WO2025051734A1 - Materials for organic electroluminescent devices - Google Patents

Abstract

The present invention relates to compounds containing at least one of indolocarbazole moiety Zⁱ, at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z^t represented by Formula (1), mixtures and electronic devices containing these compounds, in particular organic electroluminescence devices containing these compounds as matrix materials, electron transport materials or hole blocker materials.

Description

Materials for organic electroluminescent devices

Field of the Invention

The present invention relates to compounds containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) and electronic devices containing these compounds, in particular organic electroluminescence devices containing these compounds as matrix materials, optionally in combination with another compound.

Background of the Invention

Phosphorescent organometallic complexes are often used in organic electroluminescent devices (OLEDs). In general, there is still room for improvement with 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 in these materials can therefore also lead to significant improvements in the OLED properties.

According to the prior art, compounds containing indolocarbazole group and N-heteroaryl group are used as matrix materials.

WO18236092 A1 , US 20160163995 AA and US 2023019297 AA describe the compound containing indolocarbazole group, N-heteroaryl group and dibenzofuran group as as matrix materials.

WO1 8198844 A1 and US2013248849 AA describes the compound containing indolocarbazole group, N-heteroaryl group and phenyl group as as matrix materials.

However, there is still need for improvement in the case of use of these materials or in the case of use of mixtures of the materials, especially in relation to efficiency, operating voltage and/or lifetime of the electronic devices, in particular of the organic electroluminescent device.

The problem addressed by the present invention is therefore providing a host material which is suitable for use in an electronic device, especially in a fluorescent or phosphorescent organic electroluminescent device, and which lead to good device properties, especially with regard to an improved lifetime, and providing the corresponding electronic device.

It has now been found that this problem is solved, and the disadvantages from the prior art are eliminated, by the compound containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1). The use of such a compound for production of an electronic device leads to very good properties of these devices, especially with regard to lifetime, especially with improved efficiency and/or operating voltage. The advantages are especially also manifested in the presence of the combination of at least one compound containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) as the first host material and further compound as the second host material, for example in combination with one or more compounds of the formulae (HH- 1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6).

Summary of the Invention

The present invention therefore first provides a compound containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1):

where the groups and indices that occur are as follows:

Y¹¹ is S or O;

X¹¹ is CR¹¹ or N, X¹² is CR¹² or N, X¹³ is CR¹³ or N, X¹⁴ is CR¹⁴ or N, X¹⁵ is CR¹⁵ or N, X¹⁶ is CR¹⁶ or N, X¹⁷ is CR¹⁷ or N, X¹⁸ is CR¹⁸ or N, X¹⁹ is CR¹⁹ or N, X¹⁹ is CR¹⁹ or N, and X²⁰ is CR²⁰ or N, wherein at least one of X¹¹ to X²⁰ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’;

R¹¹ to R²⁰ at each instance are each independently H, D, F, Cl, Br, I, CHO, CN, N(R⁴)2, C(=O)R⁴, P(=O)(R⁴)₂, S(=O)R⁴, S(=O)₂R⁴, NO₂, Si(R⁴)₃, Ge(R⁴)₃, B(R⁴)₂, B(OR⁴)₂, OSO₂R⁴, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R⁴, where in each case one or more non-adjacent CH₂ groups may be replaced by R⁴C=CR⁴, C=C, Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C=O, C=S, C=Se, P(=O)(R⁴), SO, SO₂, O, S or CONR⁴ and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R⁴, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, which may be substituted by one or more radicals R⁴; wherein two of radicals R¹¹ to R²⁰ may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R⁴;

Lⁿ is the same or different at each instance and is a single bond 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 R⁵; na is 1 , 2 or 3;

* and *’ stand on each occurrence, a binding site to adjacent atom;

R⁴ and R⁵ at each instance are each independently H, D, F, Cl, Br, I, CHO, CN, N(Ar)₂, C(=O)Ar, P(=O)(Ar)₂, S(=O)Ar, S(=O)₂Ar, NO₂, Si(R )₃, Ge(R')₃, B(OR')₂, OSO₂R , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R', where in each case one or more non- adjacent CH₂ groups may be replaced by R'C=CR', C=C, Si(R')₂, Ge(R')₂, Sn(R')₂, C=O, C=S, C=Se, P(=O)(R'), SO, SO₂, O, S or CONR' and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, 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', or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, which may be substituted by one or more radicals R'; wherein R³ and R⁴ may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R’;

Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case also be substituted by one or more radicals R'; and

R is the same or different at each instance and is H, D, F, Cl, Br, I, CN, a straightchain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH2 groups may be replaced by SO, SO2, O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms.

The invention further provides a mixture containing at least one compound containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) as described above or hereinafter and at least one further compound and/or at least one solvent, wherein the further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, TADF (Thermally activated delayed fluorescence) emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, n-dopants, wide band gap materials, electron blocking materials and hole blocking materials.

The invention further provides a mixture containing at least one compound containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) as described above or hereinafter and at least one compound of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6)

, where the symbols and indices used are as follows. The invention further provides an electronic device containing at least one compound containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) as described above or described in following preferece or at least one mixture as described above or described in following preferece.

The invention further provides the use of a compound containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) as described above or described in following preferece in an electronic device.

Detailed Description of the Invention

"D" or "D-atom" in the context of this invention means deuterium.

"Indolocarbazole moiety" in the context of this invention means the moiety including an indolocarbazole group.

"N-heteroaryl moiety" in the context of this invention means the moiety including a heteroaryl group including at least one N atom as a ring formation atom.

An aryl group in the context of this invention contains 6 to 60 ring atoms, preferably carbon atoms. A heteroaryl group in the context of this invention contains 5 to 60 ring atoms, where the ring atoms include carbon atoms and at least one heteroatom, with the proviso that the sum total of carbon atoms and heteroatoms adds up to at least 5. The heteroatoms are preferably selected from N, O and/or S. An aryl group or heteroaryl group is understood here to mean either a simple aromatic cycle, i.e. phenyl, derived from benzene, or a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene, or a fused aryl or heteroaryl group, for example derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline. An aryl group having 6 to 18 carbon atoms is therefore preferably phenyl, naphthyl, phenanthryl or triphenylenyl, with no restriction in the attachment of the aryl group as substituent. The aryl or heteroaryl group in the context of this invention may bear one or more R radicals, where the substituent R is described below.

An aromatic ring system in the context of this invention contains 6 to 60 ring atoms in the ring system. The aromatic ring system also includes aryl groups as described above. An aromatic ring system having 6 to 18 carbon atoms is preferably selected from phenyl, fully deuterated phenyl, biphenyl, naphthyl, phenanthryl and triphenylenyl.

A heteroaromatic ring system in the context of this invention contains 5 to 60 ring atoms and at least one heteroatom. A preferred heteroaromatic ring system has 10 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 in the context of this invention is understood to mean a system which does not necessarily contain only aryl or heteroaryl groups, but in which it is also possible for a plurality of aryl or heteroaryl groups to be interrupted by a nonaromatic unit (preferably less than 10% of the atoms other than H), for example a carbon, nitrogen or oxygen atom or a carbonyl group. For example, systems such as 9,9'- spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ethers, stilbene, etc. shall thus also be regarded as aromatic or heteroaromatic ring systems in the context of this invention, and likewise systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group. In addition, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, for example biphenyl, terphenyl, quaterphenyl or bipyridine, are likewise encompassed by the definition of the aromatic or heteroaromatic ring system.

An aromatic or heteroaromatic ring system which has 5 to 60 ring atoms and may be joined to the aromatic or heteroaromatic system via any desired positions is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzofluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- ortrans-indenofluorene, cis- ortrans-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, benzopyrimidine, quinoxaline, 1 ,5-diazaanthracene, 2,7- diazapyrene, 2,3-diazapyrene, 1 ,6-diazapyrene, 1 ,8-diazapyrene, 4,5-diazapyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubine, 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 abbreviation Ar at each instance is in each case independently an aromatic or heteroaromatic ring system having 5 to 60 ring atoms and may be substituted by one or more R' radicals, where the details for the aromatic ring system or heteroaromatic ring system apply here correspondingly. The R’ radical or the R’ radicals has/have a definition as described above or described hereinafter. The abbreviation Ar at each instance is preferably in each case independently an aryl group which has 6 to 40 ring atoms and may be substituted by one or more R’ radicals, or a heteroaryl group having 5 to 40 ring atoms and containing O or S as heteroatom, which may be substituted by one or more R’ radicals, where the details for the aryl group or heteroaryl group and R’ as described above or hereinafter are applicable correspondingly.

The abbreviation Ars is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more nonaromatic R⁷ radicals; at the same time, two Ars radicals bonded to the same nitrogen atom, phosphorus atom or boron atom may also be bridged to one another by a single bond or a bridge selected from N(R⁷), C(R⁷)2, O and S, where the R⁷ radical or the substituents R⁷ has/have a definition as described above or hereinafter. Preferably, Ars is an aryl group having 6 to 20 ring atoms as described above.

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

In the context of the present invention, a straight-chain alkyl group having 1 to 40 C atoms, branched or cyclic alkyl group having 3 to 40 C atoms is understood to mean, for example, the 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, neopentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1 -methylcyclopentyl, 2-methylpentyl, n- heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1 -methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7- dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1 ,1- dimethyl-n-hex-1-yl, 1 , 1-dimethyl-n-hept-1-yl, 1 ,1-dimethyl-n-oct-1-yl, 1 ,1-dimethyl-n-dec- 1-yl, 1 ,1-dimethyl-n-dodec-1-yl, 1 ,1-dimethyl-n-tetradec-1-yl, 1 ,1-dimethyl-n-hexadec-1-yl, 1 ,1-dimethyl-n-octadec-1-yl, 1 , 1-diethyl-n-hex-1-yl, 1 , 1 -diethyl-n-hept-1 -yl, 1 , 1 -diethyl-n- oct-1-yl, 1 , 1-diethyl-n-dec-1-yl, 1 ,1-diethyl-n-dodec-1-yl, 1 , 1-diethyl-n-tetradec-1-yl, 1 ,1- diethyl-n-hexadec-1-yl, 1 ,1-diethyl-n-octadec-1-yl, 1-(n-propyl)cyclohex-1-yl, 1-(n- butyl)cyclohex-1-yl, 1-(n-hexyl)cyclohex-1-yl, 1-(n-octyl)cyclohex-1-yl and 1-(n- decyl)cyclohex-1-yl radicals.

A straight-chain alkoxy group having 1 to 40 C atoms or branched alkoxy group having 3 to 40 C atoms is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n- propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2-methylbutoxy.

A straight-chain thioalkyl group having 1 to 40 C atoms is understood to mean, for example, S-alkyl groups, for example thiomethyl, 1-thioethyl, 1-thio-i-propyl, 1-thio-n- propyl, 1-thio-i-butyl, 1-thio-n-butyl or 1 -thio-t-butyl.

An aryloxy or heteroaryloxy group having 5 to 60 ring atoms means O-aryl or O-heteroaryl and means that the aryl or heteroaryl group is bonded via an oxygen atom, where the aryl or heteroaryl group is defined as described above.

An aralkyl or heteroaralkyl group having 5 to 40 ring atoms means that an alkyl group as described above is substituted by an aryl group or heteroaryl group, where the aryl or heteroaryl group is defined as described above.

The wording that two or more radicals together may form a ring, in the context of the present description, shall be understood to mean, inter alia, that the two radicals are joined to one another by a chemical bond. This is illustrated by the following scheme:

In addition, however, the abovementioned wording shall also be understood to mean that, if one of the two radicals is hydrogen, the second radical binds to the position to which the hydrogen atom was bonded, forming a ring. This shall be illustrated by the following scheme:

In one embodiment of the compound or preferred embodiments of the host material of the compound above, all X¹¹ to X²⁰ is not N.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the N-heteroaryl moiety Z^h is selected from pyridine, pyrimidine and triazine, which may be substituted by one or more radicals R³, R³ is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, CN, N(R⁴)₂, C(=O)R⁴, P(=O)(R⁴)₂, S(=O)R⁴, S(=O)₂R⁴, NO₂, Si(R⁴)₃, Ge(R⁴)₃, B(R⁴)₂, B(OR⁴)₂, OSO₂R⁴, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R⁴, where in each case one or more non-adjacent CH₂ groups may be replaced by R⁴C=CR⁴, C=C, Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C=O, C=S, C=Se, P(=O)(R⁴), SO, SO₂, O, S or CONR⁴and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R⁴, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, which may be substituted by one or more radicals R⁴; wherein two of radicals R¹¹ to R²⁰ may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R⁴; and R⁴ has the definition given above or given hereinafter.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the indolocarbazole moiety Z' is represented by Formula (2):

Formula (2) Formula 2A wherein in Formula (2) and 2A, X^2a is CR^20a or C, X^2b is CR^20b or C, X^2c is CR^20c or C, and X^2d is CR^20d or C, X^2a and X^2b, X^2b and X^2c, and X^2c and X^2d are the same or different at each instance and are linked by a single bond or double bond, wherein X^2a and X^2b is C and X^2a--X^2b in Formula (2) is binding with the dotted line in Formula 2A, X^2b and X^2c is C and X^2b--X^2c in Formula (2) is binding with the dotted line in Formula 2A, or X^2c and X^2d is C and X^2c--X^2d in Formula (2) is binding with the dotted line in Formula 2A; R^20a, R^20b, R^20c, R^20d and R²¹ to R³⁰ at each instance are each independently H, D, F, Cl, Br, I, CHO, CN, N(R⁴)₂, C(=O)R⁴, P(=O)(R⁴)₂, S(=O)R⁴, S(=O)₂R⁴, NO₂, Si(R⁴)₃, Ge(R⁴)₃, B(R⁴)₂, B(OR⁴)₂, OSO₂R⁴, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R⁴, where in each case one or more non-adjacent CH2 groups may be replaced by R⁴C=CR⁴, C≡C, Si(R⁴)2, Ge(R⁴)2, Sn(R⁴)2, C=O, C=S, C=Se, P(=O)(R⁴), SO, SO₂, O, S or CONR⁴ and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R⁴, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, which may be substituted by one or more radicals R⁴; wherein two of radicals R¹¹ to R²⁰ may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R⁴; wherein at least one of R^20a, R^20b, R^20c, R^20d and R²¹ to R³⁰ is a binding site to the moiety Z^t represented by Formula (1) or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)na-*’; and R⁴, Lⁿ, na, *, and *’ have the definition given above or given hereinafter. In one embodiment of the compound or preferred embodiments of the host material of the compound above, the indolocarbazole moiety Zⁱ is represented by Formula 2-1:

wherein in Formula 2-1, R^20c, R^20d, and R²¹ to R³⁰ have the definition given above or given hereinafter. In one embodiment of the compound or preferred embodiments of the host material of the compound above, in Formula (2), Formula 2A, or Formula 2-1 , at least one of R²¹ and R²² is a binding site to the moiety Z* represented by Formula (1) or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the compound satisfies at least one of Conditions A and B:

<Condition A>

At least one of X¹¹ to X¹³ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition B>

At least one of X¹⁴ to X¹⁷ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, characterized in that the compound satisfies at least one of Conditions A-1 to A-3, B-1 and B-2, preferrably satisfies at least one of Conditions A-1 , A-2, A-3, and B-2, particularly preferrably satisfies at least one of Conditions A-1 and B-2, and very particularly preferrably satisfies Condition A-1 :

<Condition A-1 >

X¹¹ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition A-2>

X¹² is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition A-3>

X¹³ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition B-1 >

X¹⁴ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition B-2>

X¹⁵ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’. In one embodiment of the compound or preferred embodiments of the host material of the compound above, the compound satisfies at least one of Conditions 1-A-1 to 1-A-3, 1-B-1 , 1-B-2, 2-A-1 to 2-A-3, 2-B-1 and 2-B-2, preferrably satisfies at least one of Conditions 1-A- 1 , 1-A-2, 1-A-3, 1-B-2, 2-A-1 , 2-A-2, 2-A-3 and 2-B-2, particularly preferrably satisfies at least one of Conditions 1-A-1 , 1-B-2, 2-A-1 and 2-B-2, and very particularly preferrably satisfies at least one of Conditions 1-A-1 and 2-A-1 :

<Condition 1-A-1>

X¹¹ is not N and is a binding site to the indolocarbazole moiety Z' via linker *-(Lⁿ)_na-*’

<Condition 1-A-2>

X¹² is not N and is a binding site to the indolocarbazole moiety Z' via linker *-(Lⁿ)_na-*’ <Condition 1-A-3>

X¹³ is not N and is a binding site to the indolocarbazole moiety Z' via linker *-(Lⁿ)_na-*’ <Condition 1-B-1 >

X¹⁴ is not N and is a binding site to the indolocarbazole moiety Z' via linker *-(Lⁿ)_na-*’

<Condition 1-B-2>

X¹⁵ is not N and is a binding site to the indolocarbazole moiety Z' via linker *-(Lⁿ)_na-*’ <Condition 2-A-1>

X¹¹ is not N and is a binding site to the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition 2-A-2>

X¹² is not N and is a binding site to the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition 2-A-3>

X¹³ is not N and is a binding site to the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’

<Condition 2-B-1>

X¹⁴ is not N and is a binding site to the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition 2-B-2>

X¹⁵ is not N and is a binding site to the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’..

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the moiety Z‘ represented by Formula (1) is binding to either the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the compound satisfies only one of Conditions A-1 to A-3, B-1 and B-2. In one embodiment of the compound or preferred embodiments of the host material of the compound above, the compound satisfies only one of Conditions 1-A-1 to 1-A-3, 1-B-1 , 1- B-2, 2-A-1 to 2-A-3, 2-B-1 and 2-B-2.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the compound represented by Formula 1-1 or Formula 1-2:

wherein in Formulae 1-1 and 1-2,

X³¹ is CR³¹ or N, X³² is CR³² or N, X³³ is CR³³ or N, wherein at least one of X³¹ to X³³ is N;

R³¹ to R³⁵ at each instance are each independently H, D, F, Cl, Br, I, CHO, CN, N(R⁴)2, C(=O)R⁴, P(=O)(R⁴)₂, S(=O)R⁴, S(=O)₂R⁴, NO₂, Si(R⁴)₃, Ge(R⁴)₃, B(R⁴)₂, B(OR⁴)₂, OSO₂R⁴, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R⁴, where in each case one or more non- adjacent CH₂ groups may be replaced by R⁴C=CR⁴, C=C, Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C=O, C=S, C=Se, P(=O)(R⁴), SO, SO₂, O, S or CONR⁴and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R⁴, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, which may be substituted by one or more radicals R⁴; wherein two of radicals R¹¹ to R²⁰ may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R⁴;

L¹ to L³ at each instance are each independently refer to the definition of Lⁿ; a1 to a3 at each instance are each independently refer to the definition of na; and R⁴, Z‘ and Z' have the definition given above or given hereinafter.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, all X³¹ to X³³ are N.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, at least one of N atoms in the indolocarbazole moiety Z' is a binding site to the N-heteroaryl moiety Z^h or the moiety Z* represented by Formula (1).

In one embodiment of the compound or preferred embodiments of the host material of the compound above, one of N atoms in the indolocarbazole moiety Z' is a binding site to the N-heteroaryl moiety Z^h or the moiety Z* represented by Formula (1).

In one embodiment of the compound or preferred embodiments of the host material of the compound above, one of N atoms in the indolocarbazole moiety Z' is a binding site to the N-heteroaryl moiety Z^h and the other N atom in the indolocarbazole moiety Z' is a binding site to the moiety Z* represented by Formula (1).

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the compound satisfies at least one of Conditions C-1 and C-2: <Condition C-1>

One of N atoms in the indolocarbazole moiety Z' is a binding site to the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition C-2>

One of N atoms in the indolocarbazole moiety Z' is a binding site to the moiety Z‘ represented by Formula (1) via linker *-(Lⁿ)_na-*’.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the compound satisfies only one or both of Conditions C-1 and C-2.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the compound comprises at least one of deuterium.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the compound is partially deuterated or fully deuterated. In one embodiment of the compound or preferred embodiments of the host material of the compound above, the indolocarbazole moiety Z' comprises at least one of deuterium.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the N-heteroaryl moiety Z^h comprises at least one of deuterium.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the moiety Z* represented by Formula (1) comprises at least one of deuterium.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, (i) both the indolocarbazole moiety Z' and the N-heteroaryl moiety Z^h comprise at least one of deuterium, (ii) both the indolocarbazole moiety Z' and the moiety Z* represented by Formula (1) comprise at least one of deuterium, (iii) both the N- heteroaryl moiety Z^h and the moiety Z* represented by Formula (1) comprise at least one of deuterium, or (iv) both the indolocarbazole moiety Z', the N-heteroaryl moiety Z^h and the moiety Z* represented by Formula (1) comprise at least one of deuterium.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, at least one of R¹¹ to R²⁰ in Formula (1) comprises at least one of deuterium, wherein at least one of R¹¹ to R²⁰ is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, at least one of R^20a, R^20b, R^20c, R^20d and R²¹ to R³⁰ in Formula (2) and Formula 2A, or at least one of R^20c, R^20d, and R²¹ to R³⁰ in Formula 2-1 comprises at least one of deuterium, wherein at least one of R^20a, R^20b, R^20c, R^20d and R²¹ to R³⁰ is a binding site to the moiety Z‘ represented by Formula (1) or the N-heteroaryl moiety Z^h via linker *- (Lⁿ)_na-*’.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, at least one of R³¹ to R³⁵, L¹ to L³, Z‘ and Z' in Formula 1-1 or 1-2 comprises at least one of deuterium.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, the degree of deuteration of the compound is about 1 mol% to 100 mol%, is preferably at least 10 mol% to 100 mol%, is particularly preferably 50 mol% to 95 mol% and is particularly preferably 70 mol% to 90 mol%.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, R¹¹ to R²⁰ at each instance are each independently H, D, F, CN, Si(R³)3, N(R³)₂, Ge(R³)3, B(R³)₂, straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, each of which may be substituted by one or more radicals R³, where in each case one or more non-adjacent CH₂ groups may be replaced by R³C=CR³ or 0=0; aromatic ring systems having 6 to 40 ring atoms or heteroaromatic ring systems having 5 to 40 ring atoms, which may in each case be substituted by one or more radicals R³; or an aryloxy group having 6 to 40 ring atoms, which may in each case be substituted by one or more radicals R³, and R³ has the definition given above or given hereinafter.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, R^20a, R^20b, R^20c, R^20d and R²¹ to R³⁰ at each instance are each independently H, D, F, CN, Si(R³)3, N(R³)₂, Ge(R³)3, B(R³)₂, straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, each of which may be substituted by one or more radicals R³, where in each case one or more non-adjacent CH₂ groups may be replaced by R³C=CR³ or C=C; aromatic ring systems having 6 to 40 ring atoms or heteroaromatic ring systems having 5 to 40 ring atoms, which may in each case be substituted by one or more radicals R³; or an aryloxy group having 6 to 40 ring atoms, which may in each case be substituted by one or more radicals R³, and R³ has the definition given above or given hereinafter. More preferred, R²¹ and R²² are identically or differently at each occurrence, aromatic ring systems having 6 to 40 ring atoms, heteroaromatic ring systems having 5 to 40 ring atoms or a binding site to the moiety Z* represented by Formula (1) or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, R³¹ to R³⁵ at each instance are each independently H, D, F, CN, Si(R³)3, N(R³)₂, Ge(R³)3, B(R³)₂, straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, each of which may be substituted by one or more radicals R³, where in each case one or more non- adjacent CH₂ groups may be replaced by R³C=CR³ or C=C; aromatic ring systems having 6 to 40 ring atoms or heteroaromatic ring systems having 5 to 40 ring atoms, which may in each case be substituted by one or more radicals R³; or an aryloxy group having 6 to 40 ring atoms, which may in each case be substituted by one or more radicals R³, and R³ has the definition given above or given hereinafter.

In one embodiment of the compound or preferred embodiments of the host material of the compound above, R⁴ and R⁵ at each instance are each independently H, D, F, CN, Si(R’)3, N(R’)₂, Ge(R‘)3, straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, each of which may be substituted by one or more radicals R’, where in each case one or more non- adjacent CH₂ groups may be replaced by R’C=CR’ or 0=0; aromatic ring systems having 6 to 40 ring atoms or heteroaromatic ring systems having 5 to 40 ring atoms, which may in each case be substituted by one or more radicals R’; or an aryloxy group having 6 to 40 ring atoms, which may in each case be substituted by one or more radicals R’, and R’ has the definition given above or given hereinafter.

Examples of suitable compounds are the structures listed below in Table 1.

Table 1

w w ro ro cn cn o cn o cn o

The compounds according to the invention can be prepared by means of known synthesis methods, such as following methods. The following synthesis schemes show the compounds used to simplify structures with a small number of substituents. This does not exclude the presence of any other substituents in the procedures.

Particularly suitable compounds of the formula (1), are the compounds E1 to E24 of table o

Table 2

The compounds of the invention can be prepared by synthesis steps known to those skilled in the art, for example bromination, Suzuki coupling, Ullmann coupling, Hartwig- Buchwald coupling, etc.

The methods shown for the synthesis of the compounds according to the invention are to be understood by way of example. The skilled person may develop alternative methods of synthesis within the framework of his general knowledge. (R¹ corresponds to R¹¹ to R²⁰, R² corresponds to R^20a, R^20b, R^20c, R^20d and R²¹ to R³⁰, R³ corresponds to R³¹ to R³⁵, and X corresponds to a halogen atom in Schemes 1 and 2)

Scheme 1

Detailed reaction conditions are known to those skilled in the art or are described in the example part.

It is possible by these processes, if necessary followed by purification, for example recrystallization or sublimation, to obtain the compounds in high purity, preferably more than 99% (determined by means of ¹H NMR and/or HPLC).

For the processing of the compounds of the invention from liquid phase, for example by spin-coating or by printing methods, formulations of the compounds of the invention or of mixtures of compounds of the invention with further functional materials, such as matrix materials, fluorescent emitters, phosphorescent emitters and/or emitters that exhibit TADF, are required. These formulations may, for example, be solutions, dispersions or emulsions. For this purpose, it may be preferable to use mixtures of two or more solvents. 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, especially 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, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2- methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1 -ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate or mixtures of these solvents.

The inventive compounds, (optionally the compounds of formulae 1-1 or 1-2) as described above or described as preferred, are suitable for use in an organic electroluminescent device, especially as matrix material.

When the compound of the invention is used as matrix material or, synonymously, host material in an emitting layer, it is preferably used in combination with a further compound. The invention therefore further provides a mixture containing at least one inventive compound or at least one preferred compound of the formulae 1-1 or 1-2 as defined, or a compound from table 1 or one of compounds E1 to E24 and at least one further compound selected from the group of the matrix materials, phosphorescent emitters, fluorescent emitters and/or emitters that exhibit TADF (thermally activated delayed fluorescence). Suitable matrix materials and emitters that can be used in this mixture of the invention are described hereinafter.

The present invention likewise further provides a formulation containing at least one compound of the invention, as described above, or a mixture of the invention, as described above, and at least one solvent. The solvent may be an abovementioned solvent or a mixture of these solvents.

The present invention further provides an organic electronic device containing an anode, a cathode and at least one organic layer, containing at least one inventive compound or at least one preferred compound of the formulae 1-1 or 1-2 as defined, or a compound from table 1 or one of compounds E1 to E24.

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

The organic electronic device is preferably an organic electroluminescent device.

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

The organic layer of the device of the invention preferably comprises, as well as a lightemitting layer (EML), a hole injection layer (HIL), a hole transport layer (HTL), a hole blocker layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), an exciton blocker layer, an electron blocker layer and/or charge generation layers. It is also possible for the device of the invention to include two or more layers from this group, preferably selected from EML, HIL, HTL, ETL, EIL and HBL. It is likewise possible for interlayers having an exciton-blocking function, for example, to be introduced between two emitting layers.

If a plurality of emission layers are present, these preferably have several emission maxima between 380 nm and 750 nm overall, such that the overall result is white emission; in other words, various emitting compounds which may fluoresce or phosphoresce are used in the emitting layers. It is also possible for two or more fluorescent and/or phosphorescent compounds to be present in an emitting layer. Especially preferred are systems having three emitting layers, where the three layers show blue, green and orange or red emission. As an alternative to the combination as described above, an emitting layer may also show yellow emission. Combinations of this kind are known to those skilled in the art. The organic electroluminescent device of the invention may also be a tandem electroluminescent device, especially for white-emitting OLEDs.

The device may also comprise inorganic materials or else layers formed entirely from inorganic materials.

It presents no difficulties at all to the person skilled in the art to consider a multitude of materials known in the prior art in order to select suitable materials for use in the abovedescribed layers of the organic electroluminescent device. The person skilled in the art here will reflect in a customary manner on the chemical and physical properties of materials, since he knows that the materials interact with one another in an organic electroluminescent device. This relates, for example, to the energy levels of the orbitals (HOMO, LUMO) or else the triplet and singlet energy levels, but also other material properties.

The inventive compound as described above or as described as preferred can be used in different layers, according to the exact structure. Preference is given to an organic electroluminescent device containing the inventive compound or the above-recited preferred embodiments in an emitting layer as matrix material for fluorescent emitters, phosphorescent emitters or for emitters that exhibit TADF (thermally activated delayed fluorescence), especially for phosphorescent emitters. In addition, the compound of the invention can also be used in an electron transport layer and/or in a hole transport layer and/or in an exciton blocker layer and/or in a hole blocker layer. Particular preference is given to using the compound of the invention as matrix material in an emitting layer or as electron transport material or hole blocker material in an electron transport layer or hole blocker layer.

The present invention further provides an organic electronic device as described above, wherein the organic layer comprises at least one light-emitting layer containing at least one inventive compound or at least one preferred compound of the formulae 1-1 or 1-2 as defined, or a compound from table 1 or one of compounds E1 to E24.

In one embodiment of the invention, for the device of the invention, at least one further matrix material is selected in the light-emitting layer, and this is used together with inventive compounds as described above or described as preferred or with the compounds from table 1 or the compounds E1 to E24.

The present invention accordingly further provides an organic electronic device as described above, wherein the organic layer comprises at least one light-emitting layer containing at least one inventive compound or at least one preferred compound of the formulae 1-1 or 1-2 as defined, or a compound from table 1 or one of compounds E1 to E24, and at least one further matrix material.

The present invention accordingly further provides an organic electronic device as described above, wherein the organic layer comprises at least one light-emitting layer containing at least one inventive compound or at least one preferred compound of the formulae 1-1 or 1-2 as defined, or a compound from table 1 or one of compounds E1 to E24, and two further matrix materials.

Suitable matrix materials that can be used in combination with the compounds of the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, biscarbazoles, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasilole or tetraazasilole derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives or dibenzofuran derivatives. It is likewise possible for a further phosphorescent emitter having shorter-wavelength emission than the actual emitter to be present as co-host in the mixture, or a compound not involved in charge transport to a significant extent, if at all, for example a wide band-gap compound. A wide-band gap material is understood herein to mean a material within the scope of the disclosure of US 7,294,849 which is characterized by a band gap of at least 3.5 eV, the band gap being understood to mean the gap between the HOMO and LUMO energy of a material.

Particularly suitable hole-transporting materials that can advantageously be combined with inventive compound or compounds of the formulae 1-1 or 1-2 as defined, as described above or described with preference, in a mixed matrix system may be selected from the compounds of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), as described hereinafter.

The invention accordingly further provides an organic electronic device containing 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 comprises at least one inventive compound as matrix material 1, as described above or as described with preference, and at least one compound of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) as matrix material 2,

, where the symbols and indices used are as follows:

A¹ is C(R⁷)₂, NR⁷, O or S;

L is a bond, O, S, C(R⁷)₂ or NR⁷;

A at each instance is 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 instance and is CH, CR⁶ or N, where not more than 2 symbols X2 can be N;

* indicates the binding site to the formula (HH-4);

II¹, II² where they occur are a bond, O, S, C(R⁷)2 or NR⁷;

R⁶ at each instance is the same or different and is D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group made in each case be substituted by one or more R⁷ radicals and where one or more nonadjacent CH2 groups may be replaced by Si(R⁷)2, C=O, NR⁷, O, S or CONR⁷, or an aromatic or heteroaromatic ring system which has 5 to 60 ring atoms and may be substituted in each case by one or more R⁷ radicals; it is also possible here for two R⁶ radicals together to form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;

Ars is the same or different at each instance and is independently an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R⁷ radicals;

R⁷ is the same or different at each instance and is D, F, Cl, Br, I, N(R⁸)2, CN, NO2, OR⁸, SR⁸, Si(R⁸)₃, B(OR⁸)₂, C(=O)R⁸, P(=O)(R⁸)₂, S(=O)R⁸, S(=O)₂R⁸, OSO2R⁸, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R⁸ radicals and where one or more nonadjacent CH2 groups may be replaced by Si(R⁸)2, C=O, NR⁸, O, S or CONR⁸, or an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted in each case by one or more R⁸ radicals; at the same time, two or more R⁷ radicals together may form an aromatic, heteroaromatic, aliphatic or heteroaromatic ring system; preferably, the R⁷ radicals do not form any such ring system; R⁸ is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; c, c1 , c2 at each instance are each independently 0 or 1 , where the sum total of the indices at each instance c+c1+c2 = 1 ; d, d1 , d2 at each instance are each independently 0 or 1 , where the sum total of the indices at each instance d+d1+d2 = 1 ; q, q1 , q2 at each instance is independently 0, 1 , 2, 3 or 4; s is the same or different at each instance and is 0, 1 , 2, 3 or 4; t is the same or different at each instance and is 0, 1 , 2 or 3; u is the same or different at each instance and is 0, 1 or 2; u1 , u2 at each instance are each independently 0 or 1 , where the sum total u1 + u2 = 1 ; and v is 0, 1 , 2 or 3.

In compounds of the formulae (HH-1), (HH-2), (HH-3), (HH-5) or (HH-6), s is preferably 0 or 1 when the R⁶ radical is not D, or more preferably 0.

In compounds of the formulae (HH-1), (HH-2) or (HH-3), t is preferably 0 or 1 when the R⁶ radical is not D, or more preferably 0.

In compounds of the formulae (HH-1), (HH-2), (HH-3) or (HH-5), u is preferably 0 or 1 when the R⁶ radical is not D, or more preferably 0.

The sum total of the indices s, t and u in compounds of the formulae (HH-1), (HH-2), (HH- 3), (HH-5) or (HH-6) is preferably not more than 6, especially preferably not more than 4 and more preferably not more than 2. This is preferably the case when R⁶ is not D.

In compounds of the formula (HH-4), c, c1 , c2 at each instance are each independently 0 or 1 , where the sum total of the indices at each instance c+c1+c2 is 1. c2 is preferably defined as 1.

In compounds of the formula (HH-4), L is preferably a single bond or C(R⁷)2 where R⁷ has a definition given above; more preferably, L is a single bond.

In formula (HH-4-1), v is preferably 0 or 1 when the R⁶ radical is not D.

In formula (HH-4-2), II¹ or II² where they occur are preferably a single bond or C(R⁷)2 where R⁷ as a definition given above; more preferably, II¹ or II² where they occur are a single bond.

In formula (HH-4-2), q, q1 , q2 are preferably 0 or 1 when the R⁶ radical is not D. In a preferred embodiment of the compounds of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) that can be combined in accordance with the invention with inventive compounds or preferred inventive compounds, as described above, R⁶ is the same or different at each instance and is selected from the group consisting of D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl group may in each case be substituted by one or more R⁷ radicals, or an aromatic heteroaromatic ring system which has 5 to 60 aromatic ring atoms, preferably 5 to 40 ring atoms, and may be substituted in each case by one or more R⁷ radicals.

In a preferred embodiment of the compounds of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) that can be combined in accordance with the invention with inventive compounds or preferred inventive compounds, as described above, R⁶ is the same or different at each instance and is selected from the group consisting of D or an aromatic heteroaromatic ring system which has 6 to 30 ring atoms and may be substituted by one or more R⁷ radicals.

Preferably, Ars in compounds of the formulae (HH-1), (HH-2), (HH-3), (HH-5) or (HH-6) is selected from phenyl, biphenyl, especially ortho-, meta- or para-biphenyl, terphenyl, especially ortho-, meta- or para-terphenyl or branched terphenyl, quaterphenyl, especially ortho-, meta- or para-quaterphenyl or branched quaterphenyl, fluorenyl which may be joined via the 1 , 2, 3 or 4 position, spirobifluorenyl which may be joined via the 1 , 2, 3 or 4 position, naphthyl, especially 1- or 2-bonded naphthyl, or radicals derived from indole, benzofuran, benzothiophene, carbazole which may be joined via the 1 , 2, 3 or 4 position, dibenzofuran which may be joined via the 1 , 2, 3 or 4 position, dibenzothiophene which may be joined 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 R⁷ radicals. Ars is preferably unsubstituted.

When A¹ in formula (HH-2) or (HH-3) or (HH-6) is NR⁷, the substituent R⁷ bonded to the nitrogen atom is preferably an aromatic or heteroaromatic ring system which has 5 to 24 aromatic ring atoms and may also be substituted by one or more R⁸ radicals. In a particularly preferred embodiment, this substituent R⁷ is the same or different at each instance and is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, especially having 6 to 18 aromatic ring atoms. Preferred embodiments of R⁷ 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 R⁸ radicals.

When A¹ in formula (HH-2) or (HH-3) or (HH-6) is C(R⁷)2, the substituents R⁷ bonded to this carbon atom are preferably the same or different at each instance and are a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more R⁵ radicals. Most preferably, R⁷ is a methyl group or a phenyl group. In this case, the R⁷ radicals together may also form a ring system, which leads to a spiro system.

In a preferred embodiment of the compounds of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), these compounds are partly or fully deuterated, more preferably fully deuterated.

The preparation of the compounds of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6) is generally known, and some of the compounds are commercially available.

Compounds of the formula (HH-4) are disclosed, for example, in W02021/180614, pages 110 to 119, especially as examples on pages 120 to 127. The preparation thereof is disclosed in W02021/180614 A1 on page 128, and in the synthesis examples on pages 214 to 218.

The preparation of the triarylamines of the formula (HH-6) is known to the person 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 of the same chemical base structure that differ merely by the level of deuteration.

In a preferred embodiment of the at least one further matrix material, this is a mixture of deuterated compounds of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6), as described above, wherein the deuteration level of these compounds is at least 50% to 90%, preferably 70% to 100%.

In a preferred embodiment of the at least one further matrix material, this is a mixture of deuterated compounds of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and/or (HH-6), as described above, wherein the deuteration level of these compounds is at least 50% to 90%, preferably 70% to 100%. Corresponding deuteration methods are known to the person skilled in the art and are described, for example, in KR2016041014 A, WO2017/122988 A1 , KR2020052820 A, KR101978651 B1 and WO2018/110887 A1 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 of deuterating a compound by exchange of one or more hydrogen atoms for deuterium atoms is a treatment of 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 deuterium atoms and is able to release them under suitable conditions.

The platinum catalyst is preferably dry platinum on charcoal, preferably 5% dry platinum on charcoal. The palladium catalyst is preferably dry palladium on charcoal, preferably 5% dry palladium on charcoal. 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, where the fully deuterated solvent here is not restricted. 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 conducted with heating, more preferably with heating to temperatures between 100°C and 200°C.ln addition, the reaction is preferably conducted under pressure.

Examples of suitable further matrix materials for a combination with compounds of the formula (1), as described above or described as preferred, are the compounds described in WO2019/229011 A1 , table 3, pages 137 to 203, which may also be partly or fully deuterated.

Examples of suitable further matrix materials for a combination with compounds of the formula (1) or preferred compounds of the formula (1), as described above or described as preferred, 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 partly or fully deuterated.

Examples of suitable further matrix materials for a combination with inventive compounds or preferred inventive compounds, as described above or described as preferred, are the compounds described in WO2011/088877 A1 , table on page 30, compounds 1 to 166, which may also be partly or fully deuterated.

Examples of suitable further matrix materials for a combination with inventive compounds or preferred inventive compounds, as described above or described as preferred, are the compounds described in WO2011/128017 A1 , table on page 23, compounds 1 to 151 , which may also be partly or fully deuterated.

Examples of suitable further matrix materials for a combination with inventive compounds or preferred inventive compounds, as described above or described as preferred, 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],

For a combination with inventive compounds or preferred compounds of the formulae 1-1 or 1-2, as described above or described with preference, especially suitable compounds are those of the formula (HH-1) and/or of the formula (HH-4) and/or of the formula (HH-5), as described above or described as preferred.

For a combination with inventive compounds or preferred compounds of the formulae 1-1 or 1-2, as described above or described with preference, especially suitable compounds are those of the formula (HH-1) in which at least one Ars group is a heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R⁷ radicals and/or compounds of the formula (HH-4) and/or compounds of the formula (HH-5).

For a combination with inventive compounds or preferred compounds of the formulae 1-1 or 1-2, as described above or described with preference, very particular preference is given to compounds of the formula (HH-4) or (HH-5).

Further examples of suitable host materials of the formulae (HH-1), (HH-2), (HH-3), (HH- 4), (HH-5) and (HH-6) for a combination with inventive compounds or preferred compounds of the inventive compounds or formula 1-1 or 1-2, as described above or described as preferred, are the structures in table 3 and table 4 that are given below.

Table 3:

Particularly suitable compounds of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6) that are selected in accordance with the invention and are preferably used in combination with at least one inventive compound in the electroluminescent device of the invention are the compounds in table 4.

Table 4:

The aforementioned host materials of the inventive compounds or formulae 1-1 or 1-2 and the embodiments thereof that are described as preferred or the compounds from table 1 and compounds E1 to E24 can be combined as desired in the device of the invention with the aforementioned matrix materials/host materials, the matrix materials/host materials of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) and their embodiments in table 3 that are described as preferred or the compounds from table 3, or compounds H1 to H33.

Very particularly preferred mixtures of the inventive compounds with the host materials of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) for the device of the invention are obtained by combination of the compounds E1 to E24 with the compounds H1 to H33 as shown hereinafter in table 5. The first mixture M1, for example, is a combination of compound E1 with H1. Table 5:

The concentration of the host material of the inventive compound or formulae 1-1 or 1-2 as described above or described as preferred in the mixture of the invention or in the lightemitting layer of the device of the invention is typically in the range from 5% by weight to 90% by weight, preferably in the range from 10% by weight to 85% by weight, more preferably in the range from 20% by weight to 85% by weight, even more preferably in the range from 30% by weight to 80% by weight, very especially preferably in the range from 20% by weight to 60% by weight and most preferably in the range from 30% by weight to 50% by weight, based on the overall mixture or based on the overall composition of the light-emitting layer.

The concentration of the sum total of all host materials of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), as described above or described as preferred, in the mixture of the invention or in the light-emitting layer of the device of the invention is typically in the range from 10% by weight to 95% by weight, preferably in the range from 15% by weight to 90% by weight, more preferably in the range from 15% by weight to 80% by weight, even more preferably in the range from 20% by weight to 70% by weight, very especially preferably in the range from 40% by weight to 80% by weight and most preferably in the range from 50% by weight to 70% by weight, based on the overall mixture or based on the overall composition of the light-emitting layer. The present invention also relates to a mixture which, as well as the aforementioned host materials of inventive compounds, called host material 1 hereinafter, and the host material of at least one of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), called host material 2 hereinafter, as described above or described as preferred, also comprises at least one phosphorescent emitter.

The present invention also relates to a mixture selected from M1 to M693 that also comprises at least one phosphorescent emitter.

The present invention also relates to an organic electroluminescent device as described above or described as preferred, wherein the light-emitting layer, as well as the aforementioned host materials of the formulae (1) and at least one of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), as described above or described as preferred, especially the material combinations M1 to M693, also comprises at least one phosphorescent emitter.

The term “phosphorescent emitters” typically encompasses compounds where the light is emitted through a spin-forbidden transition from an excited state having higher spin multiplicity, i.e. a spin state > 1 , for example through a transition from a triplet state or a state having an even higher spin quantum number, for example a quintet state. This is preferably understood to mean a transition from a triplet state.

Suitable phosphorescent emitters (= triplet emitters) are especially compounds which, when suitably excited, emit light, preferably in the visible region, and also contain at least one atom of atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially a metal having this atomic number. Preferred phosphorescence emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium or platinum. In the context of the present invention, all luminescent compounds containing the abovementioned metals are regarded as phosphorescent emitters.

In general, all phosphorescent complexes as used for phosphorescent OLEDs according to the prior art and as known to those skilled in the art in the field of organic electroluminescent devices are suitable. Preferred phosphorescent emitters according to the present invention conform to the formula (Illa)

Formula (Illa) where the symbols and indices for this formula (Illa) are defined as follows: n+m is 3, n is 1 or 2, m is 2 or 1,

X is the same or different at each instance and is N or CR,

R is the same or different at each instance and is H, D, F, CN or a branched or linear alkyl group having 1 to 10 carbon atoms or a partly or fully deuterated, branched or linear alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, which may be partly or fully substituted by deuterium, or an aromatic heteroaromatic ring system which has 5 to 60 ring atoms and may be partly or fully substituted by deuterium.

The invention accordingly further provides an organic electroluminescent device as described above or described as preferred, characterized in that the light-emitting layer, as well as the host materials 1 and 2, comprises at least one phosphorescent emitter conforming to the formula (Illa) as described above.

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

In emitters of the formula (Illa), preferably, one X is selected from N and the other X are CR, or all X are the same or different at each instance and are CR.

In emitters of the formula (Illa), at least one R is preferably different from H. In emitters of the formula (Illa), preferably two R are different from H and have one of the other definitions given above for the emitters of the formula (Illa).

Preferred phosphorescent emitters according to the present invention conform to the formulae (I), (II), (III), (IV) or (V)

Formula

where the symbols and indices for these formulae (I), (II), (III), (IV) and (V) are defined as follows:

Ri is H or D, R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 carbon atoms or a partly or fully deuterated branched or linear alkyl group having 1 to 10 carbon atoms or a cycloalkyl group which has 4 to 10 carbon atoms and may be partly or fully substituted by deuterium.

Preferred phosphorescent emitters according to the present invention conform to the formulae (VI), (VII) or (VIII)

follows:

Ri is H or D, R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 carbon atoms or a partly or fully deuterated branched or linear alkyl group having 1 to 10 carbon atoms or a cycloalkyl group which has 4 to 10 carbon atoms and may be partly or fully substituted by 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 description by this reference.

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

Table 6:



In the mixtures of the invention or in the light-emitting layer of the device of the invention, any mixture selected from the sum of the mixtures M1 to M693 is preferably combined with a compound of the formula (Illa) or a compound of the formulae (I) to (VIII) or a compound from table 6.

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

A yellow-emitting layer is understood here to mean a layer having a photoluminescence maximum within the range from 540 to 570 nm. An orange-emitting layer is understood to mean a layer having a photoluminescence maximum within the range from 570 to 600 nm. A red-emitting layer is understood to mean a layer having a photoluminescence maximum within the range from 600 to 750 nm. A green-emitting layer is understood to mean a layer having a photoluminescence maximum within the range from 490 to 540 nm. A blueemitting layer is understood to mean a layer having a photoluminescence maximum within the range from 440 to 490 nm. The photoluminescence maximum of the layer is determined here by measuring the photoluminescence spectrum of the layer having a layer thickness of 50 nm at room temperature, where the layer comprises the inventive combination of the host material 1 of the inventive compound or formulae 1-1 or 1-2 and of the host material 2 consisting of at least one of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) and (HH-6), and the corresponding emitter.

The photoluminescence spectrum of the layer is recorded, for example, with a commercial photoluminescence spectrometer.

The photoluminescence spectrum of the emitter chosen is generally measured in oxygen- free solution, 10^-5 molar, at room temperature, a suitable solvent being any in which the chosen emitter dissolves in the concentration mentioned. Particularly suitable solvents are typically toluene or 2-methyl-THF, but also dichloromethane. Measurement is effected with a commercial photoluminescence spectrometer. The triplet energy T1 in eV is determined from the photoluminescence spectra of the emitters. First the peak maximum Plmax. (in nm) of the photoluminescence spectrum is determined. The peak maximum Plmax. (in nm) is then converted to eV by: E(T 1 in eV) = 12401 E(T 1 in nm) = 12401 PLmax. (in nm).

Preferred phosphorescent emitters are accordingly yellow emitters, preferably of the formula (Illa), of the formulae (I) to (VIII) or from table 6, the triplet energy Ti of which is preferably ~2.3 eV to ~2.1 eV.

Preferred phosphorescent emitters are accordingly green emitters, preferably of the formula (Illa), of the formulae (I) to (VIII) or from table 6, the triplet energy Ti of which is preferably ~2.5 eV to ~2.3 eV.

Particularly preferred phosphorescent emitters are accordingly green emitters, preferably of the formula (Illa), of the formulae (I) to (VIII) or from table 6 as described above, the triplet energy Ti of which is preferably ~2.5 eV to ~2.3 eV.

Most preferably, green emitters, preferably of the formula (Illa), of the formulae (I) to (VIII) or from table 6, as described above, are selected for the mixture of the invention or emitting layer of the invention.

It is also possible for fluorescent emitters to be present in the light-emitting layer of the device of the invention or in the mixture of the invention.

Preferred fluorescent emitting compounds are selected from the class of the arylamines, where preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, more preferably having at least 14 ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines 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 anthracenediamine is understood to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10 positions. Aromatic pyreneamines, pyrenediamines, chryseneamines and chrysenediamines are defined analogously, where the diarylamino groups are bonded to the pyrene preferably in the 1 position or 1,6 positions. Further preferred emitting compounds are indenofluoreneamines or -diamines, benzoindenofluoreneamines or - diamines, and dibenzoindenofluoreneamines or -diamines, and indenofluorene derivatives having fused aryl groups. Likewise preferred are pyrenearylamines. Likewise preferred are benzoindenofluoreneamines, benzofluoreneamines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives joined to furan units or to thiophene units. The light-emitting device or the mixture of the invention may additionally also comprise materials that exhibit TADF (thermally activated delayed fluorescence).

In a further preferred embodiment of the invention, the at least one light-emitting layer of the organic electroluminescent device may have three or four different matrix materials, preferably three different matrix materials. These corresponding mixed matrix systems may consist of the matrix materials described for the host material 1 and the host material 2, but they may also comprise, as a third or fourth matrix material, for example alongside a host material 1 or host material 2, wide-band-gap materials, bipolar host materials, electron transport materials (ETM) or hole transport materials (HTM).

Preferably, the mixed matrix system is optimized for an emitter of the formula (Illa), of the formulae (I) to (VIII), or for an emitter from table 6.

In one embodiment of the present invention, the mixture, aside from the constituents of the host material of the inventive compound and the host material 2 as described above or described with preference, does not comprise any further constituents, i.e. functional materials. These are material mixtures that are used as such for production of the lightemitting layer. These mixtures are also referred to as premix systems that are used as the sole material source in the vapor deposition of the host materials for the light-emitting layer and have a constant mixing ratio in the vapor deposition. In this way, it is possible in a simple and rapid manner to achieve the vapor deposition of a layer with homogeneous distribution of the components without the need for precise actuation of a multitude of material sources.

In an alternative embodiment of the present invention, the mixture, aside from the constituents of the host material of the inventive compound and the host material 2, as described above or described with preference, also comprises a phosphorescent emitter, as described above. In the case of a suitable mixing ratio in the vapor deposition, this mixture may also be used as the sole material source. Preference is given to premix systems consisting of two matrix materials, namely one compound of the inventive compounds or the formula 1-1 or 1-2 and one compound of one of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6).

Preference is given to premix systems consisting of three matrix materials, namely one compound of the inventive compounds or the formulae 1-1 or 1-2 and two compounds of one of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6).

The components or constituents of the light-emitting layer of the device of the invention may thus be processed by vapor deposition or from solution. The material combination of host materials 1 and 2, as described above or described as preferred, optionally with the phosphorescent emitter, as described above or described as preferred, are provided for that purpose in a formulation containing at least one solvent. Suitable formulations have been described above.

The light-emitting layer in the device of the invention, according to the preferred embodiments and the emitting compound, contains preferably between 99.9% and 1% by volume, further preferably between 99% and 10% by volume, especially preferably between 98% and 60% by volume, very especially preferably between 97% and 80% by volume, of matrix material composed of at least one compound of the inventive compounds or the formula 1-1 or 1-2 and at least one compound of one of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH-6) according to the preferred embodiments, based on the overall composition of emitter and matrix material.

Correspondingly, the light-emitting layer in the device of the invention preferably contains between 0.1% and 99% by volume, further preferably between 1% and 90% by volume, more preferably between 2% and 40% by volume, most preferably between 3% and 20% by volume, of the emitter based on the overall composition of the light-emitting layer composed of emitter and matrix material. If the compounds are processed from solution, preference is given to using the corresponding amounts in % by weight rather than the above-specified amounts in % by volume.

The present invention also relates to an organic electroluminescent device as described above or described as preferred, wherein the organic layer comprises a hole injection layer (HIL) and/or a hole transport layer (HTL), the hole-injecting material and holetransporting material of which belongs to the class of the arylamines.

The sequence of layers in the organic electroluminescent device of the invention is preferably as follows: anode I hole injection layer I hole transport layer I emitting layer I hole blocker layer I electron transport layer / electron injection layer / cathode.

This sequence of the layers is a preferred sequence.

At the same time, it should be pointed out again that not all the layers mentioned need be present and/or that further layers may additionally be present.

Materials used for the electron transport layer may be any materials as used according to the prior art as electron transport materials in the electron transport layer. Especially 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.

Suitable cathodes of the device of the invention are metals having a low work function, metal alloys or multilayer structures composed of various metals, for example alkaline earth metals, alkali metals, main group metals or lanthanoids (e.g. Ca, Ba, Mg, Al, In, Yb, Sm, etc.). Additionally suitable are alloys composed of an alkali metal or alkaline earth metal and silver, for example an alloy composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, it is also possible to use further metals having a relatively high work function, for example Ag or Al, in which case combinations of the metals such as Ca/Ag, Mg/Ag or Ba/Ag, for example, are generally used. It may also be preferable to introduce a thin interlayer of a material having a high dielectric constant between a metallic cathode and the organic semiconductor. Examples of useful materials for this purpose 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.). It is also possible to use lithium quinolinate (LiQ) for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 nm.

Preferred anodes are materials having a high work function. Preferably, the anode has a work function of greater than 4.5 eV versus vacuum. Firstly, metals having a high redox potential are suitable for this purpose, for example Ag, Pt or Au. Secondly, metal/metal oxide electrodes (e.g. Al/N i/N iO_x, AI/PtO_x) may also be preferred. For some applications, at least one of the electrodes has to be transparent or partly transparent in order to enable either the irradiation of the organic material (organic solar cell) or the emission of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is further given to conductive doped organic materials, especially conductive doped polymers. In addition, the anode may also consist of two or more layers, for example of 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 of the invention, in the course of production, is appropriately (according to the application) structured, contact-connected and finally sealed, since the lifetime of the devices of the invention is shortened in the presence of water and/or air.

The production of the device of the invention is not restricted here. It is possible that one or more organic layers, including the light-emitting layer, are coated by a sublimation method. In this case, the materials are applied by vapor deposition in vacuum sublimation systems at an initial pressure of less than 10'⁵ mbar, preferably less than 10'⁶ mbar. In this case, however, it is also possible that the initial pressure is even lower, for example less than 10^-7 mbar.

The organic electroluminescent device of the invention is preferably characterized in that one or more layers are coated by the OVPD (organic vapor phase deposition) method or with the aid of a carrier gas sublimation. In this case, the materials are applied at a pressure between 10'⁵ mbar and 1 bar. A special case of this method is the OVJP (organic vapor jet printing) method, in which the materials are applied directly by a nozzle and thus structured (for example M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

The organic electroluminescent device of the invention is further preferably characterized in that one or more organic layers containing the composition of the invention are produced from solution, for example by spin-coating, or by any printing method, for example screen printing, flexographic printing, nozzle printing or offset printing, but more preferably LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble host materials 1 and 2 and phosphorescent emitters are needed. Processing from solution has the advantage that, for example, the light-emitting layer can be applied in a very simple and inexpensive manner. This technique is especially suitable for the mass production of organic electroluminescent devices.

In addition, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition. These methods are known in general terms to those skilled in the art and can be applied to organic electroluminescent devices.

The invention therefore further provides a process for producing the organic electroluminescent device of the invention as described above or described as preferred, characterized in that the organic layer, preferably the light-emitting layer, the hole injection layer and/or hole transport layer, is applied by gas phase deposition, especially by a sublimation method and/or by an OVPD (organic vapor phase deposition) method and/or with the aid of a carrier gas sublimation, or from solution, especially by spin-coating or by a printing method.

In the case of production by means of gas phase deposition, there are in principle two ways in which the organic layer, preferably the light-emitting layer, of the invention can be applied or vapor-deposited onto any substrate or the prior layer. Firstly, the materials used can each be initially charged in a material source and ultimately evaporated from the different material sources ("co-evaporation"). Secondly, the various materials can be premixed (premix systems) and the mixture can be initially charged in a single material source from which it is ultimately evaporated ("premix evaporation"). In this way, it is possible in a simple and rapid manner to achieve the vapor deposition of the light-emitting layer with homogeneous distribution of the components without the need for precise actuation of a multitude of material sources.

The following methods are possible:

A process for producing the organic electroluminescent device of the invention as described above or described as preferred, characterized in that the organic layer, preferably the light-emitting layer, the electron transport layer and/or hole blocker layer, is applied by gas phase deposition, especially by a sublimation method and/or by an OVPD (organic vapor phase deposition) method and/or with the aid of a carrier gas sublimation, or from solution, especially by spin-coating or by a printing method.

A process for producing the organic electroluminescent device of the invention, as described above or described as preferred, 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 inventive compounds or the formulae 1-1 or 1-2 deposited from the gas phase together with the further materials that form the light-emitting layer, successively or simultaneously from at least two material sources. A process for producing the device of 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 inventive compounds or the formulae 1-1 or 1-2 is deposited from the gas phase together with at least one further matrix material as premix, successively or simultaneously with the light-emitting materials selected from the group of the phosphorescent emitters, fluorescent emitters and/or emitters that exhibit TADF (thermally activated delayed fluorescence).

The electronic devices of the invention, especially organic electroluminescent devices, are notable for one or more of the following surprising advantages over the prior art:

1 . Electronic devices, especially organic electroluminescent devices, containing compounds containing at least one of indolocarbazole moiety Z', at least one of N- heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) or the preferred embodiments recited above and hereinafter, especially as matrix material or as electron-conducting materials, have a very good lifetime. In this context, these compounds especially bring about low roll-off, i.e. a small drop in power efficiency of the device at high luminances.

2. Electronic devices, especially organic electroluminescent devices, containing compounds containing at least one of indolocarbazole moiety Z', at least one of N- heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) or the preferred embodiments recited above and hereinafter, as electron-conducting materials and/or matrix materials, have excellent efficiency. In this context, compounds of the invention having at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) or the preferred embodiments recited above and hereinafter bring about a low operating voltage when used in electronic devices.

3. The compounds containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) or the preferred embodiments recited above and hereinafter exhibit very high stability and lifetime.

4. The compounds containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) or the preferred embodiments recited above and hereinafter exhibit increased thermal stability with high decomposition temperatures (Td and Tg). This leads to an enhanced likelihood of successful purification and device fabrication processes. Moreover, devices utilizing these compounds demonstrate a reduction in heat- induced morphology changes and increased stability.

5. With compounds containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) or the preferred embodiments recited above and hereinafter, it is possible to avoid the formation of optical loss channels in electronic devices, especially organic electroluminescent devices. As a result, these devices feature a high PL efficiency and hence high EL efficiency of emitters, and excellent energy transmission of the matrices to dopants.

6. The use of compounds containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) or the preferred embodiments recited above and hereinafter in layers of electronic devices, especially organic electroluminescent devices, leads to high mobility of the electron conductor structures.

7. Compounds containing at least one of indolocarbazole moiety Z', at least one of N- heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) or the preferred embodiments recited above and hereinafter have excellent glass film formation.

8. Compounds containing at least one of indolocarbazole moiety Z', at least one of N- heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) or the preferred embodiments recited above and hereinafter form very good films from solutions.

9. The compounds containing at least one of indolocarbazole moiety Z', at least one of N-heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1) or the preferred embodiments recited above and hereinafter have a triplet level Ti which may, for example, be in the range of 2.50 eV-2.90 eV.

These abovementioned advantages are not accompanied by an inordinately high deterioration in the further electronic properties.

It should be pointed out that variations of the embodiments described in the present invention are covered by the scope of this invention. Any feature disclosed in the present invention may, unless this is explicitly ruled out, be exchanged for alternative features which serve the same purpose or an equivalent or similar purpose. Any feature disclosed in the present invention, unless stated otherwise, should therefore be considered as an example from a generic series or as an equivalent or similar feature.

All features of the present invention may be combined with one another in any manner, unless particular features and/or steps are mutually exclusive. This is especially true of preferred features of the present invention. Equally, features of non-essential combinations may be used separately (and not in combination).

The technical teaching disclosed with the present invention may be abstracted and combined with other examples.

The invention is illustrated in detail by the examples which follow, without any intention of restricting it thereby.

Examples

Synthesis examples

1 ) 2-Chloro-4-(1 -triphenyleno[1 , 12-bcoQfuran-l -yl-]-6-phenyl-1 ,3,5-triazine

43 g (153.0 mmol) triphenyleno[1,12-bcd]furan-1-boronic acid, 34.4 g (153.0 mmol) 2-4- dichloro-6-phenyl-1,3,5-triazine and 17 g (168.0 mmol ) Sodium carbonate is suspended in 140 mL toluene, 350 mL dioxane and 300 mL water. 1.7 g (1.5 mmol) of 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 off, filtered through silica gel, washed three times with 200 mL water and then concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane/heptane. The yield is 53 g (124 mmol), corresponding to 83% of theory. The following compounds can be synthesized in an analogous way:

10

20

2) 11-[4-(2-Triphenyleno[1,12-bcc/]thiophene-3-yl)-6-phenyl-1,3,5-triazin-2-yl]-11,12- dihydro-12-phenylindolo[2,3-a]carbazole

Method 1 :

22.9 g (63 mmol) of 11 ,12-dihydro-11-phenylindolo[2,3-a]carbazole are dissolved in 200 mL of dimethylformamide under Nitrogen atmosphere, and 7.7 g (194 mmol) of 60% NaH (suspension in paraffin oil) are added. After 1 h at room temperature, a solution of 29.7 g (69 mmol) of 2-chloro-4-(1-triphenyleno[1,12-bcd]furan-2-yl-]-6-phenyl-1,3, 5-triazine in 300 mL dimethylformamide is added dropwise. The reaction mixture is then stirred at room temperature for 12 h. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na2SC>4 and concentrated. The residue is washed with toluene extracted hot and recrystallized from dichloromethane/isopropanol and finally sublimed under high vacuum, purity is 99.9% The yield is 25.7 g (34.4 mmol), corresponding to 50% of theory.

Method 2 :

16.2 g (49 mmol) of 11 ,12-dihydro-11-phenylindolo[2,3-a]carbazole are placed in tetrahydrofuran (120 ml) and cooled to -5°C. It is then cooled and 24.5 mL n-hexyllithium (33% 2.47 mol/L in hexane) is added and the mixture is stirred at -5° C for 1 hour. A solution of 23.7 g (55 mmol) 2-chloro-4-(1- triphenyleno[1 ,12-bcd]furan-2-yl-]-6-phenyl- 1,3, 5-triazine and tetrahydrofuran (245 ml) are added and the mixture is stirred for a further 1.5 h at -5° C. The mixture is left overnight allowed to come to room temperature and then treated with 500 mL MeOH. The precipitated solid is filtered off with suction and washed with n-heptane. Then it is basic hot-extracted three times with o-xylene over Alox and then sublimated twice in a high vacuum. The yield is 19.1 g (26.3 mmol), corresponding to 54% of theory.

The following compounds can be synthesized in an analogous way:

3) 11 -(4,6-Diphenyl-1 ,3,5-triazin-2-yl)-12-[ triphenyleno[1,12-bccf]thiophen-3-yl- ]11H,12H-indolo[2,3-a]carbazole

87 g (0.18 mol) 11-(4,6-diphenyl-1,3,5-triazin-2-yl)-11,12-dihydroindolo[2,3-a]carbazole and 60 g (0.18 mmol) 3- Bromotriphenyleno[1,12-bcd]thiophene are placed in 2.5 L of xylene. After addition of 50 g (0.52 mol) of sodium tert-butanolate, this suspension is degassed by bubbling with nitrogen for 15 min. and then 10 ml (10 mmol) of tri-tert- butylphosphine and 1.5 g (6.7 mmol) of palladium acetate are added. The batch is heated under reflux for 47 h. After the reaction has ended, the reaction mixture is washed with water, the aqueous phase is extracted with toluene and the combined organic phases are dried over sodium sulfate. The solvent is removed on a rotary evaporator and the residue is extracted hot with toluene. After three hot extractions over Alox and subsequent sublimation under high vacuum, the purified product is obtained as a colorless solid with an HPLC purity of >99.9% (93 g, 0.12 mol, 70%).

The following compounds can be synthesized in an analogous way:

4) 11-phenyl-12-(4-phenyl-6-(triphenyleno[1,12-bcd]furan-9-yl)-1,3,5-triazin-2-yl)- 11,12-dihydroindolo[2,3-a]carbazole-d₂9

E23

36 g (49.0 mmol; 1.0 eq.) of 11-phenyl-12-(4-phenyl-6-(triphenyleno[1,12-bcd]furan-9-yl)- 1,3,5-triazin-2-yl)-11 ,12-dihydroindolo[2,3-a]carbazole is suspended in 640 mL (120 eq.) of toluene-ds. To this mixture 17 mL (6.00 eq.) of trifluoromethanesulfonic acid is added under cooling. The reaction mixture is stirred at ambient temperature for 6 hours.

Subsequently, 120 mL (130 eq.) deuterium oxide [CAS 7789-20-0] is added at 0°C. After neutralization with a potassium sulfate solution, extract with toluene and wash the combined organic phases with saline and dry over sodium sulfate. After filtration, the solvent is removed under reduced pressure. 23.5 g (31 mmol, 63 % of theory) of the product shown above in mixture with proportions of H/D isotopomers and H/D isotopologues are obtained after chromatographic purification (purity 99.9%) and finally sublimated in high vacuum (p = 5 x 10'⁷ mbar).

The following compounds are prepared analogously:

Example: Fabrication of vapor processed OLED devices

The use of the material combinations according to the invention in OLEDs is presented in the following examples B1 to B10 (see Table 7). Substrate pre-treatment of examples V1 to V5, B1 to B10:

Glass plates with structured ITO (50 nm, indium tin oxide) form the substrates on which the OLED devices are fabricated.

The OLED devices have in principle the following layer structure:

Substrate, . ITO (50 nm),

Hole injection layer (HIL)

Hole transporting layer (HTL),

Electron blocking layer (EBL),

Emissive layer (EML), Hole blocking layer (HBL),

Electron transporting layer (ETL), Electron injection layer (EIL), Cathode.

The cathode is formed by an aluminium layer with a thickness of 100 nm. The detailed stack sequence is shown in table 7. The materials used for the OLED fabrication are presented in table 8.

All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material and one emitting dopant, which is mixed with the matrix material or matrix materials in a certain proportion by volume by co-evaporation. An expression such as H1 :H2:TEG1 (42%:50%:8%) here means that material H1 is present in the layer in a proportion by volume of 42%, material H2 is present in the layer in a proportion by volume of 50%, and material TEG1 is present in the layer in a proportion by volume of 8%. Analogously, the electron-transport layer and hole-injection layer may also consist of a mixture of two or more materials.

The OLED devices are characterized by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), power efficiency (Im/W) and the external quantum efficiency (EQE, measured in % at 1000 cd/m²) are determined from current/voltage/luminance characteristic lines (IUL characteristic lines) assuming a Lambertian emission profile. The electroluminescence (EL) spectra are recorded at a luminous density of 1000 cd/m² and the CIE 1931 x and y coordinates are then calculated from the EL spectrum. U1000 is defined as the voltage at luminous density of 1000 cd/m². EQE1000 is the external quantum efficiency at luminous density of 1000 cd/m². The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion L1 in the course of operation with constant current jO. A figure of L1=90% in Table 9 means that the lifetime reported in the LT column corresponds to the time after which the starting luminance falls to 90% of its starting value.

Use of mixtures according to the invention in OLEDs

The material combinations according to the invention can be used in the emission layer in phosphorescent green OLEDs. The combinations according to the invention of the compounds H3, H10, H13, H18, or H21 are used as matrix material in the emission layer in Examples B1 to B10. The examples are explained in more detail below in order to clarify the advantages of the OLEDs according to the invention. Table 7: Structure of the OLEDs

Table 8: Structural formulas of the materials for the OLEDs

Table 9: Data of the OLEDs

Claims

Patent Claims

1. Compound comprising at least one of indolocarbazole moiety Z', at least one of N- heteroaryl moiety Z^h, and at least one of moiety Z* represented by Formula (1):

where the groups and indices that occur are as follows:

Y¹¹ is S or O;

X¹¹ is CR¹¹ or N, X¹² is CR¹² or N, X¹³ is CR¹³ or N, X¹⁴ is CR¹⁴ or N, X¹⁵ is CR¹⁵ or N, X¹⁶ is CR¹⁶ or N, X¹⁷ is CR¹⁷ or N, X¹⁸ is CR¹⁸ or N, X¹⁹ is CR¹⁹ or N, X¹⁹ is CR¹⁹ or N, and X²⁰ is CR²⁰ or N, wherein at least one of X¹¹ to X²⁰ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’;

R¹¹ to R²⁰ at each instance are each independently H, D, F, Cl, Br, I, CHO, CN, N(R⁴)2, C(=O)R⁴, P(=O)(R⁴)₂, S(=O)R⁴, S(=O)₂R⁴, NO₂, Si(R⁴)₃, Ge(R⁴)₃, B(R⁴)₂, B(OR⁴)₂, OSO₂R⁴, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R⁴, where in each case one or more non-adjacent CH₂ groups may be replaced by R⁴C=CR⁴, C=C, Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C=O, C=S, C=Se, P(=O)(R⁴), SO, SO₂, O, S or CONR⁴ and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R⁴, or an aryloxy group or heteroaryloxy group having 5 to 60 ring atoms, which may be substituted by one or more radicals R⁴; wherein two of radicals R¹¹ to R²⁰ may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R⁴; Lⁿ is the same or different at each instance and is a single bond 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 R⁵; na is 1 , 2 or 3;

* and *’ stand on each occurrence, a binding site to adjacent atom;

R⁴ and R⁵ at each instance are each independently H, D, F, Cl, Br, I, CHO, CN, N(Ar)2, C(=O)Ar, P(=O)(Ar)₂, S(=O)Ar, S(=O)₂Ar, NO₂, Si(R')₃, Ge(R')₃, B(OR')₂, OSO₂R , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R', where in each case one or more non-adjacent CH₂ groups may be replaced by R'C=CR', C=C, Si(R')₂, Ge(R')₂, Sn(R')₂, C=O, C=S, C=Se, P(=O)(R'), SO, SO₂, O, S or CONR' and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, 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', or an aryloxy group or heteroaryloxy group having 5 to 60 ring atoms, which may be substituted by one or more radicals R'; wherein R³ and R⁴ may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R’;

Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case also be substituted by one or more radicals R'; and

R is the same or different at each instance and is H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH₂ groups may be replaced by SO, SO₂, O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms.

2. Compound according to claim 1 , wherein the N-heteroaryl moiety Z^h is selected from pyridine, pyrimidine and triazine, which may be substituted by one or more radicals R³, R³ is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, CN, N(R⁴)2, C(=O)R⁴, P(=O)(R⁴)₂, S(=O)R⁴, S(=O)₂R⁴, NO₂, Si(R⁴)₃, Ge(R⁴)₃, B(R⁴)₂, B(OR⁴)₂, OSO₂R⁴, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R⁴, where in each case one or more non-adjacent CH₂ groups may be replaced by R⁴C=CR⁴, C=C, Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C=O, C=S, C=Se, P(=O)(R⁴), SO, SO₂, O, S or CONR⁴ and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R⁴, or an aryloxy group or heteroaryloxy group having 5 to 60 ring atoms, which may be substituted by one or more radicals R⁴; wherein two of radicals R¹¹ to R²⁰ may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R⁴; and R⁴ has the definition given in Claim 1.

3. Compound according to claim 1 or 2, wherein the indolocarbazole moiety Z' is represented by Formula (2):

Formula (2) Formula 2A wherein in Formula (2) and 2A,

X^2a is CR^20a or C, X^2b is CR^20b or C, X^2c is CR^20c or C, and X^2d is CR^20d or C,

X^2a and X^2b, X^2b and X^2c, and X^2c and X^2d are the same or different at each instance and are linked by a single bond or double bond, wherein X^2a and X^2b is C and X^2a-X^2b in Formula (2) is binding with the dotted line in Formula 2A, X^2b and X^2c is C and X^2b-X^2c in Formula (2) is binding with the dotted line in Formula 2A, or X^2c and X^2d is C and X^2c-X^2d in Formula (2) is binding with the dotted line in Formula 2A;

R^20a, R20b R20C R2od _anc| ^21 _to j_nstance are each independently H, D, F, Cl, Br, I, CHO, CN, N(R⁴)₂, C(=O)R⁴, P(=O)(R⁴)₂, S(=O)R⁴, S(=O)₂R⁴, NO₂, Si(R⁴)₃, Ge(R⁴)₃, B(R⁴)₂, B(OR⁴)2, OSO2R⁴, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R⁴, where in each case one or more non-adjacent CH₂ groups may be replaced by R⁴C=CR⁴, C=C, Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C=O, C=S, C=Se, P(=O)(R⁴), SO, SO₂, O, S or CONR⁴ and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R⁴, or an aryloxy group or heteroaryloxy group having 5 to 60 ring atoms, which may be substituted by one or more radicals R⁴; wherein two of radicals R¹¹ to R²⁰ may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R⁴; wherein at least one of R^20a, R^20b, R^20c, R^20d and R²¹ to R³⁰ is a binding site to the moiety Z* represented by Formula (1) or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’; and

R⁴, Lⁿ, na, *, and *’ have the definition given in Claim 1.

4. Compound according to one or more of claims 1 to 3, wherein the indolocarbazole moiety Z' is represented by Formula 2-1 :

wherein in Formula 2-1 ,

R2°c, R^20d, and R²¹ to R³⁰ have the definition given in Claim 3.

5. Compound according to one or more of claims 1 to 4, characterized in that the compound satisfies at least one of Conditions A and B:

<Condition A> At least one of X¹¹ to X¹³ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition B>

At least one of X¹⁴ to X¹⁷ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’.

6. Compound according to one or more of claims 1 to 5, characterized in that the compound satisfies at least one of Conditions A-1 to A-3, B-1 and B-2:

<Condition A-1>

X¹¹ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition A-2>

X¹² is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition A-3>

X¹³ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition B-1>

X¹⁴ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’ <Condition B-2>

X¹⁵ is not N and is a binding site to the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h via linker *-(Lⁿ)_na-*’.

7. Compound according to one or more of claims 1 to 6, characterized in that the moiety Z* represented by Formula (1) is binding to either the indolocarbazole moiety Z' or the N-heteroaryl moiety Z^h.

8. Compound according to one or more of claims 1 to 7, characterized in that the compound represented by Formula 1-1 or Formula 1-2:

wherein in Formulae 1-1 and 1-2,

X³¹ is CR³¹ or N, X³² is CR³² or N, X³³ is CR³³ or N, wherein at least one of X³¹ to X³³ is N;

R³¹ to R³⁵ at each instance are each independently H, D, F, Cl, Br, I, CHO, CN, N(R⁴)2, C(=O)R⁴, P(=O)(R⁴)₂, S(=O)R⁴, S(=O)₂R⁴, NO₂, Si(R⁴)₃, Ge(R⁴)₃, B(R⁴)₂, B(OR⁴)₂, OSO₂R⁴, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R⁴, where in each case one or more non-adjacent CH₂ groups may be replaced by R⁴C=CR⁴, C=C, Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C=O, C=S, C=Se, P(=O)(R⁴), SO, SO₂, O, S or CONR⁴ and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic or heteroaromatic ring system having 5 to 60 ring atoms, which may in each case be substituted by one or more radicals R⁴, or an aryloxy group or heteroaryloxy group having 5 to 60 ring atoms, which may be substituted by one or more radicals R⁴; wherein two of radicals R¹¹ to R²⁰ may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R⁴;

L¹ to L³ at each instance are each independently refer to the definition of Lⁿ; a1 to a3 at each instance are each independently refer to the definition of na; and

R⁴, Z’ and Z' have the definition given in Claim 1.

9. Compound according to one or more of claims 1 to 8, characterized in that at least one of N atoms in the indolocarbazole moiety Z' is a binding site to the N-heteroaryl moiety Z^h or the moiety Z* represented by Formula (1).

10. Compound according to one or more of claims 1 to 9, characterized in that compound comprises at least one of deuterium.

11. Mixture comprising at least one compound according to any one of claims 1 to 10 and at least one further compound and/or at least one solvent, wherein the further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, TADF emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, n- dopants, wide band gap materials, electron blocking materials and hole blocking materials.

12. Mixture comprising at least one compound according to any one of claims 1 to 10 and at least one compound of the formulae (HH-1), (HH-2), (HH-3), (HH-4), (HH-5) or (HH- 6)

rmula (HH-2),

, where the symbols and indices used are as follows:

A¹ is C(R⁷)₂, NR⁷, O or S;

L is a bond, O, S, C(R⁷)₂ or NR⁷;

A at each instance is independently a group of the formula (HH-4-1) or (HH-4-2),

X2 is the same or different at each instance and is CH, CR⁶ or N, where not more than 2 symbols X2 can be N;

* indicates the binding site to the formula (HH-4);

II¹, II² where they occur are a bond, O, S, C(R⁷)2 or NR⁷;

R⁶ is the same or different at each instance and is D, F, CN, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group made in each case be substituted by one or more R⁷ radicals and where one or more nonadjacent CH2 groups may be replaced by Si(R⁷)2, C=O, NR⁷, O, S or CONR⁷, or an aromatic or heteroaromatic ring system which has 5 to 60 ring atoms and may be substituted in each case by one or more R⁷ radicals; it is also possible here for two R⁶ radicals together to form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system;

Ars is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted by one or more R⁷ radicals;

R⁷ is the same or different at each instance and is D, F, Cl, Br, I, N(R⁸)2, CN, NO2, OR⁸, SR⁸, Si(R⁸)₃, B(OR⁸)₂, C(=O)R⁸, P(=O)(R⁸)₂, S(=O)R⁸, S(=O)₂R⁸, OSO2R⁸, a straightchain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R⁸ radicals and where one or more nonadjacent CH2 groups may be replaced by Si(R⁸)2, C=O, NR⁸, O, S or CONR⁸, or an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms and may be substituted in each case by one or more R⁸ radicals; at the same time, two or more R⁷ radicals together may form an aromatic, heteroaromatic, aliphatic or heteroaromatic ring system; preferably, the R⁷ radicals do not form any such ring system;

R⁸ is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; c, c1 , c2 at each instance are each independently 0 or 1 , where the sum total of the indices at each instance c+c1+c2 = 1 ; d, d1 , d2 at each instance are each independently 0 or 1 , where the sum total of the indices at each instance d+d1+d2 = 1 ; q, q1 , q2 at each instance is independently 0, 1 , 2, 3 or 4; s is the same or different at each instance and is 0, 1 , 2, 3 or 4; t is the same or different at each instance and is 0, 1 , 2 or 3; u is the same or different at each instance and is 0, 1 or 2; u1 , u2 at each instance are each independently 0 or 1 , where the sum total u1 + u2 = 1 ; and v is 0, 1 , 2 or 3.

13. Electronic device comprising at least one compound according to one or more of Claims 1 to 10 or mixture according to Claim 11 or 12.

14. Electronic device according to Claim 13, characterized in that it is an organic electroluminescent device and comprises an anode, cathode and at least one emitting layer, and in that the compound is present in a hole-transporting layer or in an emitting layer of the device.

15. Use of a compound as claimed in one or more of Claims 1 to 10 in an electronic device.