethyl ether (1000 ml) and saturated sodium chloride solution (1000 ml) were added, and the mixture was stirred. The organic phase was separated, and the aqueous phase was extracted with diethyl ether (2 x 1000 ml). The combined organic phases were dried over NaSO4, and the product was isolated by column chromatography.

[0272] 35

[0273] Yield: 5.3 g (16.2 mmol), 65% of theory c) 2-Amino-4-Bromo-3-benzofuranyl)phenylmethanone

[0274] In a heated flask under argon, 0.67 g (30 mmol) of Pd(OAc)2, 1.69 g (6 mmol) of PCya (tricyclohexylphosphine), 1.96 g (30 mmol) of zinc powder, and 3 g of 4 Ä molecular sieve (MS4A) are placed in 1200 ml of DMF. After stirring for 20 min at room temperature, 9.4 g (30 mmol) of bromo-2-cyanophenyl benzoate are added, and the mixture is stirred overnight at 100°C. Saturated NaCl solution is then added to the mixture, and the aqueous phase is extracted with Et2O (100 ml x 3). The combined organic phases are dried over MgSO4 and filtered. The organic solvent is removed in vacuo, and the residue is

[0275] 15 by flash column chromatography on silica gel (hexane / AcOEt = 7 / 1 - 2 / 1). Yield: 6.2 g (20 mmol), 67% of theory.

[0276] Analogously, the following brominated compounds are prepared:

[0277] 20

[0278] 25 d) 9-Bromo-2,4-diphenylbenzofuro[3,2-cf]pyrimidine Under argon, 107 g (316 mmol) of (3-amino-4-chloro-2-benzofuranyl)phenylmethanone and 104 g (1015 mmol) of benzonitrile are placed in 1000 ml of o-xylene, and 56 g (677 mmol) of sodium 2-methylpropan-2-olate are added. The mixture is stirred for 5 hours at 140°C. 30 ml of water is drained off via a water separator and then

[0279] 5, a little acetone is added and the mixture is stirred for another hour. After cooling, the mixture is quenched with one liter of water. The organic phase is separated, washed three times with 300 ml of water, dried over MgSO4, filtered, and the solvent is removed in vacuo. The residue is purified by column chromatography.

[0280] The yield is 64 g (160 mmol), corresponding to 48% of theory.

[0281] 15

[0282] 20

[0283] 25

[0284] 35 5

[0285] 15

[0286] 20

[0287] 25

[0288] 35 5

[0289] 15

[0290] 20

[0291] 25

[0292] 35 5

[0293] 15

[0294] 20

[0295] 25 e) 2-Chloro-4,8-diphenyl-benzofuro[3,2-d]pyrimidine

[0296] [2201128-35-8] 31.4 g (100 mmol) of 2,4-Dichloro-8-phenyl-benzofuro[3,2-d]pyrimidine, 12.2 g (100 mmol) of phenylboronic acid, and 11.8 g (111 mmol) of sodium carbonate are dissolved in 800 ml of 1,4-dioxane, 800 ml of water, and 250 ml of toluene, and stirred under argon. 1.2 g (1 mmol) of tetrakis(triphenylphosphine)palladium is added to the flask.

[0297] 5 The reaction mixture is stirred under reflux overnight. After cooling, the mixture is quenched. The organic phase is separated, washed three times with 300 ml of water, dried over MgSO 2 , filtered, and the solvent is removed in vacuo. The residue is purified by column chromatography on silica gel (eluent: DOM / heptane (1:10). The yield is 28 g (80 mmol), corresponding to 80% of theory.

[0298] Analogously, the following connections are made:

[0299] 15

[0300] 20

[0301] 25

[0302] 35 5

[0303] 15

[0304] 20

[0305] 25

[0306] 35 5

[0307] 15

[0308] 20

[0309] 25

[0310] 35 5

[0311] 15

[0312] 20

[0313] 25

[0314] 35 f) 2-Phenyl-4H-naphtho[1,2,3,4-def]carbazole l- 4H-naphtho[1,2,3,4-def]carbazole and 44.5 g (420 mmol, 2.00 eq.) of sodium carbonate [CAS 497-19-8] were suspended in a mixture of 1000 mL of dioxane [CAS 123-91-1], 1000 mL of toluene [CAS 108-88-3], and 400 mL of water. 4.85 g (4.20 mmol; 0.02 eq.) of tetrakis(triphenylphosphine)palladium(0) [CAS 14221-01-3] were added to this suspension, and the reaction mixture was heated under reflux for 16 h. After cooling, the mixture was stirred for 10 minutes.

[0315] 15, the organic phase is separated, filtered through silica gel, washed three times with 200 mL of water, and then evaporated to dryness. The yield is 38 g (121 mmol; 79% of theory).

[0316] The following compounds can be obtained analogously:

[0317] 20

[0318] 25

[0319] 35 , g ( mmol ) - ap o[ , , , - e ]car azo , g ( mmol) 1-bromo-3-iodobenzene, 22.4 g (162 mmol) potassium carbonate, 1.84 g (8.1 mmol) 1 ,3-di(2-pyridyl)-1,3-propanedione, 1.55 g (8.1 mmol) copper iodide and 1000 mL DMF are heated under reflux for 30 h. The mixture is then concentrated on a rotary evaporator until dry. The residue is dissolved in THF and filtered through a short bed of silica gel. The

[0320] 15 Solvent is removed under vacuum. The solid is then recrystallized from heptane / THF and then extracted hot over aluminum oxide with heptane / toluene. The solid that precipitates upon cooling is filtered and dried.

[0321] Yield: 28 g (71 mmol), 88%.

[0322] 20 The following connections can be made analogously:

[0323] 25

[0324] 35 5

[0325] 15

[0326] 20

[0327] 25

[0328] 35 5

[0329] 15

[0330] 20

[0331] 25 h) 4H-Naphtho[1,2,3,4-otef]carbazole-3-phenylboronic acid

[0332] 35

[0333] A solution of 51.3 g (130 mmol) of 4-(3-bromophenyl)-4 / 7-naphtho[1,2,3,4-ctef]carbazole in 1500 ml of THF, cooled to -78 °C, is added dropwise with 55 ml (138 mmol) of n-butyllithium (2.5 M in hexane). The reaction mixture is stirred for 30 min at -78 °C. It is allowed to warm to room temperature, cooled again to -78 °C, and then quickly treated with a mixture of 20 ml (176 mmol) of trimethyl borate in 50 ml of THF. After warming to -10 °C, the mixture is hydrolyzed with 135 ml of 2 N hydrochloric acid. The organic phase is separated, washed with water, dried over sodium sulfate, and evaporated to dryness. The residue is taken up in 300 ml of n-heptane, and the colorless solid is obtained.

[0334] 5 is filtered off with suction, washed with n-heptane, and dried in vacuo. Yield: 45 g (126 mmol), 97% of theory; Purity: 99% by HPLC.

[0335] The following connections can be made analogously:

[0336] 15

[0337] 20

[0338] 25

[0339] 35 5

[0340] 15

[0341] 20 i) 4-(2,4-Diphenylbenzofuro[3,2-cf]pyrimidin-8-yl)4H-naphtho[1,2,3,4-c / ef]carbazole

[0342] Route A for bromides:

[0343] [109606-75-9] E1

[0344] 17 g (43 mmol; 1.00 eq.) 8-bromo-2,4-diphenylbenzofuro[3,2-c(]pyrimidine, 9.7 g (40.7 mmol; 1.10 eq.) 4H-naphtho[1,2,3,4-c / ef|carbazole and 7.82 g (81.4 mmol; 2.00 eq.) eq.) Sodium terf-butylate [CAS 865-47-4] are dissolved in 500 mL orf / 70-xylene [CAS 95-47-6]

[0345] 35. 1.50 g (3.66 mmol; 9 mol%) of dicyclohexyl-(2',6'-dimethoxy-biphenyl-2-yl)-phosphine (SPhos) [CAS 657408-07-6] and 1.12 g (1.22 mmol, 3 mol%) of tris(dibenzylideneacetone)dipalladium [CAS 51364-51-3] were added to this suspension, and the reaction mixture was heated under reflux for 16 h. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The resulting solid was washed with 300 mL of ethanol and recrystallized several times from a mixture of heptane and xylene. After hot filtration through Alox and final sublimation under high vacuum, the purified product was obtained as a colorless solid (16 g; 28 mmol; 70%).

[0346] 5

[0347] Route B for chlorides:

[0348] [109606-75-9]

[0349] Under nitrogen, 16.0 g (66.0 mmol) of 4 / 7-naphtho[1,2,3,4-def]carbazole are mixed with 60 ml

[0350] 15 g of xylene and 6 ml of THF are added and the mixture is cooled to 5°C. A THF solution of MeMgCl (3.22 mol / l, 20.0 ml, 64.4 mmol) and 18 ml of THF is slowly added dropwise to the carbazole solution in a dropping funnel over a period of 10 min, so that the temperature does not exceed 25°C. A solution of 25 g (63.0 mmol) of 8-bromo-2,4-diphenylbenzofuro[3,2-c(]pyrimidine) and 14 ml of Pd-cBRIDP catalyst solution is then added to this solution.

[0351] 20 (prepared from PdCl(allyl)]2 (5.8 mg, 0.025 mol%) and cBRIDP (22.2 mg, 0.1 mol%) in 3 mL of THF and 11 mL of xylene) was added. The mixture was heated to reflux under nitrogen for 3 hours, then the reaction mixture was allowed to cool to room temperature. 25 mL of water and 1.7 g of NH4Cl (31.8 mmol) were added and the mixture was stirred at room temperature for 5 min. The organic phase was separated, and the solution

[0352] 25 and purified by chromatography (n-hexane, toluene 3 / 1). After three hot extractions over Alox and subsequent sublimation under high vacuum, the purified product is obtained as a colorless solid (22.7 g, 40 mmol; 65%).

[0353] Analogously, the following compounds can be obtained either via route A or route B. Other common solvents and purification methods can also be used for workup and purification.

[0354] 35 5

[0355] 15

[0356] 20

[0357] 25

[0358] 35 5

[0359] 15

[0360] 20

[0361] 25

[0362] 35 5

[0363] 15

[0364] 20

[0365] 25

[0366] 35 5

[0367] 15

[0368] 20

[0369] 25

[0370] 35 5

[0371] 15

[0372] 20

[0373] 25

[0374] 35 5

[0375] 15

[0376] 20

[0377] 25

[0378] 35

[0379] 76.1 g (211 mmol; 1.00 eq.) of 3-(4 / 7-naphtho[1,2,3,4-def|carbazole-4-yl)-phenylboronic acid, 101 g (253 mmol; 1.20 eq.) of 9-bromo-2,4-diphenylbenzofuro[3,2-c(]pyrimidine), and 44.5 g (420 mmol, 2.00 eq.) of sodium carbonate were suspended in a mixture of 1000 mL of dioxane, 1000 mL of toluene, and 400 mL of water. 4.85 g (4.20 mmol; 0.02 eq.) 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 yield is 93 g (147 mmol; 70% of theory).

[0380] The following compounds can be obtained analogously:

[0381]

[0382] 26.3 g (47.0 mmol; 1.00 eq) of 4-(2,4-diphenylbenzofuro[3,2-d]pyrimidin-8-yl)4 / 7-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. 16.1 g (27 mmol, 59% of theory) of the product shown above, in a mixture with portions of H / D isotopomers and H / D isotopologues, are obtained after chromatographic purification and finally concentrated under high vacuum (p = 5 x 10' 7 mbar) (purity 99.9%). The following products are obtained analogously:

[0383] I) 2-(3-Fluorotriphenylen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

[0384] 40 g (123 mmol) of 2-bromo-3-fluorotriphenylene, 60 g (236 mmol) of bis(pinacolato)diboron and 35 g of 1,4-dioxane are placed in 800 ml of 1,4-dioxane and inertized with argon for 30 min.

[0385] Subsequently, 3.5% (3.8 mmol) of tris(dibenzylideneacetone)dipalladium (97%) and 4% (14 mmol) of tricyclohexylphosphine are added, and the mixture is stirred under reflux for 24 h. After cooling, the solvent is removed on a rotary evaporator, and the residue is extracted with dichloromethane and water. The combined organic phases are dried over NaSO4, ethanol (150 ml) is added, and the dichloromethane is removed on a rotary evaporator. The precipitated solid is filtered off with suction and dried in a vacuum drying oven. The crude product is used in the next step without further purification.

[0386] Yield: 30.7g (82 mmol, 67%), purity 94% according to 1 H-NMR.

[0387] 63 g (156 mmol) of 8-bromo-2,4-diphenylbenzofuro[3,2-d]pyrimidine, 50 g (170 mmol) of 2-(3-fluorotriphenylen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 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(O) 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, 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) (purity 99.9%). The yield is 68 g (120 mmol), corresponding to 71% of theory.

[0388] Analogously, the following connections are made: n) 8-(3-(4H-Naphtho[1,2,3,4-def]carbazol-4-yl)triphenylen-2-yl)-2,4-diphenylbenzofuro[3,2-d]pyrimidine

[0389] E37

[0390] Under argon, 54 g (96 mmol) of 8-(3-fluorotriphenylen-2-yl)-2,4-diphenylbenzofuro[3,2-d]pyrimidine, 30 g (179 mmol) of carbazole, and 54 g (166 mmol) of cesium carbonate were suspended in 1500 mL of N,N-dimethylformamide, and the reaction mixture was heated under reflux at 150°C for 40 h. The reaction mixture was cooled to room temperature and 1500 mL of water was added. The precipitated solid was filtered off, washed with 300 mL of ethanol, and recrystallized several times from xylene. After hot filtration through Alox and final sublimation under high vacuum, the purified product was obtained as a colorless solid (58 g, 81 mmol; 85%).

[0391] Analogously, the following connections are made: o) 8-(3-(4H-Naphtho[1,2,3,4-def]carbazol-4-yl-d10)triphenylen-2-yl-

[0392] 1,4,5,6,7,8,9,10,11,12-d10)-2,4-bis(phenyl-d5)benzofuro[3,2-d]pyrimidin-6, 7, 9-ds

[0393] 34.2 g (48.0 mmol; 1.0 eq) of 2,4-diphenyl-8-(3-(4a,4b,8a,9a-tetrahydro-9H-carbazol-9-yl)triphenylen-2-yl)benzofuro[3,2-d]pyrimidine 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. 25 g (33.5 mmol, 70% of theory) of the product shown above is obtained as a mixture with portions of H / D isotopomers and H / D isotopologues after chromatographic purification and finally concentrated under high vacuum (p = 5 x 10'). 7 mbar) sublimated (purity 99.9%).

[0394] 3.7 g (15.5 mmol; 1.00 eq) 4 / 7-naphtho[1,2,3,4-def]carbazole and 20.0 g Pt 5% on

[0395] Activated carbon is 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 is stirred for 5 days at 165°C under elevated autogenous pressure. After cooling, it is extracted twice with tetrahydrofuran, and the combined organic phases are washed with brine and dried over sodium sulfate. After filtration, the solvent is removed under reduced pressure. The product shown above, a mixture containing portions of H / D isotopomers and H / D isotopologues, is obtained after further purification by extraction, recrystallization, and sublimation.

[0396] The yield is 1.7 g (6.9 mmol), corresponding to 47% of theory.

[0397] Production of OLEDs

[0398] In the following examples V1 to V8 and Ex1 to Ex8 (see Tables 7 and 8) the data of different OLEDs are presented.

[0399] Examples Ex1 to Ex8 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).

[0400] 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.

[0401] 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 SdT1:H2:TEG1 (32%:60%:8%) 30nm means that the material SdT1 is present in a volume fraction of 32% as host material 1, the compound H2 as host material 2 in a volume fraction of 60%, and TEG1 in a volume fraction of 8% in a 30nm thick layer. Similarly, the hole injection layer (HIL) and the electron transport layer (ETL), for example, can also consist of a mixture of two materials.

[0402] 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 calculated the CIE 1931 x and y color coordinates. The value U10 in Table 8 refers to the voltage that is required for a current density of 10 mA / cm 2 is required. EQE10 denotes the external quantum efficiency at a current density of 10 mA / cm 2 The lifetime LT is defined as the time after which the luminance when operated at a constant current density jo in mA / cm 2 from a starting luminance LO (in cd / m 2 ) to a certain proportion L1 (in cd / m 2). A value of L1 / L0 = 90% in Table 8 means that the lifetime given in column LT corresponds to the time (in hours) after which the luminance drops to 90% of its initial value (LO).

[0403] Use of mixtures according to the invention in OLEDs

[0404] The compounds or material combinations according to the invention can be used in the emission layer in phosphorescent green OLEDs.

[0405] The data for the various OLEDs are summarized in Table 8. Examples C1 to C8 are comparative examples according to the prior art, while examples Ex1 to Ex8 show data for OLEDs according to the invention. The inventive examples demonstrate, in particular, a significant advantage in the device's lifetime.

[0406] Table 7: Structure of the OLEDs

[0407] Table 8: Table 9: Materials used, unless previously described

Claims

Patent claims 1. Compound according to formula (1), where the symbols and indices used are: L is, identically or differently at each occurrence, a single bond or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which is linked to one or more radicals R 1 can be substituted; R° is, at each occurrence, the same or different, selected from the group consisting of 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 )a, 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 2 may 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 H 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; R 1 is selected at each occurrence, identically or differently, 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 2 may be substituted, with one or more non-adjacent CH2 groups being R 2 C=CR 2 , Si(R 2 )2, C=0, C=S, C=NR 2 , P(=O)(R 2 ), SO, SO2, NR 2 , O, S or CONR 2 and wherein one or more H 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 2may 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; * indicates the connection to L-Rx, V is O or S; R# is at each occurrence independently D, F, CN or phenyl which may be substituted with one or more radicals R 2 can be substituted; [R#]a2 represents a monosubstitution, a disubstitution, the maximum allowed substitution or no substitution with R#; 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; An , Ar2 are independently an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which may be substituted by one or more radicals R; Ars is an aromatic ring system with 6 to 40 ring atoms, which may be substituted by one or more radicals R, or a heteroaromatic ring system with 5 to 40 ring atoms, which may be substituted by one or more radicals R may be substituted and wherein the heteroaromatic ring system contains one or more heteroatoms selected from O, S, Se or Si; AM is, at each occurrence, the same or different, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by one or more radicals R; R is selected, identically or differently at each occurrence, 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 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; (D)a ,(D)b, (D)c represent a monosubstitution, a disubstitution, a trisubstitution, the maximum allowed substitution or no substitution with deuterium; a1 is 0, 1 or 2.

2. A compound according to claim 1, wherein L represents a bond or one of the Formulas L-1 to L-34, which are substituted with one or more radicals R 1 may be substituted, where R 1 has a meaning as defined in claim 1, Vi represents O, S or Se and the dashed lines indicate the bond to the remainder of formula (1).

3. A compound according to claim 1 or 2, wherein VO is.

4. A compound according to one or more of claims 1 to 3, wherein Rx corresponds to formula (1-1) or formula (1-2).

5. A mixture comprising at least one compound according to one or more of claims 1 to 4 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).

6. Formulation comprising at least one compound according to one or more of claims 1 to 4 or a mixture according to claim 5 and at least one solvent.

7. 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 4.

8. The organic electronic device of claim 7, wherein the electronic device is an electroluminescent device.

9. The organic electronic device according to claim 7 or 8, wherein the organic layer contains at least one light-emitting layer containing the compounds according to any one of claims 1 to 4.

10. Organic electronic device according to one or more of claims 7 to 9, characterized in that the light-emitting layer contains a further matrix material.

11. Organic electroluminescent device according to claim 10, characterized in that the further matrix material corresponds to a compound of the formulas (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), where the symbols and indices used are: A 1 is C(R 7 )2, NR 7 , O or S; L is a bond, O, S, C(R 7 )2 or NR 7 ; A is at each occurrence independently a group of the formula (HH-4-1) or (HH-4-2), 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 the formula (HH-4); U 1 , U 2 are a bond, O, S, C(R 7 )2or NR 7 ; 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; 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 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, where R 8 does not denote H; two or more radicals R 7 together form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system, preferably the radicals R 7 no such ring system; R 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 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 d+d1+d2 = 1; q, q1, q2 each independently denote 0, 1, 2, 3 or 4; 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, 1, 2, or 3.

12. Organic electronic device according to one or more of claims 7 to 11, characterized in that the light-emitting layer contains a phosphorescent emitter.

13. Organic electronic device according to one or more of claims 7 to 12, 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).

4. A method for producing a device according to one or more of claims 7 to 13, characterized in that the organic layer is applied by gas phase deposition or from solution.

5. A method for producing a device according to one or more of claims 7 to 13, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of the formula (1) together with at least one further matrix material as a premix, are deposited from the gas phase sequentially 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).

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