WO2024251699A1 - Materials for organic electroluminescent devices - Google Patents

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

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 often used in organic electroluminescent devices (OLEDs). In general, there is still a need for improvement in OLEDs, for example with regard to efficiency, operating voltage and service life. The properties of phosphorescent OLEDs are not only determined 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 the OLED properties. According to the prior art, carbazole derivatives, dibenzofuran derivatives, indenocarbazole derivatives, indolocarbazole derivatives, benzofurocarbazole derivatives and benzothienocarbazole derivatives are used as matrix materials for phosphorescent emitters. In WO2018060218 A1, KR20220135761 A, KR20220063428 A and WO22207678 A1, special diazadibenzofuran-carbazole derivatives or diazadibenzothiophene-carbazole derivatives are described as matrix materials, among others. In WO2012048781 A1, CN110437241 A and special 4H-naphtho[1,2,3,4- def]carbazole derivatives are described as matrix materials, among others. In KR20210036304 A, KR20210034528 A, WO22038065 A1, CN115073356 A, CN112062753 A and US2022263031 A1, complex carbazole derivatives are described, among other things, as matrix materials. In general, there is still room for improvement with these materials, particularly for use as matrix materials. The object of the present invention is to provide compounds which are particularly suitable for use as Matrix material, electron transport material or hole blocking material 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, ie emitter concentrations in the order of 3 to 20%, in particular 3 to 15%, since the device lifetime is limited in particular here.

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.

It has further been found that the combination of at least one compound of the formula (1) as a 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.

Summary of the Invention

A first object of the present invention is a compound according to formula (1),

(D) _b 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 having 5 to 40 ring atoms which may be substituted by one or more radicals R ¹ ;

R° is selected at each occurrence, identically or differently, from the group consisting of F, CI, Br, I, CN, NO ₂ , 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 with 3 to 20 C atoms or an alkenyl group with 2 to 20 C atoms, each of which can be substituted by one or more radicals R ² , where one or more non-adjacent CH ₂ groups can be replaced by R ² C=CR ² , Si(R ² ) ₂ , C=O, C=S, C=NR ² , P(=O)(R ² ), SO, SO ₂ , NR ² , O, S or CONR ² and where one or more H atoms can be replaced by D, F, CI, Br, I, CN or NO ₂ , an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which can be substituted by one or more radicals R ² , an aryloxy or heteroaryloxy group with 5 to 40 ring atoms, which can be substituted by one or more radicals R ² or an aralkyl or heteroaralkyl group having 5 to 40 ring atoms which may be substituted by one or more radicals R ² ;

* bezeichnet die Anbindung an L-Rx, R ¹ is selected on each occurrence, identically or differently, from the group consisting of D, F, CI, Br, I, CN, NO ₂ , 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 may be substituted by one or more radicals R ² , where one or more non-adjacent CH ₂ groups are replaced by R ² C=CR ² , Si(R ² ) ₂ , C=O, C=S, C=NR ² , P(=O)(R ² ), SO, SO2, NR ² , O, S or CONR ² and where one or more H atoms can 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 can be substituted by one or more radicals R ² , an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, which can be substituted by one or more radicals R ² , or an aralkyl or heteroaralkyl group having 5 to 40 ring atoms, which can be substituted by one or more radicals R ² ;

* 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 by one or more radicals R ² ;

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

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

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 can be substituted by one or more radicals R, or a heteroaromatic

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;

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, identically or differently, selected 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 O, 1 or 2.

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).

The invention further relates to 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. Another object of the invention is the use of a compound according to formula (1) in an organic electronic device.

Another object 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.

Another object of the invention is a method 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.

Description of the Invention

In the present patent application, “D” or “D atom” refers to deuterium.

An aryl group in the sense of this invention contains 6 to 40 ring atoms, preferably C atoms. A heteroaryl group in the sense of this invention contains 5 to 40 ring atoms, where the ring atoms comprise C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e. phenyl, derived from benzene, or a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene, or a condensed aryl or heteroaryl group, for example derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline. An aryl group with 6 to 18 carbon 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 in the sense of this invention can carry one or more radicals, whereby the suitable radical is described below. If no such radical is described, the aryl group or heteroaryl group is not substituted.

An aromatic ring system in the sense of this invention contains 6 to 40 C atoms in the ring system. The aromatic ring system also includes aryl groups, as previously described.

An aromatic ring system with 6 to 18 C atoms is preferably selected from phenyl, fully deuterated phenyl, biphenyl, naphthyl, phenanthryl and triphenylenyl. A heteroaromatic ring system in the sense 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.

An aromatic or heteroaromatic ring system within the meaning of this invention is understood to mean a system which does not necessarily only contain 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. For example, systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diaryl ethers, stilbene, etc. are 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 as e.g. B. biphenyl, terphenyl, quaterphenyl or bipyridine, are also included in the definition of the aromatic or heteroaromatic ring system.

An aromatic or heteroaromatic ring system with 5 to 40 ring atoms, which can be linked to the aromatic or heteroaromatic ring via any position, is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, Isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, Indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, Benzpyrimidine, quinoxaline, 1,5-diaza-anthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, Fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, Indolizine and benzothiadiazole.

The abbreviations Ar, An, Ar2 and An mean, identically or differently on 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.

The abbreviation Ars stands, identically or differently on each occurrence, 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.

The abbreviation Ars stands, identically or differently on each occurrence, for an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R ⁷ , where the radical R ⁷ or the substituents R ⁷ have a meaning as described above or below. A preferred meaning of Ars is described below.

Weiterhin soll unter der oben genannten Formulierung aber auch verstanden werden, dass für den Fall, dass einer der beiden Reste Wasserstoff darstellt, der zweite Rest unter Bildung eines Rings an die Position, an die das Wasserstoffatom gebunden war, bindet. Dies soll durch das folgende Schema verdeutlicht werden:

In the context of the present description, the phrase that two or more residues can form a ring with each other is to be understood to mean, among other things, that the two residues are linked to each other by a chemical bond with 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 bound, forming a ring. This is illustrated by the following scheme:

A cyclic alkyl, alkoxy or thioalkyl group within the meaning of this invention is understood to mean a monocyclic, a bicyclic or a polycyclic group.

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-,

1.1-Dimethyl-n-hept-1-yl-, 1,1-dimethyl-n-oct-1-yl-, 1,1-dimethyl-n-dec-1-yl-, 1,1-dimethyl- n -dodec-1-yl-, 1,1-dimethyl-n-tetradec-1-yl-, 1 ,1-Dimethyl-n-hexadec-1-yl-, 1,1-Dimethyl-n-octadec-1-yl-, 1, 1-Diethyl-n-hex-1-yl-, 1, 1-Diethyl- n-hept-1 -yl-, 1, 1-diethyl-n-oct-1 -yl-,

1,1-Diethyl-n-dec-1-yl-, 1,1-Diethyl-n-dodec-1-yl-, 1,1-Diethyl-n-tetradec-1-yl-, 1,1-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.

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.

The index a1 means 0, 1 or 2, the position of the substituents R° being unrestricted when they occur. Preferred compounds of the formula (1) are compounds of the formula (1a) in which a1 = 0, compounds of the formula (1b) in which a1 = 1 and compounds of the formula (1c) in which a1 = 2.

wobei R°, (D)_a, (D)b, (D)_c, L und Rx eine zuvor genannte oder nachfolgend bevorzugt genannte Bedeutung haben.

where R°, (D) _a , (D) b, (D) _c , L and Rx have a meaning mentioned above or preferred below.

The radical R° is, on each occurrence, identically or differently, 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 may be substituted by one or more radicals R ² , an aromatic ring system having 6 to 40 ring atoms, each of which may be substituted by one or more radicals R ² , dibenzofuranyl or dibenzothiophenyl, each of which may be substituted by one or more radicals R ² 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 given above or given below as preferred. 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 may be substituted by one or more radicals R ² .

Particularly preferred compounds of the formula (1) are the compounds of the 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 mentioned as preferred below.

Preferred compounds of formula (1) are further compounds of formula (1 d),

(1e), (1f) and (1g),

wobei R⁰, a1, (D)_a, (D)_b, (D)_c, L, [R#]_a2, R#, V, Ar₁, Ar₂, Ar₃ und Ar₄ eine zuvor genannte oder nachfolgend bevorzugt genannte Bedeutung haben. Besonders bevorzugte Verbindungen der Formel (1) sind die Verbindungen der Formeln (1d) und (1e), d.h. Verbindungen der Formel (1), bei denen Rx einer Formel (1-1) oder (1- 2) entspricht, wobei R⁰, a1, (D)_a, (D)_b, (D)_c, L, [R#]_a2, R#, V, Ar₁, Ar₂, Ar₃ und Ar₄ eine zuvor genannte oder nachfolgend bevorzugt genannte Bedeutung haben. Besonders bevorzugte Verbindungen der Formeln (1d) und (1e) sind Verbindungen der Formeln (1h) bis (1m),

where R ⁰ , a1, (D) _a , (D) _b , (D) _c , L, [R#] _a2 , R#, V, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ have a meaning given above or given below with preference. Particularly preferred compounds of the formula (1) are the compounds of the formulas (1d) and (1e), ie compounds of the 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, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ have a meaning given above or given below with preference. Particularly preferred compounds of the formulas (1d) and (1e) are compounds of the formulas (1h) to (1m),

( ) wobei R⁰, (D)a, (D)b, (D)c, L, [R#]a2, R#, V, Ar1, Ar2, Ar3 und Ar4 eine zuvor genannte oder nachfolgend bevorzugt genannte Bedeutung haben. In einer Ausführungsform der Erfindung steht der Linker L in Verbindungen der Formeln (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (1l) und (1m) für eine Bindung oder für ein aromatisches oder heteroaromatisches Ringsystem der Formeln L-1 bis L-34, die mit einem oder mehreren Resten R¹ substituiert sein können:

wobei die gestrichelten Linien die Anbindung an den Rest der Formel

( ) 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 below as preferred. 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) is a bond or an aromatic or heteroaromatic ring system of the formulas L-1 to L-34, which can be substituted by one or more radicals R ¹ :

where the dashed lines represent the connection to the rest of the formula

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

Vi means O, S or Se and where R ¹ has a meaning given above or below.

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 a single bond.

In a preferred embodiment of the invention, the linker L in compounds of the formulae (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 may be substituted by one or more radicals R ¹ , where R ¹ has a meaning given above or given below. In the linkers L-18 to L-30, Vi is preferably O or S, particularly preferably O.

From the group of linkers L-1 to L-30, which may be substituted by one or more radicals R ¹ , the following linkers are preferably selected: L-2, L-3, L-4, L-7, L-8, L-12, L-15, L-20, L-22, L-26, which may be substituted by one or more radicals R ¹ , where R ¹ has a meaning given above or given below.

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

The substituent R ¹ , when identical or different, is 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 ¹ , when identical or different, is preferably D, phenyl or dibenzofuranyl. Ar in Si(Ar)3 is preferably identical and is an aromatic ring system having 6 to 20 ring atoms, which can 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 preferably D.

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

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 V is O.

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), (D) _a , (D)b and (D) _c represent a monosubstitution, a disubstitution, a trisubstitution, the maximum permissible substitution or no substitution with deuterium.

If the compounds of formulae (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 formulae (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 differ only in the degree of deuteration and/or the deuteration patterns.

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.

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 100mol%, particularly preferably 50mol% to 95mol% and very particularly preferably 70mol% to 90mol%. 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.

A suitable method for deuterating a compound by replacing one or more H atoms with D atoms is to treat the compound to be deuterated in the presence of a platinum catalyst or palladium catalyst and a deuterium source. The term "deuterium source" means any compound that contains one or more D atoms and can release them under suitable conditions.

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, the fully deuterated solvent being 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.

In one embodiment of the invention, (D) _a , (D) b and (D) _c represent no substitution. In one embodiment of the invention, (D) _a , (D) b and (D) _c represent maximum substitution.

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 on each occurrence independently of one another D, F, CN or a non-deuterated, partially deuterated or fully deuterated phenyl, particularly preferably D. If R# is D, [R#] _a 2 preferably represents the maximum permissible substitution. If R# is F or CN, [R#] _a 2 preferably represents monosubstitution or disubstitution.

If R# represents a non-deuterated, a partially deuterated or a fully deuterated phenyl, [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 a substitution.

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.

In compounds of the formulae (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m) or preferred compounds of the formulae (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), Ar, An, Ar2 and AM on each occurrence, identically or differently, preferably represent an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by one or more radicals R; where R has a meaning mentioned above or mentioned with preference.

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 on each occurrence are the same or different and preferably represent an aromatic or heteroaromatic ring system having 5 to 40 ring atoms from the group Ar-1 to Ar-35,

wobei o

where o

Y at each occurrence is the same or different as O, S, NAr or C(R)2,

R is methyl or phenyl, o 9

RH, 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), (11) 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

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

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 as preferred. Ar is particularly preferably phenyl, 1,2-biphenyl, 1,3-biphenyl or 1,4-biphenyl.

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, particularly

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

In the structures Ar-1 to Ar-35, the substituent R is preferably selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN or an aromatic ring system having 6 to 30 ring atoms, which may each be substituted by one or more radicals R ² . In the structures Ar-1 to Ar-35, the o

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.

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

(ll) 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 on each occurrence, identically or differently, preferably represent a group selected from Ar-1 to Ar-28 and Ar-33 to Ar-35, as described above or particularly preferably represent 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.

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

R has a meaning previously specified or preferred.

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

(lm) represents the group Ar-2, where R has a meaning given previously or preferred. 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

Ar-2, where R has a previously indicated or preferred meaning and a1 stands for 1.

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 previously described, 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 o and Ar-33 to Ar-35, as previously described, with the proviso that Y represents O, S or C(R) ₂ .

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

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

P23-091 ScTable 1 :

P23-091 Sc

ro

-22-

ro

P23-091 Sc

-28-

5

15

20

25

35

Besonders geeignete Verbindungen der Formeln (1), (1a), (1 b), (1c), (1d), (1e), (1f), (1g), (1h), (1 i), (1j), (1 k), (11) und (1m) sind die Verbindungen E1 bis E45 der Tabelle 2.

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.

Table 2:

Detaillierte Reaktionsbedingungen sind aus dem Stand der Technik bekannt oder sind im Beispielteil beschrieben. The compounds according to the invention can be prepared by known synthesis 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 according to the invention are to be understood as examples. Alternative synthesis routes can be developed within the scope of general specialist knowledge.

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

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).

For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes, formulations of the compounds according to the invention or of mixtures of compounds according to the invention with further functional materials, such as matrix materials, fluorescent emitters, phosphorescent emitters and/or emitters that exhibit TADF, are required. These formulations can be, for example, solutions, dispersions or emulsions. It may be preferable 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-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, Dodecyl benzene, ethyl benzoate, indane, NMP, p-cymene, phenetol, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, Tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, Diethyl sebacate, octyloctanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents.

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 a solvent mentioned above or a mixture of these solvents.

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 are suitable for use in an organic electroluminescent device, in particular as a matrix material.

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.

The invention therefore further relates to 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.

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.

The organic electronic device can be selected from, for example, 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.

Preferably, the organic electronic device is an organic electroluminescent device.

The organic electroluminescent device according to the invention (synonymous with organic electroluminescent device) is, for example, an organic light-emitting transistor (ÖLET), 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 a organic light-emitting diode or an organic light-emitting electrochemical cell. The device according to the invention is particularly preferably an OLED.

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.

If several emission layers are present, these preferably have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, i.e. different emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. Several fluorescent and/or phosphorescent compounds can also be contained in an emitting layer. Systems with three emitting layers are particularly preferred, with the three layers showing blue, green and orange or red emission. As an alternative to the combination as described above, an emitting layer can also show 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.

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

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 with one another. 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 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 containing a compound according to formula (1) or the preferred embodiments described above in an emitting layer as matrix material for fluorescent emitters, phosphorescent emitters or for emitters that exhibit 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 matrix material in an emitting layer or as electron transport or hole blocking material in an electron transport or hole blocking layer.

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.

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.

A further subject matter of the present invention is therefore 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 and at least one further matrix material.

A further subject matter of the present invention is therefore an organic electronic device as described above, wherein the organic layer contains at least one light-emitting layer which comprises at least one compound of the formula (1) or at least one preferred compound of one of the formulae (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (11) and (1m), or a compound of the Table 1 or one of the compounds E1 to E45 and two other matrix materials.

Suitable matrix materials which 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 boron esters, triazine derivatives, zinc complexes, diazasilole or tetraazasilole derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives or dibenzofuran derivatives. Likewise, another phosphorescent emitter which emits at a shorter wavelength than the actual emitter can be present in the mixture as a co-host or a compound which does not participate or does not participate to a significant extent in the charge transport, such as a wide band-gap compound.

A wide-band-gap material is understood here to mean a material in the sense 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.

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.

Formel (HH-6), wobei für die verwendeten Symbole und Indizes gilt: A further subject matter of the invention is therefore 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:

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),

Formula (HH-4-1) Formula (HH-4-2);

X2 is the same or different at each occurrence and is CH, CR ⁶ or N, where a maximum of 2 symbols X2 N can be used;

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

R ⁶ is, identically or differently on 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 may in each case be substituted by one or more radicals R ⁷ and where one or more non-adjacent CH ₂ groups may be replaced by Si(R ⁷ ) ₂ , C=O, NR ⁷ , O, S or CONR ⁷ , or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R ⁷ ; two radicals R ⁶ can also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another;

Ars, identical or different at each occurrence, independently represents an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R ⁷ ; R ⁷ is, identically or differently on 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) ₂ R 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, where the alkyl, alkenyl or alkynyl group may each be substituted by one or more radicals R ⁸ , where one or more non-adjacent CFh groups are replaced by Si(R ⁸ )2, C=O, NR ⁸ , O, S or CONR ⁸ , or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, each of which may be substituted by one or more radicals R ⁸ , where R ⁸ is not H; two or more radicals R ⁷ can form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another, preferably the radicals R ⁷ do not form such a ring system;

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

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

wobei Ars, R⁶, s und u eine zuvor angegebene oder bevorzugt angegebene Bedeutung haben.

where Ars, R ⁶ , s and u have a previously indicated or preferred meaning.

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 if the radical R ⁶ is different from D, or particularly preferably 0.

In compounds of the formulas (HH-1), (HH-2) or (HH-3), t is preferably 0 or 1 if the radical R ⁶ is different from D, or particularly preferably 0.

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 ⁶ is 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.

In compounds of the 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.

In compounds of the formula (HH-4), L is preferably a single bond or C(R ⁷ )2, where R ⁷ has a meaning as previously mentioned, particularly preferably L is a single bond.

In formula (HH-4-1), v is preferably 0 or 1 if the radical R ⁶ is different from D.

In formula (HH-4-2), U or U when occurring is preferably a single bond or C(R ⁷ ) 2, where R ⁷ has a meaning mentioned above, particularly preferably U ¹ or U ² when occurring is a single bond.

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

In a preferred embodiment of the 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 can be combined according to the invention with compounds of the formula (1) or preferred compounds of the formula (1), as described above, R ⁶ is selected, identically or differently on 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 the alkyl group can be substituted in each case by one or more radicals R ⁷ , or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, preferably having 5 to 40 ring atoms, which can be substituted in each case by one or more radicals R ⁷ .

In a preferred embodiment of the 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 can be combined according to the invention with compounds of the formula (1) or preferred compounds of the formula (1), as described above, R ⁶ is the same or different on each occurrence and is selected from the group consisting of D or an aromatic or heteroaromatic ring system having 6 to 30 ring atoms, which may be substituted by one or more radicals R ⁷ .

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 can be linked via the 1-, 2-, 3- or 4-position, spirobifluorenyl, which can be linked via the 1-, 2-, 3- or 4-position, naphthyl, in particular 1- or 2-linked naphthyl, or residues derived from indole, benzofuran, benzothiophene, carbazole, which can 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 may be substituted by one or more radicals R ⁷ . Ars is preferably unsubstituted.

If A ¹ in formula (HH-2) or (HH-3) or (HH-6) is 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 is the same or different on each occurrence and 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 ⁷ are phenyl, biphenyl, terphenyl and quaterphenyl, which are preferably unsubstituted, and radicals derived from triazine, pyrimidine and quinazoline, which may be substituted by one or more radicals R ⁸ , where R ⁸ does not represent H.

If A ¹ in formula (HH-2) or (HH-3) or (HH-6) is C(R ⁷ ) 2 , the substituents R ⁷ which are bonded to this carbon atom are preferably identical or different on each occurrence and are 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 may also be substituted by one or more radicals R ⁸ , where R ⁸ is not H. R ⁷ is very particularly preferably a methyl group or a phenyl group. The radicals R ⁷ can also form a ring system with one another, resulting in a spiro system.

In a preferred embodiment of the 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) and (HH-6), these compounds are partially or completely deuterated, particularly preferably completely 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) are generally known and some of the compounds are commercially available.

Compounds of the 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.

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

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, which only differ in the degree of deuteration and/or the deuteration pattern. The statements on deuterated mixtures and on the production of deuterated materials, as previously described for compounds of formula (1), apply here accordingly.

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%.

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.

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 fully deuterated.

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],

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],

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.

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, particularly suitable compounds of the formula (HH-1) are those in which at least one group Ars is a heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R ⁷ and/or compounds of the formula (HH-4) and/or compounds of the formula (HH-5).

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.

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 described above or preferably described, very particularly preferably compounds of the formula (HH-4) or (HH-5) or (HH-5-A) are suitable.]

P23-091 Sc

P23-091 Sc Further examples of suitable 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) and (HH-6) for combination with compounds of formula (1) or preferred compounds of formula (1) as previously described or preferably described are the structures of Table 3 and Table 4 below.

P23-091 Sc

P23-091 Sc

5

15

20

25

P23-091 Sc 35

P23-091 Sc

- 65 -

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

5 are the compounds of Table 4.

Table 4:

15

20

25

P23-091 Sc

P23-091 Sc

35

P23-091 Sc

P23-091 Sc

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 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.

Very particularly preferred mixtures of the compounds of the formula (1) with the 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) for the device according to the invention are obtained by combining the compounds E1 to E45 with the compounds H1 to H33 as shown in Table 5 below. The first mixture M1, for example, is a combination of the compound E1 with H1. Table 5:

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 entire mixture or based on the entire composition of the light-emitting layer.

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 total mixture or based on the total composition of the light-emitting layer.

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 previously described or preferably described, contains at least one phosphorescent emitter.

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

The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the light-emitting layer contains at least one phosphorescent emitter in addition to the above-mentioned host materials of the formulas (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.

The term phosphorescent emitter typically includes compounds in which the light emission occurs through a spin-forbidden transition from an excited state with a 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, for example a quintet state. Preferably, a transition from a triplet state is understood here.

Particularly suitable as phosphorescent emitters (= triplet emitters) are compounds which emit light, preferably in the visible range, when suitably excited 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 regarded as phosphorescent emitters. In general, all phosphorescent complexes as used according to the state of the art for phosphorescent OLEDs and as known to the person skilled in the art in the field of organic electroluminescent devices are suitable.

wobei die Symbole und Indizes für diese Formel (Illa) die Bedeutung haben: n+m ist 3, n ist 1 oder 2, m ist 2 oder 1 , 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 ,

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

R is, identically or differently at each occurrence, 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.

A further subject matter of the invention is therefore 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.

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

In emitters of the formula (IIIa), one X is preferably selected from N and the other Xs are CR or all Xs, identical or different on each occurrence, are CR. In emitters of the formula (IIIa), at least one R is preferably different from H. In emitters of the formula (IIIa), two Rs are preferably different from H and have one of the meanings otherwise previously given for the emitters of the formula (IIIa). Preferred phosphorescent emitters according to the present invention correspond to the formulas (I), (II), (III), (IV) or (V),

wobei die Symbole und Indizes für diese Formeln (I), (II), (III), (IV) und (V) die Bedeutung haben:

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

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

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

R

wobei die Symbole und Indizes für diese Formeln (VI), (VII) und (VIII) die Bedeutung haben:

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

Ri is H or D, R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear

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

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.

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

Table 6:

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.

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.

A yellow-emitting layer is understood to be a layer whose photoluminescence maximum is in the range from 540 to 570 nm. An orange-emitting layer is understood to be a layer whose photoluminescence maximum is in the range from 570 to 600 nm. A red-emitting layer is understood to be a layer whose photoluminescence maximum is in the range from 600 to 750 nm.

A green-emitting layer is understood to be a layer whose photoluminescence maximum is in the range from 490 to 540 nm. A blue-emitting layer is understood to be a layer whose photoluminescence maximum is in the range from 440 to 490 nm. The photoluminescence maximum of the layer is determined by measuring the photoluminescence spectrum of the layer with a layer thickness of 50 nm at room temperature, wherein the layer contains the inventive combination of the host material 1 of the formulas (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (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.

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 ^-5 molar, with the measurement being carried out at room temperature and any solvent in which the selected emitter dissolves in the stated concentration being 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 T ₁ 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(T ₁ in eV) = 1240/E(T ₁ 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 T ₁ is preferably ~2.3 eV to ~2.1 eV. Preferred phosphorescent emitters are therefore green emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 6, whose triplet energy T ₁ is preferably ~2.5 eV to ~2.3 eV. Particularly preferred phosphorescent emitters are therefore green emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 6, as described above, whose triplet energy T ₁ is preferably ~2.5 eV to ~2.3 eV. Green emitters, preferably of formula (IIIa), formulas (I) to (VIII) or from Table 6, as described above, are very particularly preferably selected 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, wherein preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a condensed ring system, particularly preferably with at least 14 ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. An aromatic anthraceneamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. An aromatic anthracene diamine is a compound in which two diarylamino groups are directly bonded to an anthracene group are 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 in the 1,6-position. Further preferred emitting compounds are indenofluorenamines or diamines, benzoindenofluorenamines or diamines, and dibenzoindenofluorenamines or diamines, and indenofluorene derivatives with condensed aryl groups. Also preferred are pyrene-arylamines. Also preferred are benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives which are linked to furan units or to thiophene units. In addition, the light-emitting device or the mixture according to the invention can also contain materials which exhibit TADF (thermally activated delayed fluorescence).

In a further preferred embodiment of the invention, the at least one light-emitting layer of the organic electroluminescent device can 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 the host material 1 and the 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 the formula (IIIa), the formulas (I) to (VIII) or for an emitter of Table 6.

According to one embodiment of the present invention, the mixture contains no further components, i.e. functional materials, in addition to the components of the host material 1 and the host material 2, as previously described or preferably described. These are material mixtures that are used as such to produce the light-emitting layer. These mixtures are also referred to as premix systems, which are used as the only material source when vaporizing the host materials for the light-emitting layer and which have a constant mixing ratio when vaporizing. This makes it possible to vaporize a layer with a uniform distribution of the components in a simple and quick manner, without the need for precise control of a large number of material sources.

According to an alternative embodiment of the present invention, the mixture contains, in addition to the constituents 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 suitable Mixing ratio during evaporation, this mixture can also be used as the sole material source.

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).

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).

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 the host materials 1 and 2, as described above or preferably described, optionally with the phosphorescent emitter, as described above or preferably described, are provided for this purpose in a formulation which contains at least one solvent. Suitable formulations have been described above.

The light-emitting layer in the device according to the invention according to the preferred embodiments and the emitting compound preferably contains between 99.9 and 1 vol. %, more preferably between 99 and 10 vol. %, particularly preferably between 98 and 60 vol. %, very particularly preferably between 97 and 80 vol. % of matrix material made of at least one compound of the formulas (1), (1a), (1b), (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. %, most 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 amounts in vol. % given above.

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 belongs to the class of arylamines.

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

Anode / hole injection layer / hole transport layer / emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

This sequence of layers is a preferred sequence.

It should be noted again that not all of the layers mentioned above have to be present and/or that additional layers may be present.

All materials that are used according to 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.

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), (11) or (1m), as described above or preferably described.

Metals with a low work function, 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.) are suitable as the cathode of the device according to the invention. Alloys made of an alkali or alkaline earth metal and silver are also suitable, for example an alloy of magnesium and silver. In multilayer structures, in addition to the metals mentioned, other metals can be used that have a relatively high work function, such as Ag or Al, in which case combinations of the metals, such as Ca/Ag, Mg/Ag or Ba/Ag, are 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. Examples of suitable materials for this are alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (e.g. LiF, U2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). Lithium quinolinate (LiQ) can also be used for this purpose. The thickness of this layer is preferably between 0.5 and 5 nm.

Materials with a high work function are preferred as anodes. The anode preferably has a work function greater than 4.5 eV vs. vacuum. Metals with a high redox potential are suitable for this, such as Ag, Pt or Au. 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 in order to enable either the irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. 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.

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.

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

The organic electroluminescent device according to the invention is preferably characterized in that one or more layers are coated using the OVPD (Organic Vapour Phase Deposition) method or with the aid of carrier gas sublimation. The materials are applied at a pressure between 10'$ mbar and 1 bar. A special case of this method is OVJP (Organic Vapour 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).

The organic electroluminescent device according to the invention is further preferably characterized in that one or more organic layers containing the composition according to the invention are produced from solution, such as by spin coating, or using any printing method, such as screen printing, flexographic printing, nozzle printing or offset printing, but particularly preferably LITI (light induced thermal imaging, thermal transfer printing) or ink-jet printing. Soluble host materials 1 and 2 and phosphorescent emitters are required for this. Processing from solution has the advantage that, for example, the light-emitting layer can be applied very easily and inexpensively. This technique is particularly suitable for the mass production of organic electroluminescent devices.

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.

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

A further subject matter 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.

When producing by means of gas phase deposition, there are basically two ways in which the organic layer according to the invention, preferably the light-emitting layer, can be applied or vaporized onto any substrate or the previous layer. On the one hand, the materials used can be placed in a material source and then evaporated from the different material sources (“co-evaporation”). On the other hand, the different materials can be premixed (“premix systems”) and the mixture can be placed in a single material source from which it can then be evaporated (“premix evaporation”). This makes it easy and quick to evaporate the light-emitting layer with a uniform distribution of the components without the need for precise control of a large number of material sources.

The following procedures are possible:

A method for producing the organic electroluminescent device according to the invention, as previously described 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 a carrier gas sublimation, or from solution, in particular by spin coating or with a printing process.

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), (11) 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.

A method for producing the device according to the invention, 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), (11) or (1m) is deposited from the gas phase together with at least one further matrix material as a premix, one after the other or simultaneously with the light-emitting materials selected from the group of phosphorescent emitters, fluorescent emitters and/or emitters which exhibit TADF (thermally activated delayed fluorescence).

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:

1. Electronic devices, in particular organic

Electroluminescent devices containing compounds according to formula (1) or The preferred embodiments described above and below, in particular as matrix material or as electron-conducting materials, have a very good service life. In particular, these compounds cause a low roll-off, ie a small drop in the power efficiency of the device at high luminance levels.

2. Electronic devices, in particular organic electroluminescent devices containing compounds according to formula (1) or the preferred embodiments set out above and below as electron-conducting materials and/or matrix materials, have excellent efficiency. In this case, compounds according to the invention according to formula (1) or the preferred embodiments set out above and below result in a low operating voltage when used in electronic devices.

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

4. Using compounds according to formula (1) or the preferred embodiments set out above and below, the formation of optical loss channels can be avoided in electronic devices, in particular organic electroluminescent devices. As a result, these devices are characterized by a high PL and thus high EL efficiency of emitters or an excellent energy transfer from the matrices to dopants.

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

6. Compounds according to formula (1) or the preferred embodiments set out above and below have excellent glass film formation.

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

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

It should be understood that variations of the embodiments described in the present invention are 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 as an example of a generic series or as an equivalent or similar feature.

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).

The teaching of technical action disclosed by the present invention can be abstracted and combined with other examples.

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

examples

General methods:

The Gaussian16 (Rev. B.01) program package is used in 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.

From the energy calculation, the HOMO is obtained as the last orbital occupied by two electrons (Alpha occ. eigenvalues) and LUMO as the first unoccupied orbital (Alpha virt. eigenvalues) in Hartree units, where HEh and LEh represent the HOMO energy in Hartree units or the LUMO energy in Hartree units. From this, the HOMO and LUMO values in electron volts calibrated using cyclic voltammetry measurements are determined as follows:

HOMOcorr = 0.90603 * HOMO - 0.84836

LUMOcorr = 0.99687 * LUMO - 0.72445

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

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 resulting from the quantum chemical energy calculation.

The lowest energy singlet state is called SO.

The method described here is independent of the software package used and always delivers the same results. Examples of frequently 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.

synthesis examples

The following syntheses are carried out under a protective gas atmosphere in dried solvents, unless otherwise stated. The compounds according to the invention can be prepared by means of synthesis methods known to those skilled in the art.

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 are added portionwise under argon at room temperature.

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

a) 6-Brom-2-cyanophenyl-benzoat

The yield is 107 g (316 mmol), corresponding to 69% of theory. Analogously, the following brominated compounds are prepared:

a) 6-Bromo-2-cyanophenyl benzoate

[73289-85-7]

A solution of 10 g (50 mmol) of 2-bromo-6-hydroxy-benzonitrile, 10.4 ml (75 mmol) of triethylamine and 61 mg (0.5 mmol) of 4-N,N-dimethylaminopyridine in 200 ml of CH2CI2 is initially charged, cooled to 0°C and then 10.5 g (75 mmol) of benzoyl chloride are added. The mixture is stirred for 3 h at room temperature. 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 MgSC>4. The organic solvent

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

Yield: 10.4 g (33 mmol), 70% of theory. b) S-(2-cyano-3-bromo-phenyl)-benzenecarbothionate

20

[1245648-93-4]

In a baked 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 are added to 20 ml of degassed toluene under nitrogen and stirred at 100 °C for 24 h. The reaction mixture is cooled to room temperature. Diethyl ether (1000 ml) and saturated sodium chloride solution (1000 ml) are added and the mixture is stirred. The organic phase is separated and the aqueous phase is extracted with diethyl ether (2 x 1000 ml). The combined organic phases are dried over Na2SC>4 and the product is isolated by column chromatography.

35

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

In a heated flask under argon, 0.67 g (30 mmol) Pd(OAc)2, 1.69 g (6 mmol) PCya (tricyclohexylphosphine), 1.96 g (30 mmol) zinc powder and 3 g 4 Ä molecular sieve (MS4A) are placed in 1200 ml DMF. After stirring for 20 min at room temperature, 9.4 g (30 mmol) bromo-2-cyanophenyl benzoate are added and the mixture is then stirred at 100 C° overnight. The mixture is then treated with saturated NaCl solution and the aqueous phase is extracted with Et ₂ O (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

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

Analogously, the following brominated compounds are prepared:

20

d) 9-Bromo-2,4-diphenylbenzofuro[3,2-cf]pyrimidin

llnter Argon werden 107g (316 mmol) (3-Amino-4-chloro-2-benzofuranyl)phenyl- methanon und 104g (1015 mmol) Benzonitril in 1000 ml o-Xylol vorgelegt und mit 56 g (677 mmol) Natrium-2-methylpropan-2-olat versetzt. Die Mischung wird 5 Stunden bei 140°C gerührt. Es werden 30 ml Wasser am Wasserabscheider abgelassen und danach25

d) 9-Bromo-2,4-diphenylbenzofuro[3,2-cf]pyrimidine

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 under argon 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 are drained off at the water separator and then

5, a little acetone is added and the mixture is stirred for a further 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 and dried over MgSO4, filtered and the solvent is removed in vacuo. The residue is purified by column chromatography.

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

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e) 2-Chloro-4,8-diphenyl-benzofuro[3,2-d]pyrimidin

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

[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 atmosphere. 1.2 g (1 mmol) of tetrakis(triphenylphosphine)-palladium is added to the flask. The

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 MgSO4, 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.

Analogously, the following compounds are prepared:

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f) 2-Phenyl-4H-naphtho[1 ,2,3,4-def]carbazol l-

4H-naphtho[1,2,3,4-def]carbazol und 44.5 g (420 mmol, 2.00 eq.) Natriumcarbonat [CAS 497-19-8] werden in einer Mischung aus 1000 mL Dioxan [CAS 123-91-1], 1000 mL Toluol [CAS 108-88-3] und 400 mL Wasser suspendiert. Zu dieser Suspension werden 4.85 g (4.20 mmol; 0.02 eq.) Tetrakis(triphenylphosphin)-palladium(0) [CAS 14221-01-3] zugegeben, und die Reaktionsmischung wird 16 h unter Rückfluss erhitzt. Nach Erkalten35

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.) sodium carbonate [CAS 497-19-8] are suspended in a mixture of 1000 mL dioxane [CAS 123-91-1], 1000 mL toluene [CAS 108-88-3] and 400 mL water. 4.85 g (4.20 mmol; 0.02 eq.) tetrakis(triphenylphosphine)palladium(0) [CAS 14221-01-3] are added to this suspension and the reaction mixture is heated under reflux for 16 h. After cooling

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

The following compounds can be obtained analogously:

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, g ( mmo ) - ap o[ , , , - e ]car azo , g ( mmol) 1-Brom-3-lodbenzol, 22.4 g (162 mmol) Kaliumcarbonat, 1.84 g (8.1 mmol) 1 ,3-Di(2-pyridyl)-1,3-propandion, 1.55 g (8.1 mmol) Kupferiodid und 1000 mL DMF werden und 30 h unter Rückfluss erhitzt. Anschließend wird am Rotationsverdampfer bis zur Trocknen eingeengt. Der Rückstand wird in THF gelöst und über ein kurzes Kieselgel-Bett filtriert. Es wird dann das 35

, g ( mmo ) - 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. Then it is concentrated on a rotary evaporator until dry. The residue is dissolved in THF and filtered through a short bed of silica gel. The

15 solvents are removed using a vacuum. The solid is then recrystallized from heptane/THF and then extracted hot over aluminum oxide with heptane/toluene. The solid that precipitates on cooling is filtered and dried.

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

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h) 4H-Naphtho[1,2,3,4-otef]carbazol-3-phenylboronsäure

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

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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 treated 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 reach room temperature, cooled again to -78 °C and added then quickly with a mixture of 20 ml (176 mmol) trimethyl borate in 50 ml THF. After warming to -10 °C, hydrolyze with 135 ml 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 n-heptane, the colorless solid

5 is filtered off with suction, washed with n-heptane and dried in vacuo. Yield: 45 g (126 mmol), 97% of theory; purity: 99% according to HPLC.

The following connections can be made analogously:

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i) 4-(2,4-Diphenylbenzofuro[3,2-cf]pyrimidin-8-yl)4H-naphtho[1,2,3,4-c/ef]carbazol20

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

Path A for bromides:

[109606-75-9] E1

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.) Sodium terf-butylate [CAS 865-47-4] are dissolved in 500 mL orf/70-xylene [CAS 95-47-6]

35. 1.50 g (3.66 mmol; 9 mol%) of dicyclohexyl-(2',6'-dimethoxy-biphenyl-2-yl)-phosphane (SPhos) [CAS 657408-07-6] and 1.12 g (1.22 mmol, 3 mol%) of tris(dibenzylideneacetone)dipalladium [CAS 51364-51-3] are added to this suspension and the reaction mixture is heated under reflux for 16 h. The reaction mixture is cooled to room temperature and the solvent is removed under reduced pressure. The The resulting solid is washed with 300 mL 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 is obtained as a colorless solid 16 g (28 mmol; 70%).

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Path B for chlorides:

[109606-75-9]

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

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

20 (prepared from PdCI(allyl)]2 (5.8 mg, 0.025 mol%) and cBRIDP (22.2 mg, 0.1 mol%) in 3 ml THF and 11 ml 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 and the mixture was treated with 25 ml water and 1.7 g NH4CI (31.8 mmol) and stirred for 5 min at room temperature. The organic phase was separated and the solution

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%).

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.

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76.1 g (211 mmol; 1.00 eq.) 3-(4/7-naphtho[1,2,3,4-def|carbazole-4-yl)-phenylboronic acid, 101 g (253 mmol; 1.20 eq.) 9-bromo-2,4-diphenylbenzofuro[3,2-c(]pyrimidine and 44.5 g (420 mmol, 2.00 eq.) sodium carbonate are suspended in a mixture of 1000 mL dioxane, 1000 mL toluene and 400 mL water. 4.85 g (4.20 mmol; 0.02 eq.) tetrakis(triphenylphosphine)palladium(0) are added to this suspension and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated, filtered through silica gel, washed three times with 200 mL water and then evaporated to dryness. The yield is 93 g (147 mmol; 70% of theory).

The following compounds can be obtained analogously:

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. Then 120 mL (130 eq) of deuterium oxide [CAS 7789-20-0] is added dropwise at 0°C. After neutralization with a potassium sulfate solution, it 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 sublimated under high vacuum (p = 5 x 10' ⁷ mbar) (purity 99.9%). The following products are obtained analogously:

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

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

Then 3.5 (3.8 mmol) 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 Na2SC>4, 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 cabinet. The crude product is used in the next step without further purification.

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

63 g (156 mmol) 8-bromo-2,4-diphenylbenzofuro[3,2-d]pyrimidine, 50 g (170 mmol) 2-(3-fluorotriphenylen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 36 g (340 mmol) sodium carbonate are suspended in 1000 mL ethylene glycol diamine ether and 280 mL water. 1.8 g (1.5 mmol) tetrakis(triphenylphosphine)palladium(O) are added to this suspension and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is 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 sublimated under high vacuum (p = 5 x 10' ⁷ mbar) (purity 99.9%). The yield is 68 g (120 mmol), corresponding to 71% of theory.

n) 8-(3-(4H-Naphtho[1,2,3,4-def]carbazol-4-yl)triphenylen-2-yl)-2,4- diphenylbenzofuro[3,2-d]pyrimidin Analogously, the following compounds are prepared:

n) 8-(3-(4H-Naphtho[1,2,3,4-def]carbazol-4-yl)triphenylen-2-yl)-2,4-diphenylbenzofuro[3,2-d]pyrimidine

E37

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 are suspended in 1500 mL of N,N-dimethylformamide and the reaction mixture is heated under reflux at 150°C for 40 h. The reaction mixture is cooled to room temperature and 1500 ml of water are added. The precipitated solid is filtered off and 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 is obtained as a colorless solid 58 g (81 mmol; 85%).

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

o) 8-(3-(4H-Naphtho[1,2,3,4-def]carbazol-4-yl-d10)triphenylen-2-yl-

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

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. Then 120 mL (130 eq) of deuterium oxide [CAS 7789-20-0] are added dropwise at 0°C. After neutralization with a potassium sulfate solution, it 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 in a mixture with portions of H/D isotopomers and H/D isotopologues after chromatographic purification and finally sublimated under high vacuum (p = 5 x 10' ⁷ mbar) (purity 99.9%).

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

Activated carbon is dissolved in 400 g (502 mmol; 1.00 eq) deuterium oxide [CAS 7789-20-0] and 200 g (778 mmol; 1.55 eq) of toluene-d8 [CAS 2037-26-5] are suspended. The reaction mixture is stirred for 5 days at 165°C and increased 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 in a mixture with portions of H/D isotopomers and H/D isotopologues is obtained after further purification by extraction, recrystallization and sublimation.

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

production of OLEDs

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

Examples Ex1 to Ex8 show data from OLEDs according to the invention. Glass plates coated with structured ITO (indium tin oxide) with a thickness of 50 nm are used as the substrate for the OLEDs in Table 7.

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

All materials are thermally vapor-deposited in a vacuum chamber. The emission layer always consists of at least one matrix material (also known as host material) and an emitting dopant (dopant, emitter), which is mixed into the matrix material or materials by co-evaporation in a certain volume proportion. A specification such as SdT1:H2:TEG1 (32%:60%:8%) 30nm means that the material SdT1 is present in a volume proportion of 32% as host material 1, the compound H2 as host material 2 in a proportion of 60% and TEG1 in a proportion of 8% in a 30nm thick layer. Analogously, the hole injection layer (HIL) and the electron transport layer (ETL) can also consist of a mixture of two materials.

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 carried out assuming a Lambertian radiation characteristic. The electroluminescence spectra are determined at a luminance of 1000 cd/m ² and the CIE 1931 x and y color coordinates are calculated from this. The U10 in Table 8 refers to the voltage required for a current density of 10 mA/cm ² . EQE10 refers to 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 drops from an initial luminance LO (in cd/m ² ) to a certain proportion L1 (in cd/m ² ) when operated at a constant current density jo in mA/cm 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).

Use of mixtures according to the invention in OLEDs

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

The data of the various OLEDs are summarized in Table 8. Examples V1 to V8 are comparative examples according to the prior art, examples Ex1 to Ex8 show data from OLEDs according to the invention. The examples according to the invention show in particular a clear advantage in the service life of the device.

Table 7: Structure of the OLEDs

Tabelle 9: Verwendete Materialien, sofern nicht zuvor beschrieben

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 having 5 to 40 ring atoms which may be substituted by one or more radicals R ¹ ; R° is on each occurrence, identically or differently, selected from the group consisting of F, CI, Br, I, CN, NO ₂ , 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 may be substituted by one or more radicals R ² , where one or more non-adjacent CH ₂ groups are replaced by R ² C=CR ² , Si(R ² ) ₂ , C=O, C=S, C=NR ² , P(=O)(R ² ), SO, SO ₂ , NR ² , O, S or CONR ² and where one or more H atoms can be replaced by D, F, CI, Br, I, CN or NO ₂ , an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, each of which can be substituted by one or more radicals R ² , an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, which can be substituted by one or more radicals R ² , or an aralkyl or heteroaralkyl group having 5 to 40 ring atoms, which can be substituted by one or more radicals R ² ; R ¹ is on each occurrence the same or different and is selected from the group consisting of D, F, CI, Br, I, CN, NO ₂ , 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 may be substituted by one or more radicals R ² , where one or more non-adjacent CH ₂ groups are substituted by R ² can be replaced by C=CR ² , Si(R ² ) ₂ , C=O, C=S, C=NR ² , P(=O)(R ² ), SO, SO ₂ , NR ² , O, S or CONR ² and where one or more H atoms can be replaced by D, F, CI, Br, I, CN or NO ₂ , an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, each of which can be substituted by one or more R ² radicals, an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, which can be substituted by one or more R ² radicals, or an aralkyl or heteroaralkyl group having 5 to 40 ring atoms, which can be substituted by one or more R ² radicals;

* 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 by one or more radicals R ² ; [R#]a2 represents a monosubstitution, a disubstitution, the maximum allowed substitution or no substitution with R#; Ar is, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms which may be substituted by one or more radicals R; An, Ar2 are independently an aromatic or heteroaromatic ring system having 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 can be substituted with one or more residues R, or a heteroaromatic ring system with 5 to 40 ring atoms, which can be substituted with one or more residues 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, 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; (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 is a bond or one of the formulas L-1 to L-34, which may be substituted by one or more radicals R ¹ , where R ¹ has a meaning given in claim 1,

Vi represents O, S or Se and the dashed lines indicate the connection to the rest of formula (1). 3. A compound according to claim 1 or 2, wherein V is O. 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. 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 which exhibit 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. 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. 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 and is CH, CR ⁶ or N, where a maximum of 2 symbols X2 N can be used; * indicates the binding site to the formula (HH-4); U ¹ , U ² are, when occurring, a bond, O, S, C(R ⁷ ) ₂ or NR ⁷ ; R ⁶ is, on each occurrence, identical or different, 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 may in each case be substituted by one or more radicals R ⁷ and where one or more non-adjacent CH ₂ groups may be replaced by Si(R ⁷ ) ₂ , C=O, NR ⁷ , O, S or CONR ⁷ , or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R ⁷ ; two radicals R ⁶ can also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another; Ars, identical or different at each occurrence, independently represents an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be substituted by one or more radicals R ⁷ ; R ⁷ is, identically or differently on each occurrence, D, F, CI, Br, I, N(R ⁸ )2, CN, NO ₂ , 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) ₂ R ⁸ , OSO ₂ R 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, where the alkyl, alkenyl or alkynyl group may each be substituted by one or more radicals R ⁸ , where one or more non-adjacent CH ₂ groups are replaced by Si(R ⁸ ) ₂ , C=O, NR ⁸ , O, S or CONR ⁸ , or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, each of which may be substituted by one or more radicals R ⁸ , where R ⁸ is not H; two or more radicals R ⁷ can form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system with one another, preferably the radicals R ⁷ do not form such a ring system; R ⁸ is, identically or differently on each occurrence, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms can also be replaced by F; c, c1, c2 each independently on each occurrence is 0 or 1, where the sum of the indices on each occurrence is c+c1+c2 = 1; d, d1, d2 each independently on each occurrence is 0 or 1, where the sum of the indices on each occurrence is d+d1+d2 = 1; q, q1, q2 each independently on each occurrence is 0, 1, 2, 3 or 4; s is, identically or differently on each occurrence, 0, 1, 2, 3 or 4; t is, identically or differently on each occurrence, 0, 1, 2 or 3; u is the same or different at each occurrence and is 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 which is selected from the 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. Process 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. Process 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, one after the other or simultaneously with the light-emitting materials selected from the group of phosphorescent emitters, fluorescent emitters and/or emitters which exhibit TADF (thermally activated delayed fluorescence), are deposited from the gas phase.