Composition for organic electronic devices

Abstract

The present invention relates to a composition comprising an electron-transporting host and a hole-transporting host, to the use thereof in electronic devices and to electronic devices containing said composition. The electron-transporting host corresponds to a compound of formula (1) from the class of N-bridged triphenylenes that contain a linker bonded via the N atom, to which a substituted pydridine, pyrimidine or triazine moiety is bonded.

Description

[0001] Composition for organic electronic devices

[0002] The present invention relates to a composition comprising an electron-transporting host and a hole-transporting host, the use thereof in electronic devices, and electronic devices containing this composition. The electron-transporting host corresponds to a compound of formula (1) from the class of N-bridged triphenylenes containing a linker bonded via the N atom to which a substituted pyridine, pyrimidine, or triazine unit is bonded.

[0003] The construction of organic electroluminescent devices (e.g., OLEDs - organic light-emitting diodes or OLECs - organic light-emitting electrochemical cells), which use organic semiconductors as functional materials, has long been known. In addition to fluorescent emitters, organometallic complexes that exhibit phosphorescence instead of fluorescence are increasingly being used as emitting materials. For quantum mechanical reasons, the use of organometallic compounds as phosphorescence emitters allows for up to fourfold increases in energy and power efficiency. However, there is still room for improvement in OLEDs in general, and especially in OLEDs that exhibit triplet emission (phosphorescence), for example, with regard to efficiency, operating voltage, and lifetime.

[0004] The properties of organic electroluminescent devices are not only determined by the emitters used. The other materials used, such as host and matrix materials, hole-blocking materials, electron-transport materials, and electron- or exciton-blocking materials, are also of particular importance, especially the host and matrix materials. Improvements to these materials can lead to significant improvements in electroluminescent devices.

[0005] Host materials for use in organic electronic devices are well known to those skilled in the art. In the prior art, the term "matrix material" is often used to refer to a host material for phosphorescent emitters. This use of the term also applies to the present invention. A variety of host materials have now been developed for both fluorescent and phosphorescent electronic devices.

[0006] US Pat. No. 6,392,250 B1 discloses the use of a mixture consisting of an electron-transport material, a hole-transport material, and a fluorescent emitter in the emission layer of an OLED. Using this mixture, the lifetime of the OLED could be improved compared to the prior art.

[0007] US Pat. No. 6,803,720 B1 discloses the use of a mixture containing a phosphorescent emitter and a hole- and electron-transport material in the emission layer of an OLED. Both the hole- and electron-transport materials are small organic molecules.

[0008] Another possibility to improve the performance of electronic devices, in particular organic electroluminescent devices, is to use combinations of two or more materials, in particular host materials or matrix materials.

[0009] WO 2012 / 048781 describes for the first time N-bridged triphenylenes with electron and hole transporting properties, which are used in a green phosphorescent OLED in the emission layer as a hole transporting host and / or electron transporting host and / or in the hole transport layer as a hole transport material.

[0010] US 2014 / 0361254 describes N-substituted N-bridged phenanthrenes substituted with carbazole via a C atom of the backbone, which in turn is substituted with a pyrimidine or triazine unit at the N atom. These compounds are used as host materials in the emission layer of green and phosphorescent OLEDs and as electron transport materials. US 2014 / 0361268 also describes N-bridged phenanthrenes substituted with an aryl group at the N atom, which in turn is substituted with an aryl, heteroaryl, or polycyclic group. These compounds are used as electron transport materials in blue fluorescent devices.

[0011] US 2014 / 0361267 describes N-substituted N-bridged phenanthrenes bonded to an N-substituted carbazole via a C atom of the backbone. These compounds are used as host materials in the emission layer of green and red phosphorescent OLEDs and as electron transport materials.

[0012] US 2019 / 315759 describes indolo-naphto-carbazoles. These compounds are used as host materials together with an electron-transporting host in the emission layer in green phosphorescent OLEDs.

[0013] KR2021-0036304 describes N-substituted benzonaphthocarbazoles. These compounds are used as host materials in red-phosphorescent OLEDs.

[0014] KR 2021-0036857 describes N-substituted benzo-naphto-carbazoles to which a dibenzofuran (or dibenzothiophene) is bound, which in turn is bound to a pyrimidine or triazine group. These compounds are used as host materials in red phosphorescent OLEDs.

[0015] In WO 2022 / 015084, biscarbazoles in combination with triazyl-indeno- and indolocarbazoles as well as triazine-dibenzofuran-N-carbazoles are described as a composition in green phosphorescent OLEDs.

[0016] WO 2020 / 169241 describes triazine-1-dibenzofuran-8-N-carbazoles with carbazole derivatives for use in green phosphorescent OLEDs. CN1156269 A, filed on November 4, 2022 and published on January 20, 2023, discloses similar compounds.

[0017] However, there is still room for improvement when using these materials or when using mixtures of the materials, particularly with regard to efficiency, operating voltage and / or lifetime of the organic electroluminescent device.

[0018] An object of the present invention is therefore to provide a combination of materials which are suitable for use in an organic electroluminescent device, in particular in a fluorescent or phosphorescent OLED and which lead to good device properties, in particular with regard to an improved lifetime, as well as to provide the corresponding electroluminescent device.

[0019] It has now been found that the combination of at least one compound of formula (1) and at least one hole-transporting compound of formula (2) or (3) in an organic layer of an organic electroluminescent device solves this problem and eliminates the disadvantages of the prior art. The use of such a material combination for producing an organic layer in an organic electroluminescent device leads to very good properties of these devices, in particular with regard to lifetime, in particular with the same or improved efficiency and / or operating voltage. The advantages are also apparent in particular in the presence of a light-emitting component in the emission layer, in particular in combination with emitters of formula (IIIa) or emitters of formulas (I) to (VI) at concentrations between 2 and 20 wt. %, in particular concentrations of 6 wt. % and 12 wt. %.

[0020] A first subject of the present invention is therefore a composition comprising at least one compound of formula (1) and at least one compound of formula (2) or formula (3), where the symbols and indices used are:

[0021] R* is a group of the following formula (1a)

[0022] Formula (1a) where the dashed bond represents the bond to the N atom of formula (1);

[0023] X is the same or different at each occurrence N or CR C , with the proviso that at least one group X stands for N and in the case that X stands for CR C stands, this no ring with Ar a or Ar b forms;

[0024] L is, identically or differently at each occurrence, an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 may be substituted, where L is substituted by a radical R or radical R a can also form an aliphatic, heteroaliphatic or heteroaromatic ring system, or L is a group of the formula --L 1 -QL 2 -- where L 2 to the heteroaryl group of formula (1a) and L 1 to the N atom of the parent structure of formula (1);

[0025] Q is a group of formula (4), where the dashed bonds represent the connection to L 1 or L 2 represent and L 1 and L 2at each occurrence may be bonded either to the same or to different phenyl rings of the group of formula (4), with the proviso that the sum of aromatic ring atoms including all heteroatoms of the groups L 1 , L 2 and Q is 13 to 40;

[0026] G is the same or different as O or S at each occurrence;

[0027] L 1 , L 2 are each independently of one another on each occurrence, identically or differently, a single bond, an aryl group having 6 to 24 aromatic ring atoms or a heteroaryl group having 5 to 24 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted;

[0028] Ar a , Ar bare each independently of one another on each occurrence, identically or differently, an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted;

[0029] Ar c , Ar d are each independently of one another, identically or differently on each occurrence, an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R d can be substituted;

[0030] Y is the same or different at each occurrence and is selected from O, S or C(R g )2;

[0031] Ar 1 , Ar 2are each independently of one another, identically or differently on each occurrence, an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted;

[0032] R, R a , R b are each independently of one another at each occurrence, the same or different H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2,OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted, with one or more non-adjacent CH2 groups being replaced by -R 1 C=CR 1 - , -C=C-, Si(R 1 )2, CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, where two or more radicals R and / or R bound to the same cycle a and / or R b can form an aliphatic or heteroaliphatic ring system which can be substituted with one or more radicals R 1may be substituted, and wherein two radicals R and / or R bonded to the same carbon, silicon, germanium or tin atom a and / or R b can form a monocyclic or polycyclic, aliphatic or aromatic ring system which can be substituted by one or more radicals R 1 can be substituted;

[0033] R c , R e , R f , R g , R h , R' are each independently, identically or differently, at each occurrence, H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2, OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by - R 1 C=CR 1 -, -C=C-, Si(R 1 )2, NR 1 , CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, where two or more R residues bound to the same cycle c , R e , R f , R g , R hor R' can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system which can be substituted with one or more radicals R 1 may be substituted, and wherein two radicals R bonded to the same carbon, silicon, germanium or tin atom c , R e , R f , R g , R h or R' may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more radicals R 1 can be substituted;

[0034] R d is the same or different at each occurrence H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2, OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted, with one or more non-adjacent CH2 groups being substituted by -R 1 C=CR 1 -, -C=C-, Si(R 1 )2, NR 1 , CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, where two or more R residues bound to the same cycle d can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system which can be substituted with one or more radicals R 1may be substituted, and wherein two radicals R bonded to the same carbon, silicon, germanium or tin atom d can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more radicals R 1 can be substituted;

[0035] R x is H, D or (L x ) y -Ar x ;

[0036] L x is at each occurrence, identically or differently, a single bond, or an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted;

[0037] Ar x is at each occurrence, identically or differently, an unsubstituted or substituted 9-Ar d-carbazolyl or an unsubstituted or substituted carbazol-9-yl which is substituted with one or more radicals R 1 may be substituted and wherein independently of one another one or more times two radicals R 1 or a residue R 1 together with a remainder of Ar d or R f can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring or for y=0, two adjacent R f and Ar x together form a ring of formula (5), where the positions marked with * represent the bonds to the phenyl ring of formula (2), and the other R f are, identically or differently, H or a substituent as defined above at each occurrence;

[0038] Formula (5)

[0039] Ar' is at each occurrence, identically or differently, an aromatic ring system with 6 to 40 aromatic ring atoms or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is substituted by one or more radicals R 1 can be substituted;

[0040] R 1 is the same or different at each occurrence D, F, I, B(OR 2 )2, N(R 2 )2, CHO, C(=O)R 2 , CR 2 =C(R 2 )2, CN, C(=O)OR 2 , Si(R 2 )3, NO2, P(=O)(R 2 )2, OSO2R 2 , SR 2 , OR 2 , S(=O)R 2 , S(=O)2R 2 , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 2and wherein one or more CH2 groups in the above-mentioned groups are substituted by -R 2 C=CR 2 - , -C C-, Si(R 2 )2, C=O, C=S, -C(=O)O-, NR 2 , CONR 2 , P(=O)(R 2 ), O, S, SO or SO2 and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, where two or more radicals R 1 can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system;

[0041] R 2is, identically or differently at each occurrence, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by D or F; two or more substituents R 2 be linked together and form a ring;

[0042] I, m, p, q are each independently the same or different at each occurrence: 0, 1, 2 or 3; n, o, r, z, s, t are each independently the same or different at each occurrence: 0, 1, 2, 3 or 4; y is each independently 0 or 1.

[0043] An aryl group within the meaning of this invention contains 6 to 40 C atoms; a heteroaryl group within the meaning of this invention contains 2 to 39 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc., or a condensed (fused) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatics linked to one another by a single bond, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as an aromatic ring system.

[0044] An aromatic ring system within the meaning of this invention contains 6 to 40 C atoms in the ring system. A heteroaromatic ring system within the meaning of this invention contains 2 to 39 C atoms and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system within the meaning of this invention is to be understood as a system which does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be linked by a non-aromatic unit, such as a C, N or O atom. Likewise, this is to be understood as systems in which two or more aryl or heteroaryl groups are directly linked to one another, such as biphenyl, terphenyl, bipyridine or phenylpyridine.For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ethers, stilbene, etc., are also to be understood as aromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are linked, for example, by a short alkyl group. Preferred aromatic or heteroaromatic ring systems are simple aryl or heteroaryl groups, as well as groups in which two or more aryl or heteroaryl groups are directly linked to one another, for example, biphenyl or bipyridine, as well as fluorene or spirobifluorene.

[0045] An electron-rich heteroaromatic ring system is characterized by the fact that it is a heteroaromatic ring system that does not contain any electron-deficient heteroaryl groups. An electron-deficient heteroaryl group is a six-membered ring heteroaryl group with at least one nitrogen atom or a five-membered ring heteroaryl group with at least two heteroatoms, one of which is a nitrogen atom and the other oxygen, sulfur, or a substituted nitrogen atom, to which further aryl or heteroaryl groups may be fused. In contrast, electron-rich heteroaryl groups are five-membered ring heteroaryl groups with exactly one heteroatom selected from oxygen, sulfur, or substituted nitrogen, to which further aryl groups and / or further electron-rich five-membered ring heteroaryl groups may be fused.Examples of electron-rich heteroaryl groups include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, and indenocarbazole. An electron-rich heteroaryl group is also called an electron-rich heteroaromatic radical.

[0046] An electron-poor heteroaromatic ring system is characterized in that it contains at least one electron-poor heteroaryl group, and particularly preferably no electron-rich heteroaryl groups.

[0047] In the context of the present invention, the term "alkyl group" is used as a generic term for both linear and branched alkyl groups and cyclic alkyl groups. Similarly, the terms "alkenyl group" and "alkynyl group" are used as generic terms for both linear and branched alkenyl and alkynyl groups, respectively, as well as for cyclic alkenyl and alkynyl groups.

[0048] In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which may contain 1 to 20 C atoms and in which individual H atoms or CH2 groups may be substituted by the above-mentioned groups, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neo-pentyl, cyclopentyl, n-hexyl, neo-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, Cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentinyl, hexynyl, heptynyl or octynyl. Under an alkoxy group OR 1mit 1 bis 40 C-Atomen werden bevorzugt Methoxy, Trifluormethoxy, Ethoxy, n-Propoxy, i-Propoxy, n-Butoxy, i-Butoxy, s-Butoxy, t-Butoxy, n- Pentoxy, s-Pentoxy, 2-Methylbutoxy, n-Hexoxy, Cyclohexyloxy, n-Heptoxy, Cycloheptyloxy, n-Octyloxy, Cyclooctyloxy, 2-Ethylhexyloxy, Pentafluorethoxy und 2,2, 2-Trifluorethoxy verstanden. Unter einer Thioalkylgruppe SR 1mit 1 bis 40 C-Atomen werden insbesondere Methylthio, Ethylthio, n-Propylthio, i-Propylthio, n-Butylthio, i-Butylthio, s-Butylthio, t-Butylthio, n-Pentylthio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclooctylthio, 2-Ethylhexylthio, Trifluormethylthio, Pentafluor- ethylthio, 2,2,2-Trifluorethylthio, Ethenylthio, Propenylthio, Butenylthio, Pentenylthio, Cyclopentenylthio, Hexenylthio, Cyclohexenylthio, Heptenylthio, Cycloheptenylthio, Octenylthio, Cyclooctenylthio, Ethinylthio, Propinylthio, Butinylthio, Pentinylthio, Hexinylthio, Heptinylthio oder Octinylthio verstanden.In general, alkyl, alkoxy, or thioalkyl groups according to the present invention may be straight-chain, branched, or cyclic, wherein one or more non-adjacent CH2 groups may be replaced by the above-mentioned groups; furthermore, one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, preferably F, Cl, or CN, particularly preferably F or CN.

[0049] An aromatic ring system with 6 to 40 aromatic ring atoms or heteroaromatic ring system with 5 - 40 aromatic ring atoms, which is furthermore each with the above-mentioned radicals R 1or a hydrocarbon radical and which can be linked to the aromatic or heteroaromatic ring via any desired positions are understood to mean, in particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, 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,Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1,2-Thiazol, 1 ,3- Thiazol, Benzothiazol, Pyridazin, Hexaazatriphenylen, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1,5-Diazaanthracen, 2,7-Diazapyren, 2,3- Diazapyren, 1,6-Diazapyren, 1,8-Diazapyren, 4,5-Diazapyren, 4,5,9,10-Tetra- azaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1,2,3-Triazol, 1,2,4- Triazol, Benzotriazol, 1,2,3-Oxadiazol, 1,2,4-Oxadiazol, 1,2,5-Oxadiazol, 1 ,3,4- Oxadiazol, 1,2,3-Thiadiazol, 1 ,2,4-Thiadiazol, 1,2,5-Thiadiazol, 1,3,4-Thiadiazol, 1 ,3,5-Triazin, 1 ,2,4-Triazin, 1 ,2,3-Triazin, Tetrazol, 1,2,4,5-Tetrazin, 1 , 2,3,4- Tetrazin, 1 ,2,3,5-Tetrazin, Purin, Pteridin, Indolizin und Benzothiadiazol oder Gruppen, die abgeleitet sind von Kombination dieser Systeme.,

[0050] The phrase "two or more residues can form a ring system" is understood, in the context of this description, to mean, among other things, that the two residues are linked to each other by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme: Ring formation

[0051] Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring. This is illustrated by the following scheme:

[0052] For the indices I, m and n and the residues R, R a and R b it should hold that the remainder R occurs l times, the remainder R a occurs m times and the remainder R boccurs n times and all other positions on the basic structure of the compounds of formula (1) are substituted with H or D, where I and m are the same or different at each occurrence and each stand for 0, 1, 2 or 3 and n stands for 0, 1,

[0053] 2, 3 or 4.

[0054] For the indices o, p, q and r and the residues R e , R f , R h and R' it should hold that the remainder R e o times, the R f p occurs, the remainder R h q times and the residue R' r times and all other positions on the basic structure of the compounds of formula (2) or (3) are substituted with H or D, where o, p, q are the same or different at each occurrence and each represent 0, 1, 2,

[0055] 3, or 4 stand.

[0056] The invention further relates to a process for producing the organic electroluminescent devices, as well as mixtures containing at least one compound of formula (1) and at least one compound of formula (2) or formula (3), and specific material combinations. The corresponding preferred embodiments, as described below, are also subject of the present invention. The surprising and advantageous effects are achieved by specifically selecting the compounds of formula (1) and the compounds of formula (2) or formula (3).

[0057] The organic electronic device according to the invention is, for example, an organic integrated circuit (OIC), an organic field-effect transistor (OFET), an organic thin-film transistor (OTFT), an organic solar cell (OSC), an organic optical detector, an organic photoreceptor, an organic light-emitting transistor (OLET), an organic field quench device (OFQD), an organic light-emitting electrochemical cell (OLEC, LEO, LEEC), an organic laser diode (Cf laser), or an organic light-emitting diode (OLED). The electronic device is preferably an electroluminescent device or, synonymously, a light-emitting device.

[0058] The organic electroluminescent device according to the invention is, for example, an organic light-emitting transistor (OLET), an organic field quench device (OFQD), an organic light-emitting electrochemical cell (OLEC, LEO, LEEC), an organic laser diode (CF laser), or an organic light-emitting diode (OLED). The organic electroluminescent device according to the invention is, in particular, an organic light-emitting diode or an organic light-emitting electrochemical cell. The device according to the invention is particularly preferably an OLED.

[0059] The organic layer of the device according to the invention, which contains the material combination of at least one compound of formula (1) and at least one compound of formula (2) or formula (3), as described above or below, preferably contains, as organic layer, a light-emitting layer (EML), a hole-injection layer (HIL), a hole-transport layer (HTL), an electron-transport layer (ETL), an electron-injection layer (EIL), and / or a hole-blocking layer (HBL). The device according to the invention can also contain several layers from this group selected from EML, HIL, HTL, ETL, EIL, and HBL.Particularly preferably, the material combination of at least one compound of formula (1) and at least one compound of formula (2) or formula (3), as described above or described below, is used in the EML together with a fluorescent or phosphorescent emitter, in particular with a phosphorescent emitter.

[0060] However, the device can also contain inorganic materials or layers that are made entirely of inorganic materials.

[0061] It is preferred that the organic layer containing at least one compound of formula (1) and at least one compound of formula (2) or formula (3) is a light-emitting phosphorescent layer characterized by containing, in addition to the material combination of the compounds of formula (1) and formula (2) or (3) as described above, at least one phosphorescent emitter. A suitable selection of emitters and preferred emitters are described below.

[0062] A phosphorescent emitter within the meaning of the present invention is a compound that exhibits luminescence from an excited state with a higher spin multiplicity, i.e., a spin state > 1, particularly from an excited triplet state. For the purposes of this application, all luminescent complexes with transition metals or lanthanides are considered phosphorescent emitters. A more precise definition is provided below.

[0063] If the materials of the organic layer comprising at least one compound of formula (1), as described above or preferably described below, and at least one compound of formula (2) or formula (3), as described above or described below, are used in the light-emitting layer as host or matrix material for a phosphorescent emitter, it is preferred if their triplet energy is greater than or equal to, but not significantly lower than, the triplet energy of the phosphorescent emitter. Preferably, the triplet level Ti (emitter) - Ti (matrix) is <0.2 eV, particularly preferably <0.15 eV, very particularly preferably <0.1 eV. Ti (matrix) is the triplet level of the host material in the emission layer, this condition applying to each of the two host materials, and Ti (emitter) is the triplet level of the phosphorescent emitter.If the emission layer contains more than two matrix materials, the above relationship preferably also applies to each additional matrix material.

[0064] In a preferred embodiment of the invention, the composition consists of a compound of formula (1) in combination with a compound of formula (2) or formula (3).

[0065] The following describes the material of formula (1) and its preferred embodiments, which is / are contained in the device according to the invention. The preferred embodiments of material 1 of formula (1) also apply to the mixture and / or formulation according to the invention.

[0066] In a preferred embodiment of formula (1a), at least two X are N and the third X is CR C; in a particularly preferred embodiment of formula (1a), all three X are N. Preferred embodiments of the compounds of formula (1) are accordingly compounds in which formula (1a) is a formula (1b), (1c) or (1d), particularly preferably formula (1b) or (1c), in particular formula (1b). In a further preferred embodiment, R c in formulas (1c) or (1d) for H or D.

[0067] Formula (1 b) Formula (1c) Formula (1d)

[0068] In a preferred embodiment of the formula (1), the index I, m and n are 0, 1, 2 or 3, particularly preferably 0 or 1, in particular the sum of the indices m+n+l is 0 or 1. In the event that the radicals R, R a and R bFor D, the sum of the indices is preferably l+m+n=10. The group R* in formulas (1-1a) to (1-11) preferably represents formulas (1b), (1c) or (1d), particularly preferably formula (1b). Preferred embodiments are the following compounds of formulas (1-1a) to (1-1t),

[0069]

[0070] Formula (1-1m) Formula (1-1n) Formula (1-1o) Formula (1-1p)

[0071] Formula (1-1 q) Formula (1-1 r) Formula (1-1s) Formula (1-11) where the symbols used have the meanings given above.

[0072] In a preferred embodiment of formula (1a), Ar a and Ar bat each occurrence, identically or differently, represents an aromatic ring system having 6 to 30 aromatic ring atoms or a heteroaromatic ring system having 5 to 30 aromatic ring atoms, particularly preferably an aromatic ring system having 6 to 24 aromatic ring atoms or a heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, in particular for aromatic ring system with 6 to 14 aromatic ring atoms or a heteroaromatic ring system with 5 to 14 aromatic ring atoms.

[0073] In a preferred embodiment of formula (1a), the radicals Ar a and Ar b of the compounds of formula (1) are different.

[0074] In a preferred embodiment of the invention, the group L represents a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, each of which is substituted by one or more radicals R 1 L particularly preferably represents an aromatic ring system having 6 to 12 aromatic ring atoms, which is substituted by one or more radicals R 1 may be substituted, or for a dibenzofuran or dibenzothiophene group which may be substituted with one or more radicals R 1 may be substituted. Most preferably, L represents a meta- or para-linked phenylene group which is substituted by one or more radicals R 1 may be substituted, or a dibenzofuran or dibenzothiophene group, each of which may be substituted by one or more radicals R 1 may be substituted, where the group R 1preferably represents H or D. If L represents an aromatic or heteroaromatic ring system, this is preferably selected from the structures of the following formulas (L-1) to (L-57),

[0075] L-13

[0076]

[0077] L L-54

[0078] L-52 -53

[0079] L-55 L-56 L-57 wherein the symbols used have the meanings given above and the dashed bonds represent the bonds to the heteroaryl group of formula (1a) and to the N atom of the basic structure of the compound of formula (1).

[0080] Particularly preferably, L represents an optionally substituted phenylene, dibenzothiophene or dibenzofuran group, i.e. a group of the formulas (L-1) to (L-3), (L-19) to (L-33) or (L-34) to (L-49), in particular the groups (L-1), (L-2) or (L-19) to (L-33).

[0081] Particularly preferably, L represents an optionally substituted triphenylene group, i.e. a group of the formulas (L-55) to (L-57), in particular the group (L-57).

[0082] The invention also further relates to compounds of formula (1), where the symbols and indices used are:

[0083] R* is a group of the following formula (1a),

[0084] Formula (1 a) wherein the dashed bond represents the bond to the N atom of formula (1);

[0085] X is the same or different at each occurrence N or CR C , with the proviso that at least one group X stands for N and in the case that X stands for CR C stands, this no ring with Ar a or Ar b forms;

[0086] L is, identically or differently at each occurrence, an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 may be substituted, where L is substituted by a radical R or radical R a can also form an aliphatic, heteroaliphatic or heteroaromatic ring system, or L is a group of the formula -L 1 -QL 2 - where L 2 to the heteroaryl group of formula (1a) and L 1 to the N atom of the parent structure of formula (1);

[0087] Q is a group of formula (4) where the dashed bonds represent the connection to L 1 or L 2 represent and L 1 and L 2at each occurrence may be bonded either to the same or to different phenyl rings of the group of formula (4), with the proviso that the sum of aromatic ring atoms including all heteroatoms of the groups L 1 , L 2 and Q is 13 to 40;

[0088] G is the same or different as O or S at each occurrence;

[0089] L 1 , L 2 are each independently of one another on each occurrence, identically or differently, a single bond, an aryl group having 6 to 24 aromatic ring atoms or a heteroaryl group having 5 to 24 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted;

[0090] Ar a , Ar bare each independently of one another on each occurrence, identically or differently, an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted;

[0091] R, R a , R b are each independently of one another at each occurrence, the same or different H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2,OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted, with one or more non-adjacent CH2 groups being replaced by -R 1 C=CR 1 - , -C=C-, Si(R 1 )2, CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, where two or more radicals R and / or R bound to the same cycle a and / or R b can form an aliphatic or heteroaliphatic ring system which can be substituted with one or more radicals R 1may be substituted, and wherein two radicals R and / or R bonded to the same carbon, silicon, germanium or tin atom a and / or R b can form a monocyclic or polycyclic, aliphatic or aromatic ring system which can be substituted by one or more radicals R 1 can be substituted;

[0092] R c is the same or different at each occurrence H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2, OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted, with one or more non-adjacent CH2 groups being substituted by -R 1 C=CR 1 -, -C=C-, Si(R 1 )2, NR 1 , CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, where two or more R residues bound to the same cycle c can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system which can be substituted with one or more radicals R 1may be substituted, and wherein two radicals R bonded to the same carbon, silicon, germanium or tin atom c can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more radicals R 1 can be substituted;

[0093] R 1 is the same or different at each occurrence D, F, I, B(OR 2 )2, N(R 2 )2, CHO, C(=O)R 2 , CR 2 =C(R 2 )2, CN, C(=O)OR 2 , Si(R 2 )3, NO2, P(=O)(R 2 )2, OSO2R 2 , SR 2 , OR 2 , S(=O)R 2 , S(=O)2R 2 , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 2and wherein one or more CH2 groups in the above-mentioned groups are substituted by -R 2 C=CR 2 - , -C C-, Si(R 2 )2, C=O, C=S, -C(=O)O-, NR 2 , CONR 2 , P(=O)(R 2 ), O, S, SO or SO2 and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, where two or more radicals R 1 can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system;

[0094] R 2is, identically or differently at each occurrence, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by D or F; two or more substituents R 2 be linked together to form a ring; s,t are, independently of one another, the same or different, 0, 1, 2, 3 or 4 at each occurrence;

[0095] I, m are, at each occurrence, independently of one another, the same or different: 0, 1, 2, or 3; n is, at each occurrence, independently of one another, the same or different: 0, 1, 2, 3, or 4.

[0096] Preferred embodiments of formula (1) are compounds of formula (1-2) and formula (1-3), where the symbols used are X, Ar a , Ar b , L 1 , L 2 , Q, R, R a , R b and indices I, m and n have the meaning given above and where:

[0097] L 3 is at each occurrence, identically or differently, an aromatic ring system with 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted, where L 3 with a residue R or residue R a can also form an aliphatic, heteroaliphatic or heteroaromatic ring system. L is preferred 3 selected from the structures of formulas (L-1) to (L18) or (L-50) to (L-57).

[0098] Preferred embodiments of formula (1-2) and formula (1-3) are compounds of formulas (1-2a), (1-2b), (1-2c), (1-2d), (1-2e), (1-2f), (1-2g), (1-2h), (1-2i), (1-2j), (1-2k), (1-2l), (1-2m), (1-2n), (1-2o); (1-3a), (1-3b), (1-3c) and (1-3d), particularly preferred are compounds of formulas (1-2a), (1-2d), (1-2h), (1-2j), (1-3a) and (1-3b), in particular compounds of formulas (1-2a) and (1-3b) and (1-2o),

[0099] Formula (1-2d) Formula (1-2e)

[0100]

[0101] Formula (1-2h) Formula (1-2i)

[0102]

[0103] Formula (1-2m) Formula (1-2n)

[0104] Formula (1-3c) Formula (1 -3d) where the symbols and indices used are X, Ar a , Ar b , L 1 , L 2 , R, R a , R b , R 1 , 1, m, n, s and t have the meaning given above, where the hydrogen atoms of the compounds may be wholly or partly replaced by deuterium and where: u is on each occurrence, independently of one another, the same or different: 0, 1 or 2 v is on each occurrence, independently of one another, the same or different: 0, 1, 2 or 3 w is on each occurrence, independently of one another, the same or different: 0, 1 or 2.

[0105] In a preferred embodiment of the compounds of the formulas (1-2a), (1-2b), (1-2c), (1-2d), (1-2e), (1-2f), (1-2g), (1-2h), (1-2i), (1-2j), (1-2k), (1-2l), (1-2m), (1-2n), the indices s, t, v, u, w, l, m and n, identically or differently, represent 0 or 1 at each occurrence. Particularly preferably, the sum of the indices s+l+m+n= 0 or 1, or the sum of the indices u+s+l+m+n= 0 or 1 or the sum of the indices v+l+m+n= 0 or 1, or the sum of the indices s+t+l+m+n= 0 or 1 or the sum of the indices w+l+m+n= 0 or 1 , except for the case that R and / or R 1 and / or R a and / or R b for D, then preferably the sum of the above indices is maximal.

[0106] In a preferred embodiment of the compounds of formulas (1-2) and (1-2a), L 3at each occurrence represents a meta- or para-linked phenyl group and the indices s, t, l, m and n at each occurrence, identically or differently, represent 0 or 1. Particularly preferably, the sum of the indices s+l+m+n= 0, except for the case where R and / or R 1 and / or R a and / or R b for D, then preferably the sum of the above indices is maximal.

[0107] In a preferred embodiment of the compounds of formula (1-2o), the indices s, t, l, m and n are, identically or differently, 0 or 1 at each occurrence. Particularly preferably, the sum of the indices s+t+l+m+n= 0, except for the case where R and / or R 1 and / or R a and / or R b for D, then preferably the sum of the above indices is maximal.

[0108] In preferred embodiments of the compounds of formulas (1-3a), (1-3b), (1-3c) and (1-3d), L 1 and L 2at each occurrence, identically or differently, independently of one another, each represents a single bond, a phenyl or dibenzofuran group, very particularly preferably a single bond or an ortho-, meta- or para-linked phenylene group or a dibenzofuran group to which the heteroaryl group and / or the N-bridged triphenylene are bonded either in the meta- or para-position on the same phenyl ring of the dibenzofuran or to the different phenyl rings of the dibenzofuran, and the indices s, t, l, m and n are identically or differently at each occurrence and represent 0 or 1. Particularly preferably, the sum of the indices s+t+l+m+n= 0 or 1 except for the case that R and / or R 1 and / or R a and / or R b for D; then preferably the sum of the indices s+t+l+m+n is maximal, especially in the case that all R, R 1 , R a and R b for D the sum is s+t+l+m+n=16.

[0109] Further preferred embodiments of the compounds of formulas (1-2a), (1-2b), (1-2c), (1-2d), (1-2e), (1-2f), (1-2g), (1-2h), (1-2i), (1-2j), (1-2k), (1-2I), (1-2m), (1-2n), (1-2o), (1-3a), (1-3b), (1-3c) and (1-3d) are the following compounds of formulas (1-2a-1) to (1-2a-3), (1-2b-1), (1-2c-1), (1-2d-1) to (1-2d-3), (1-2j-1) to (1-2j-5), (1-2k-1) to (1-2k-2), (1-2n-1) to (1-2n-2), (1-2o-1) to (1-2o-3), (1-3a-1) to (1-3a-6), formulas (1-3b-1) to (1-3b-17), formulas (1-3c-1) to (1-3c-6) and formulas (1-3d-1) to (1-3d-17), particularly preferred are formulas (1-2a-1) to (1-2a-3), (1-2d-1) to (1-2d-3), (1-2j-1) to (1-2j-5), (1-2k-1) to (1-2k-2), (1-3a-1) to (1-3a-6) and formulas (1-3b-1) to (1-3b-17), in particular compounds of the formulas (1-2a-2) and (1-2a-3), (1-2o-1), (1-3b-1) to (1-3b-17),

[0110] Formula (1-2a-1) Formula (1-2a-2) Formula (1-2a-3)

[0111]

[0112] Formel (1 -2j-2) Formel (1 -2j-3) Formel (1-2j-4)

[0113]

[0114] Formula (1-2o-1) Formula (1-2o-2)

[0115]

[0116] Formula (1-3b-5) Formula (1-3b-6)

[0117]

[0118] Formula (1-3b-11) Formula (1-3a-12)

[0119]

[0120] Formula (1-3b-17)

[0121]

[0122] Formula (1-3d-14) Formula (1 -3d-15)

[0123] Formula (1-3d-16) Formula (1-3d-17) where the symbols used have the meanings given above and the H atoms of the compounds of the formulas (1-2a-1) to (1-2a-3), (1-2b-1), (1-2C-1), (1-2d-1) to (1-2d-3), (1-2j-1) to (1-2j-5), (1-2k-1) to (1-2k-2), (1-2n-1) to (1-2n-2), (1-2o-1) to (1-2o-3), (1-3a-1) to (1-3a-6), formulas (1-3b-1) to (1-3b-17), formulas (1-3c-1) to (1-3c-6) and formulas (1-3d-1) to (1-3d-17) are completely or partially represented by D atoms can be replaced.

[0124] In further particularly preferred embodiments of the compounds of the formulas (1-2a-1) to (1-2a-3), (1-2b-1), (1-2c-1), (1-2d-1) to (1-2d-3), (1-2j-1) to (1-2j-5), (1-2k-1) to (1-2k-2), (1-2n-1) to (1-2n-2), (1-2o-1) to (1-2o-3), (1-3a-1) to (1-3a-6), (1-3b-1) to (1-3b-17), (1-3c-1) to (1-3c-6) and (1-3d-1) to (1-3d-17), at least two X are N, in particular all three X are N.

[0125] Examples of suitable compounds of formulas (1), (1-1a) to (1-11), (1-2) and (1-3) selected according to the invention are the structures shown below in Table 1.

[0126] Table 1 :

[0127]

[0128] Particularly suitable compounds of formulas (1), (1-1a) to (1-11), (1-2) and (1-3), which are preferably used in combination with at least one compound of formula (2) or (3) in the electroluminescent device according to the invention, are compounds E1 to E33. Table 2:

[0129] The preparation of the compounds of formulas (1-2) and (1-3) can be carried out according to the following schemes, where the symbols used have the meanings given above.

[0130] Formula (1-2)

[0131] Compounds of formula (2) can be represented by the following formulas (2-1), (2-2), and (2-3), where the symbols used have the meanings mentioned above.

[0132] Preferred compounds of formula (2) or (2-1) are compounds of formulas (2-1 a) to (2-1 g), particularly preferred are compounds of formulas (2-1a), (2-1c), (2-1e) and (2-1 f), in particular compounds of formula (2-1c). where the symbols used have the meanings given above, L x1 in formulas (2-1a) and (2-1b) denotes an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is substituted by one or more radicals R 1 may be substituted, where a substituent R f on the carbazole with a substituent R 1can form a ring, V = C(R 1 )2, NAr', O or S, and where o1 and z1 are, identically or differently, 0, 1, 2, 3 or 4 at each occurrence, p1 is, identically or differently, 0, 1, 2 or 3 at each occurrence, p2 is, identically or differently, 0, 1 or 2 at each occurrence. In the compounds of the formulas (2), (2-1), (2-2), (2-3), (2-1 a), (2-1 b), (2-1c), (2-1 d) and (2-1 e), a substituent R f and a substituent R 1 form a ring, for example in formula (2-1 e) also defined by V, wherein preferably the following rings V-1 to V-7 are formed and the dashed lines each represent the bond to the carbazoles:

[0133] In the compounds of formulas (2), (2-1), (2-2), (2-3), (2-1a), (2-1b), (2-1c), (2-1d) and (2-1e) two substituents R f one or more times together form a ring, or two substituents R 1can form one or more times together a ring which is preferably selected from the following structures (S1) to (S9), where # and # represent the respective linkage point with the C atoms and the structures are each substituted with one or more substituents R 1 can be substituted:

[0134] R 1 in the partial structures (S1) to (S9) is preferably H, D or an aromatic or heteroaromatic ring system with 5 to 30 ring atoms, which is represented by R 2 may be substituted, particularly preferably H, D or phenyl. If the structures (S1) to (S9) are structures formed by ring formation of two substituents R 1 arise, these structures are marked with R 2 instead of R 1 substituted.

[0135] In the compounds of formulas (2), (2-1), (2-2), (2-3), (2-1a), (2-1b), (2-1c), (2-1d) and (2-1e) a substituent Ar cand a substituent R e or a substituent Ar c and a substituent R f form a ring. Furthermore, a substituent Ar d with a substituent R 1 form a ring. The ring formation is indicated by the group U, where U = a single bond, O, S, NAr' or C(R 1 )2, is preferably a single bond and the indices a, b, c and d are the same or different at each occurrence and independently of one another are 0 or 1.

[0136] Likewise preferred compounds of the formulas (2) or (2-1) are compounds of the formulas (2-2a) to (2-2e), particularly preferred are compounds of the formulas (2-2a), (2-2c) and (2-2e, in particular (2-2c). where the symbols used have the meanings given above, L x1in formulas (2-2a) and (2-2b) means an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, which with one or more radicals R 1 can be substituted and where o1 and z1 are, identically or differently, independently of one another, 0, 1, 2, 3 or 4 at each occurrence, p1 is, identically or differently, independently of one another, 0, 1, 2 or 3 at each occurrence, p2 is, identically or differently, independently of one another, 0, 1 or 2 at each occurrence.

[0137] In a preferred embodiment of the compounds of formulas (2-2a) to (2-2e), the sum of the indices, if present, a+b and / or the sum of the indices c+d is independently equal to 1, very particularly preferably the sum of the indices a+b and the sum of the indices is each independently equal to 1.

[0138] In preferred embodiments of the compounds of formulas (2-2a) to (2-2e), the indices, if present, are a=1 and b, c and d=0; or a, b, c = 0 and d = 1, or a, d = 1 and b, c = 0.

[0139] In a preferred embodiment of the compounds of the formulas (2), (2-1 a) to (2-1f) and (2-2a) to (2-2e), the indices o1, p1, p2 and z, identically or differently, independently of one another at each occurrence are 0, 1 or 2, particularly preferably 0 or 1, in particular all indices are equal to 0. In the event that the radicals R e , R f and R 1 for D it is preferred that the indices take the maximum possible number, i.e. o1=4, p1 =3, p2=2 and z=4.

[0140] In a further preferred embodiment of the compounds of formula (2), at least one of the carbazoles is linked to the second carbazole via the 3-position.

[0141] If in compounds of formulas (2), (2-1a) to (2-1f) and (2-2a) to (2-2e) o1 and / or p1 and / or p2 and / or z1 is greater than 0, the respective substituent R e , R f and R 1 at each occurrence, identically or differently, preferably selected from the group consisting of D, F, an alkyl group having 1 to 10 C atoms or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which is substituted by one or more radicals R 1 can be substituted and in the case of R 1 with further residues R 2 The aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms in these radicals R e , R f and R 1 is preferably derived from benzene, dibenzofuran, dibenzothiophene, 9-phenylcarbazole, biphenyl and terphenyl, which is substituted with one or more radicals R 1 can be substituted and in the case of R 1 with several residues R2 The preferred position of the substituents is position 1, 2, 3 or 4 or the combinations of positions 1 and 4 and 1 and 3, particularly preferably 1 and 3, 2 or 3, most preferably 3, where R e , R f and R 1 have one of the preferred meanings given above and o1 , p1 , p2 and z1 are each independently greater than 0. Particularly preferred substituents R e , R f and R 1 are carbazol-9-yl, biphenyl, terphenyl, triphenylenyl and dibenzofuranyl.

[0142] Ar' in N(Ar')2 is preferably derived from benzene, dibenzofuran, fluorene, spirobiflurene, dibenzothiophene, 9-phenylcarbazole, biphenyl and terphenyl, which is substituted with one or more substituents R 1 may be substituted or combinations of these groups. Ar' is preferably unsubstituted.

[0143] In compounds of formulas (2), (2-1a) to (2-1f) and (2-2a) to (2-2e), as previously described, Ar c and Ar d each independently of one another preferably an aromatic ring system having 6 to 30 aromatic ring atoms or a heteroaromatic ring system having 6 to 30 aromatic ring atoms, which is substituted by one or more radicals R d can be substituted. Ar c and Ar d are preferably derived from benzene, dibenzofuran, fluorene, spirobifluorene, dibenzothiophene, 9-phenylcarbazole, biphenyl, naphthyl, triphenylene and terphenyl, which are substituted with one or more substituents R d may be substituted or combinations of these groups, where R d has the meaning given above.

[0144] Standing Ar c and Ar d for a heteroaromatic ring system with 6 to 40 C- atoms, which is substituted with one or more of the substituents R dmay be substituted, electron-rich ring systems are particularly preferred, wherein the optionally substituted by R d substituted ring system preferably contains only one N atom in its entirety or which is optionally substituted by R d substituted ring system as a whole contains one or more O and / or S atoms.

[0145] In the compounds of formulas (2), (2-1), (2-2), (2-3), (2-1 a), (2-1 b), (2-1c), (2-1 d), (2-1e), (2-1f), (2-2a), (2-2b), (2-2c), (2-2d) and (2-2e), the linker L', if it is not a single bond or L x1 , preferably selected from the linkers L-2.1 to L-2.33,

[0146] L-2.32 L-2.33 where W is NAr', O, S or C(CH3)2, Ar' has the meaning given above, the linkers L-2.1 to L-2.33 are replaced by one or more radicals R 1 can be substituted and the dashed lines indicate the connection to the carbazoles. For the linker L xcan a residue R 1 at one of the linkers L-2.1 to L-2.33 with a residue R f or another R 1 of the carbazole

[0147] form a ring.

[0148] Preferably, the linkers L-2.1 to L-2.33 are unsubstituted, where the H atoms may be completely or partially replaced by D or substituted by a phenyl. Preferred linkers for L x and L x1 are selected from the structures L-2.1 to L-2.33, in which W is O, S or NAr', particularly preferably O or NAr'.

[0149] In a particularly preferred embodiment of the invention, the above-mentioned preferences for linkers and indices occur together.

[0150] Preferred embodiments of formulas (2-1a) to (2-1f) are the

[0151] Compounds of the formulas (2-1a-1) to (2-1a-3), (2-1b-1) to (2-1b-3), (2-1c-1) to (2-1C-19), (2-1d-1) to (2-1d-4), (2-1e-1) to (2-1e-9) and (2-1f-1) to (2-1f-

[0152] 6), particularly preferred are compounds of the formulas (2-1a-1) and (2-1a-3),

[0153] (2-1C-1) to (2-1c-19), (2-1e-1) to (2-1e-9) and (2-1f-1) to (2-1f-6), in particular compounds of the formulas (2-1c-4), (2-1c-17), (2-1e-2), (2-1e-3),

[0154] Formula (2-1 f-4) Formula (2-1 f-5) Formula (2-1 f-6) where the symbols used have the meanings given above, W preferably represents O or NAr', V preferably represents O, S or C(R 1 )2. The hydrogen atoms can also be completely or partially replaced by deuterium. The compounds are preferably fully or partially deuterated, especially fully deuterated.

[0155] Preferred embodiments of the formulas (2-2a) to (2-2e) are the compounds of the formulas (2-2a-1) to (2-2a-5), (2-2b-1) to (2-2b-3), (2-2c-1) to (2-2c-5), (2-2d-1) to (2-2d-2), (2-2e-1) to (2-2e-19). Particularly preferred are compounds of the formulas (2-2a-1) to (2-2a-5), (2-2c-1) to (2-2c-5) and (2-2e-1) to (2-2e-19), in particular compounds of the formulas (2-2c-1), (2-2c-2), (2-2c-3), (2-2c-4), (2-2e-1), (2-2e-2), (2-2e-4), (2-2e-5), (2-2e-6), (2-2e-12), (2-2e-13) and (2-2e-16),

[0156] Formula (2-2e-18) Formula (2-2e-19) where the symbols used have the meanings given above, W preferably represents O or NAr', V preferably represents O, S or C(R 1 )2 and U preferably represents a single bond, O, S, NAr' or C(R 1)2 particularly preferably represents a single bond or NAr', especially a single bond. The hydrogen atoms can also be completely or partially replaced by deuterium.

[0157] The host material of formula (3) and its preferred embodiments are described below.

[0158] Formula (3)

[0159] In a preferred embodiment of the compounds of formula (3), Ar 1 and Ar 2 independently selected from the following groups R2-1 to R2-222 of Table 3. Table 3:

[0160] where the dashed line represents the bond to the N atom of formula (3). Preferably, the substituents R2-1 to R2-221 are partially deuterated or fully deuterated.

[0161] In a preferred embodiment of the compounds of formula (3), Y is O or C(R g )2 and the substituents R h and R' is H, D or phenyl, particularly preferably H or D, especially D. The indices q and R are preferably 0 or 1 in the case that R h and / or R' is a phenyl group and preferably q is 3 and r is 4 in the case that R h and / or R' D are.

[0162] Examples of suitable compounds of formulas (2), (2-1), (2-2), (2-1a-1) to (2-1f-6) and (2-2a-1) to (2-2e-19) as well as of formula (3) selected according to the invention are the structures listed below in Table 4.

[0163] Table 4:

[0164] Further preferred compounds of formula (2) are compounds as described in W02022038066, pages 34 to 62. Particularly preferred compounds of formula (2) are listed in the following table:

[0165] Another subject of the invention is an organic electronic device comprising an organic layer comprising the compositions comprising at least one compound of formula (1) and at least one compound of formula (2) or formula (3), where the symbols and indices used are: R* is a group of the following formula (1a),

[0166] Formula (1 a) wherein the dashed bond represents the bond to the N atom of formula (1);

[0167] X is the same or different at each occurrence N or CR C , with the proviso that at least one group X stands for N and in the case that X stands for CR Cstands, this no ring with Ar a or Ar b forms;

[0168] L is, identically or differently at each occurrence, an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 may be substituted, where L is substituted by a radical R or radical R a can also form an aliphatic, heteroaliphatic or heteroaromatic ring system, or L is a group of the formula -L 1 -QL 2 - where L 2 to the heteroaryl group of formula (1a) and L 1 to the N atom of the parent structure of formula (1);

[0169] Q is a group of formula (4), where the dashed bonds represent the connection to L 1 or L 2 represent and L 1 and L 2at each occurrence may be bonded either to the same or to different phenyl rings of the group of formula (4), with the proviso that the sum of aromatic ring atoms including all heteroatoms of the groups L 1 , L 2 and Q is 13 to 40;

[0170] G is the same or different as O or S at each occurrence;

[0171] L 1 , L 2 are each independently of one another on each occurrence, identically or differently, a single bond, an aryl group having 6 to 24 aromatic ring atoms or a heteroaryl group having 5 to 24 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted;

[0172] Ar a , Ar bare each independently of one another on each occurrence, identically or differently, an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted;

[0173] Ar c , Ar d are each independently of one another, identically or differently on each occurrence, an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R d can be substituted;

[0174] Y is the same or different at each occurrence and is selected from O, S or C(R g )2;

[0175] Ar 1 , Ar 2are each independently of one another, identically or differently on each occurrence, an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted;

[0176] R, R a , R b are each independently of one another at each occurrence, the same or different H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2,OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted, with one or more non-adjacent CH2 groups being replaced by -R 1 C=CR 1 - , -C=C-, Si(R 1 )2, CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, where two or more radicals R and / or R bound to the same cycle a and / or R b can form an aliphatic or heteroaliphatic ring system which can be substituted with one or more radicals R 1may be substituted, and wherein two radicals R and / or R bonded to the same carbon, silicon, germanium or tin atom a and / or R b can form a monocyclic or polycyclic, aliphatic or aromatic ring system which can be substituted by one or more radicals R 1 can be substituted;

[0177] R c , R e , R f , R g , R h , R' are each independently, identically or differently, at each occurrence, H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2, OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by - R 1 C=CR 1 -, -C=C-, Si(R 1 )2, NR 1 , CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, where two or more R residues bound to the same cycle c , R e , R f , R g , R hor R' can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system which can be substituted with one or more radicals R 1 may be substituted, and wherein two radicals R bonded to the same carbon, silicon, germanium or tin atom c , R e , R f , R g , R h or R' may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more radicals R 1 can be substituted;

[0178] R d is the same or different at each occurrence H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2, OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted, with one or more non-adjacent CH2 groups being substituted by -R 1 C=CR 1 -, -C=C-, Si(R 1 )2, NR 1 , CONR 1 , 0=0, C=S, -C(=O)O-, P(=O)(R 1 ), O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, where two or more R residues bound to the same cycle d can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system which can be substituted with one or more radicals R 1may be substituted, and wherein two radicals R bonded to the same carbon, silicon, germanium or tin atom d can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more radicals R 1 can be substituted;

[0179] R x is H, D or (L x ) y -Ar x ;

[0180] L x is at each occurrence, identically or differently, a single bond, or an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted;

[0181] Ar x is at each occurrence, identically or differently, an unsubstituted or substituted 9-Ar d-carbazolyl or an unsubstituted or substituted carbazol-9-yl which is substituted with one or more radicals R 1 may be substituted and wherein independently of one another one or more times two radicals R 1 or a residue R 1 together with a remainder of Ar d or R f can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring or for y=0, two adjacent R f and Ar x together form a ring of formula (5), where the positions marked with * represent the bonds to the phenyl ring of formula (2), and the other R f are, identically or differently, H or a substituent as defined above at each occurrence;

[0182] Formula (5)

[0183] Ar' is at each occurrence, identically or differently, an aromatic ring system with 6 to 40 aromatic ring atoms or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is substituted by one or more radicals R 1 can be substituted;

[0184] R 1 is the same or different at each occurrence D, F, I, B(OR 2 )2, N(R 2 )2, CHO, C(=O)R 2 , CR 2 =C(R 2 )2, CN, C(=O)OR 2 , Si(R 2 )3, NO2, P(=O)(R 2 )2, OSO2R 2 , SR 2 , OR 2 , S(=O)R 2 , S(=O)2R 2 , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 2and wherein one or more CH2 groups in the above-mentioned groups are substituted by -R 2 C=CR 2 - , -C C-, Si(R 2 )2, C=O, C=S, -C(=O)O-, NR 2 , CONR 2 , P(=O)(R 2 ), O, S, SO or SO2 and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, where two or more radicals R 1 can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system;

[0185] R 2is, identically or differently at each occurrence, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by D or F; two or more substituents R 2 be linked together and form a ring;

[0186] I, m, p, q are each independently the same or different at each occurrence: 0, 1, 2 or 3; n, o, r, z, s, t are each independently the same or different at each occurrence: 0, 1, 2, 3 or 4; y is each independently 0 or 1.

[0187] In a preferred embodiment of the organic electronic device comprising an organic layer comprising the composition comprising at least one compound of formula (1) and one compound of formula (2) or formula (3), the composition is preferably contained in the emission layer, in particular as host material in the emission layer together with a phosphorescent emitter.

[0188] The statements regarding the materials of formulas (1), (2) and (3) and their preferred embodiments apply accordingly to the composition, to the organic electronic device comprising the composition, and to the compounds of formula (1) according to the invention.

[0189] Particularly preferred compositions of the materials of formula (1) with the materials of formula (2) or (3) for the device according to the invention are obtained by combining the compounds E1 to E33 with H1 to H42 as shown below in Table 5.

[0190] Table 5:

[0191] If the composition according to the invention is used as host material in the light-emitting layer, the concentration of the electron-transporting host material of the formula (1), as described above or preferably described, in the composition according to the invention or in the light-emitting layer of the device according to the invention is in the range from 5 wt% to 90 wt%, preferably in the range from 10 wt% to 85 wt%, more preferably in the range from 20 wt% to 85 wt%, even more preferably in the range from 30 wt% to 80 wt%, very particularly preferably in the range from 20 wt% to 60 wt% and most preferably in the range from 30 wt% to 50 wt%, based on the entire mixture or based on the entire composition of the light-emitting layer.

[0192] The concentration of the hole-transporting host material of the formulas (2) or (3), as described above or described as preferred, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is in the range from 10 wt.% to 95 wt.%, preferably in the range from 15 wt.% to 90 wt.%, more preferably in the range from 15 wt.% to 80 wt.%, even more preferably in the range from 20 wt.% to 70 wt.%, very particularly preferably in the range from 40 wt.% to 80 wt.% and most preferably in the range from 50 wt.% to 70 wt.%, based on the total mixture or based on the total composition of the light-emitting layer.

[0193] The present invention also relates to a mixture which, in addition to the above-mentioned host materials of formula (1) and formula (2) or formula (3), as described above or preferably described, in particular mixtures M1 to M1386, contains at least one phosphorescent emitter.

[0194] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the light-emitting layer contains at least one phosphorescent emitter in addition to the above-mentioned host materials of formula (1) and formula (2) or formula (3) as described above or preferably described, in particular the material combinations M1 to M1386.

[0195] The concentration of the phosphorescent emitter, as described below or described as preferred, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is in the range from 1 wt.% to 30 wt.%, preferably in the range from 2 wt.% to 20 wt.%, more preferably in the range from 4 wt.% to 15 wt.%, even more preferably in the range from 8 wt.% to 12 wt.%, based on the total mixture or based on the total composition of the light-emitting layer.

[0196] The term "phosphorescent emitters" typically encompasses compounds in which light emission occurs through a spin-forbidden transition from an excited state with a higher spin multiplicity, i.e., a spin state > 1, for example, through a transition from a triplet state or a state with an even higher spin quantum number, such as a quintet state. Preferably, this refers to a transition from a triplet state.

[0197] Particularly suitable phosphorescent emitters (= triplet emitters) are compounds that emit light upon suitable excitation, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number. Preferably, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are used as phosphorescent emitters, in particular compounds containing iridium or platinum. For the purposes of the present invention, all luminescent compounds containing the above-mentioned metals are considered phosphorescent emitters.

[0198] In general, all phosphorescent complexes as used in the prior art for phosphorescent OLEDs and as known to the person skilled in the art in the field of organic electroluminescent devices are suitable.

[0199] Examples of the emitters described above can be found in the applications WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626, WO 2011 / 066898, WO 2011 / 157339, WO 2012 / 007086, WO 2014 / 008982, WO 2014 / 023377, WO 2014 / 094961, WO 2014 / 094960, WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO 2016 / 015815, WO 2016 / 124304, WO 2017 / 032439, WO 2018 / 011186, WO 2018 / 001990, WO 2018 / 019687, WO 2018 / 019688, WO 2018 / 041769, WO 2018 / 054798, WO 2018 / 069196, WO 2018 / 069197, WO 2018 / 069273, WO 2018 / 178001, WO 2018 / 177981, WO 2019 / 020538, WO 2019 / 115423, WO 2019 / 158453 and WO 2019 / 179909.

[0200] Preferred phosphorescent emitters according to the present invention correspond to compounds of formula (IIIa), where the symbols and indices for this formula (Illa) have the meaning: n'+m' is 3, n' is 1 or 2, m' is 2 or 1 ,

[0201] X is N or CR,

[0202] R is H, D, CN, F, or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 7 C atoms or a partially or fully deuterated cycloalkyl group having 4 to 7 C atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms or a heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be partially or fully deuterated.

[0203] The invention accordingly further provides an organic electroluminescent device as described above or preferably described, characterized in that the light-emitting layer contains, in addition to the host materials 1 and 2, at least one phosphorescent emitter corresponding to formula (IIIa), as described above. In emitters of formula (IIIa), n is preferably 1 and m is preferably 2.

[0204] In emitters of the formula (IIIa), one X is preferably selected from N and the other Xs are CR or all Xs are CR.

[0205] In emitters of formula (IIIa), at least one R is preferably different from H or two R are different from H and have one of the meanings otherwise previously given for the emitters of formula (IIIa).

[0206] In a further preferred embodiment of the compounds of formula (IIIa), the compounds are partially or completely deuterated.

[0207] Further preferred phosphorescent emitters according to the present invention correspond to the formulas (I), (II) or (III), where the symbols and indices for these formulas (I), (II) and (III) have the meaning:

[0208] Ri is H or D, R2 is H, D or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium.

[0209] Preferred phosphorescent emitters according to the present invention correspond to the formulas (IV), (V) or (VI), where the symbols and indices for these formulas (IV), (V) and (VI) have the meaning:

[0210] Ri is H or D, R2 is H, D, F or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium.

[0211] Preferred examples of phosphorescent emitters are listed in Table 6 below. Table 6:

[0212]

[0213] In the mixtures according to the invention or in the light-emitting layer of the device according to the invention, each mixture M1 to M1134 or M1135 to M1386 is preferably combined with a compound of the formula (IIIa) or a compound of the formulas (I) to (VI) or a compound from Table 6.

[0214] The light-emitting layer in the organic electroluminescent device according to the invention containing at least one phosphorescent emitter is preferably an infrared-emitting, yellow, orange, red, green, blue or ultraviolet-emitting layer, particularly preferably a yellow or green or red-emitting layer and very particularly preferably a green or red-emitting layer, in particular a green-emitting layer.

[0215] A yellow-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 540 to 570 nm. An orange-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 570 to 600 nm. A red-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 600 to 750 nm. A green-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 490 to 540 nm. A blue-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 440 to 490 nm.The photoluminescence maximum of the layer is determined by measuring the photoluminescence spectrum of the layer with a layer thickness of 50 nm at room temperature, wherein the layer contains the inventive combination of the host materials of formulas (1) and (2) or of formulas (1) and (3) and the corresponding emitter. The photoluminescence spectrum of the layer is recorded, for example, using a commercially available photoluminescence spectrometer.

[0216] The photoluminescence spectrum of the selected emitter is usually measured in oxygen-free solution, 10' 5 molar, measured at room temperature. Any solvent in which the selected emitter dissolves at the specified concentration is suitable. Particularly suitable solvents are usually toluene or 2-methyl-THF, but also dichloromethane.

[0217] The measurement is performed using a commercially available photoluminescence spectrometer. The triplet energy T1 in eV is determined from the photoluminescence spectra of the emitters. First, the peak maximum Plmax. (in nm) of the photoluminescence spectrum is determined. The peak maximum Plmax. (in nm) is then converted to eV using the formula: E(T1 in eV) = 1240 / E(T1 in nm) = 1240 / PLmax. (in nm).

[0218] Preferred phosphorescent emitters are therefore infrared emitters, preferably of formula (IIIa), formulas (I) to (VI) or from Table 6, whose triplet energy Ti is preferably between ~1.9 eV and -1.0 eV.

[0219] Preferred phosphorescent emitters are therefore red emitters, preferably of formula (IIIa), formulas (I) to (VI) or from Table 6, whose triplet energy Ti is preferably between -2.1 eV and -1.9 eV.

[0220] Preferred phosphorescent emitters are therefore yellow emitters, preferably of formula (IIIa), formulas (I) to (VI) or from Table 6, whose triplet energy Ti is preferably between -2.3 eV and -2.1 eV.

[0221] Preferred phosphorescent emitters are therefore green emitters, preferably of formula (IIIa), formulas (I) to (VI) or from Table 6, whose triplet energy Ti is preferably between -2.5 eV and -2.3 eV.

[0222] Preferred phosphorescent emitters are therefore blue emitters, preferably of formula (IIIa), formulas (I) to (VI) or from Table 6, whose triplet energy Ti is preferably between -3.1 eV and -2.5 eV.

[0223] Accordingly, particularly preferred phosphorescent emitters are green or yellow emitters, preferably of formula (IIIa), formulas (I) to (VI) or from Table 6, as described above. Accordingly, very particularly preferred phosphorescent emitters are green emitters, preferably of formula (IIIa), formulas (I) to (VI) or from Table 6, whose triplet energy Ti is preferably between ~2.5 eV and ~2.3 eV.

[0224] Very particular preference is given to selecting green emitters, preferably of the formula (IIIa), the formulas (I) to (VI) or from Table 6, as described above, for the composition according to the invention or the emitting layer according to the invention.

[0225] The light-emitting layer of the device according to the invention may also contain fluorescent emitters.

[0226] Preferred fluorescent emitters are selected from the class of arylamines. An arylamine or an aromatic amine within the meaning of this invention is understood to be a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, particularly preferably having at least 14 ring atoms. Preferred examples are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to be a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position.An aromatic anthracenediamine is understood to be a compound in which two diarylamino groups are directly bonded to an anthracene group, preferably in the 9,10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, with the diarylamino groups on the pyrene preferably being bonded in the 1-position or 1,6-position, respectively. Further preferred fluorescent emitters are indenofluorenamines or diamines, for example according to WO 2006 / 108497 or WO 2006 / 122630, benzoindenofluorenamines or diamines, for example according to WO 2008 / 006449, and dibenzoindenofluorenamines or diamines, for example according to WO 2007 / 140847, as well as the indenofluorene derivatives with condensed aryl groups disclosed in WO 2010 / 012328.In a further preferred embodiment of the invention, the at least one light-emitting layer of the organic electroluminescent device can comprise, in addition to the host materials 1 and 2, as described above or described as preferred, further host materials or matrix materials, so-called mixed-matrix systems. The mixed-matrix systems preferably comprise three or four different matrix materials, particularly preferably three different matrix materials (i.e., a further matrix component in addition to the host materials 1 and 2, as described above). Particularly suitable matrix materials that can be used in combination as a matrix component of a mixed-matrix system are selected from w / de-öand-gap materials, bipolar host materials, electron-transport materials (ETMs), and hole-transport materials (HTMs).

[0227] Wide-band-gap material is understood herein to mean a material within the meaning of the disclosure of US 7,294,849, which is characterized by a band gap of at least 3.5 eV, where band gap is understood to be the distance between HOMO and LUMO energy of a material.

[0228] According to one embodiment of the present invention, the mixture contains no further components, i.e., functional materials, besides the electron-transporting host material of formula (1) and the hole-transporting host material of formula (2) or (3). These are material mixtures used as such to produce the light-emitting layer. These mixtures are also referred to as premix systems, which are used as the sole material source during the vapor deposition of the host materials for the light-emitting layer and which have a constant mixing ratio during vapor deposition. This allows for the simple and rapid deposition of a layer with a uniform distribution of the components, without the need for precise control of a large number of material sources.

[0229] According to an alternative embodiment of the present invention, the mixture contains, in addition to the components electron-transporting host material of formula (1) and hole-transporting host material of formula (2), the phosphorescent emitter as described above. With a suitable mixing ratio during vapor deposition, this

[0230] Mixture can be used as the sole material source as previously described.

[0231] The components or constituents of the light-emitting layer of the device according to the invention can thus be processed by vapor deposition or from solution. The material combination of host materials 1 and 2, as described above or preferably described, optionally with the phosphorescent emitter, as described above or preferably described, is provided for this purpose in a formulation containing at least one solvent. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose.

[0232] The present invention therefore further provides a formulation comprising an inventive mixture of host materials 1 and 2, as described above, optionally in combination with a phosphorescent emitter, as described above or preferably described, and at least one solvent. The formulation preferably comprises at least one compound of formula (1) and one compound of formula (2) or (3) and a solvent. Furthermore, preference is given to a process that uses the formulation comprising at least one compound of formula (1) and one compound of formula (2) or (3) to apply the organic layer.

[0233] Geeignete und bevorzugte Lösemittel sind beispielsweise Toluol, Anisol, o-, m- oder p-Xylol, Methylbenzoat, Mesitylen, Tetralin, Veratrol, THF, Methyl-THF, THP, Chlorbenzol, Dioxan, Phenoxytoluol, insbesondere 3-Phenoxytoluol, (-)- Fenchon, 1 ,2,3,5-Tetramethylbenzol, 1 ,2,4,5-Tetramethylbenzol, 1 -Methylnaphthalin, 2-Methylbenzothiazol, 2- Phenoxyethanol, 2-Pyrrolidinon, 3- Methylanisol, 4-Methylanisol, 3,4-Dimethylanisol, 3,5-Dimethylanisol, Acetophenon, a-Terpineol, Benzothiazol, Butylbenzoat, Cumol, Cyclohexanol, Cyclohexanon, Cyclohexylbenzol, Decalin, Dodecylbenzol, Ethylbenzoat, Indan, Methylbenzoat, NMP, p-Cymol, Phenetol, 1 ,4-Diisopropylbenzol, Dibenzylether, Diethylenglycolbutylmethylether, Triethylenglycolbutylmethylether, Diethylenglycoldibutylether, T riethylenglycoldimethylether, Diethylenglycol- monobutylether, T ripropyleneglycoldimethylether, T etraethylenglycoldimethyl- ether, 2-lsopropylnaphthalin, Pentylbenzol, Hexylbenzol, Heptylbenzol, Octylbenzol, 1,1-Bis(3,4-dimethylphenyl)ethane, hexamethylindane or mixtures of these solvents.

[0234] The formulation may also contain at least one further organic or inorganic compound which is also used in the light-emitting layer of the device according to the invention, in particular a further emitting compound and / or a further matrix material.

[0235] The light-emitting layer in the device according to the invention according to the preferred embodiments and the emitting compound preferably contains between 99.9 and 1 vol.%, more preferably between 99 and 10 vol.%, particularly preferably between 98 and 60 vol.%, very particularly preferably between 97 and 80 vol.% of matrix material composed of at least one compound of formula (1) and at least one compound of formula (2) or (3) according to the preferred embodiments, based on the total composition of emitter and matrix material. Accordingly, the light-emitting layer in the device according to the invention preferably contains between 0.1 and 99 vol.%, more preferably between 1 and 90 vol.%, particularly preferably between 2 and 40 vol.%, very particularly preferably between 3 and 20 vol.% of the emitter, based on the total composition of the light-emitting layer consisting of emitter and matrix material.If the compounds are processed from solution, the corresponding amounts in wt.% are preferably used instead of the amounts in vol.% given above.

[0236] The light-emitting layer in the device according to the invention according to the preferred embodiments and the emitting compound preferably contains the matrix material of formula (1) and the matrix material of formula (2) or formula (3) in a volume percentage ratio between 4:1 and 1:4, preferably between 1:3 and 1:1, particularly preferably between 1:2 and 1:1. If the compounds are processed from solution, the corresponding ratio in wt.% is preferably used instead of the above-specified ratio in vol.%.

[0237] Preferred hole transport materials are materials that can be used in a hole transport, hole injection or electron blocking layer, such as indenofluorenamine derivatives (e.g. according to WO 06 / 122630 or WO 06 / 100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (e.g. according to WO 01 / 049806), amine derivatives with condensed aromatics (e.g. according to US 5,061,569), the amine derivatives disclosed in WO 95 / 09147, monobenzoindenofluorenamines (e.g. according to WO 08 / 006449), dibenzoindenofluorenamines (e.g. according to WO 07 / 140847), dihydroacridine derivatives (e.g. WO 2012 / 150001).

[0238] The sequence of layers in the organic electroluminescent device according to the invention is preferably as follows:

[0239] Anode / hole injection layer / hole transport layer / electron blocking layer / emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0240] This sequence of layers is a preferred sequence.

[0241] It should be noted again that not all of the layers mentioned need to be present and / or that additional layers may be present.

[0242] The organic electroluminescent device according to the invention can contain a plurality of emitting layers. Preferably, at least one of the emitting layers is the organic layer according to the invention comprising at least one compound of formula (1) as host material 1 and at least one compound of formula (2) or (3) as host material 2, as described above. In this case, these emitting layers particularly preferably have a total of several emission maxima between 380 nm and 750 nm, resulting in overall white emission, i.e., various emitting compounds that can fluoresce or phosphoresce and that emit blue, yellow, orange, or red light are used in the emitting layers. Particular preference is given to three-layer systems, i.e., systems with three emitting layers, wherein the three layers exhibit blue, green, and orange or red emission (for the basic structure, see, for example, WO 2005 / 011013).It should be noted that instead of using multiple color-emitting emitter compounds, a single emitter compound emitting in a wide wavelength range may also be suitable for generating white light.

[0243] Suitable charge transport materials which can be used in the hole injection or hole transport layer or electron blocking layer or in the electron transport layer of the organic electroluminescent device according to the invention are, for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010 or other materials which are used in these layers according to the prior art.

[0244] All materials known to be used as electron-transport materials in the electron-transport layer according to the prior art can be used as materials for the electron-transport layer. Particularly suitable are aluminum complexes, for example Alqs; zirconium complexes, for example Zrq4; benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives. Further suitable materials are derivatives of the above-mentioned compounds, as disclosed in JP 2000 / 053957, WO 2003 / 060956, WO 2004 / 028217, WO 2004 / 080975, and WO 2010 / 072300.

[0245] Suitable cathodes for the device according to the invention include metals with low work functions, metal alloys, or multilayer structures made of different metals, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys made of an alkali or alkaline earth metal and silver, for example, an alloy of magnesium and silver, are also suitable. In multilayer structures, in addition to the metals mentioned, other metals with a relatively high work function, such as Ag or Al, can also be used. Combinations of the metals, such as Ca / Ag, Mg / Ag, or Ba / Ag, are then generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor.Suitable materials for this purpose include alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, U2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). Lithium quinolinate (LiQ) can also be used. The thickness of this layer is preferably between 0.5 and 5 nm.

[0246] Materials with a high work function are preferred as the anode. The anode preferably has a work function greater than 4.5 eV vs. vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Metal / metal oxide electrodes (e.g., Al / Ni / NiOx, Al / PtOx) may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to enable either the irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Also preferred are conductive, doped organic materials, in particular conductive doped polymers.Furthermore, the anode can also consist of several layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0247] The organic electroluminescent device according to the invention is structured, contacted and finally sealed accordingly (depending on the application) during production, since the lifetime of the devices according to the invention is shortened in the presence of water and / or air.

[0248] The production of the device according to the invention is not restricted in this respect. It is possible for one or more organic layers, including the light-emitting layer, to be coated using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10' 5 mbar, preferably less than 10' 6mbar. However, it is also possible that the initial pressure is even lower, for example less than 10' 7 mbar.

[0249] The organic electroluminescent device according to the invention is preferably characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) method or by means of carrier gas sublimation. The materials are sublimated at a pressure between 10' 5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (e.g., BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0250] Furthermore, the organic electroluminescent device according to the invention is preferably characterized in that one or more organic layers comprising the composition according to the invention are produced from solution, for example by spin coating, or by any printing process, such as screen printing, flexographic printing, nozzle printing, or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or inkjet printing. Soluble host materials 1 and 2 and phosphorescent emitters are required for this purpose. Processing from solution has the advantage that, for example, the light-emitting layer can be applied very easily and cost-effectively. This technique is particularly suitable for the mass production of organic electroluminescent devices.

[0251] Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are vapor-deposited.

[0252] These methods are generally known to the person skilled in the art and can be applied to organic electroluminescent devices.

[0253] The invention therefore further provides a process for producing the organic electroluminescent device according to the invention, as described above or preferably described, characterized in that the light-emitting layer is applied by vapor deposition, in particular using a sublimation process and / or an OVPD (Organic Vapor Phase Deposition) process and / or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or using a printing process. When produced by vapor deposition, there are basically two ways in which the light-emitting layer according to the invention can be applied or vapor-deposited onto any substrate or the previous layer. Firstly, the materials used can each be initially introduced into a material source and then subsequently vaporized from the various material sources (“co-evaporation”).Alternatively, the various materials can be premixed (premix systems) and the mixture can be placed in a single material source, from which it is then evaporated (premix evaporation). This allows for a simple and rapid deposition of the light-emitting layer with a uniform distribution of the components, without the need for precise control of multiple material sources.

[0254] A further subject of the invention is therefore a process for producing the device according to the invention, characterized in that the at least one compound of the formula (1), as described above or described as preferred, and the at least one compound of the formula (2) or the formula (3), as described above or described as preferred, are deposited successively or simultaneously from at least two material sources, optionally with the at least one phosphorescent emitter, as described above or described as preferred, from the gas phase and form the light-emitting layer.

[0255] In a preferred embodiment of the present invention, the light-emitting layer is applied by vapor deposition, wherein the components of the composition are premixed and evaporated from a single material source.

[0256] The invention accordingly further provides a process for producing the device according to the invention, characterized in that the at least one compound of formula (1) and the at least one compound of formula (2) or formula (3) are deposited as a mixture, successively or simultaneously with the at least one phosphorescent emitter, from the gas phase and form the light-emitting layer. The invention further provides a process for producing the device according to the invention, as described above or preferably described, characterized in that the at least one compound of formula (1) and the at least one compound of formula (2) or formula (3), as described above or preferably described, together with the at least one phosphorescent emitter, are applied from solution in order to form the organic layer, which is preferably the light-emitting layer.

[0257] The devices according to the invention are characterized by the following surprising advantages over the prior art:

[0258] The use of the described material combination of the compounds of formula (1) and compounds of formula (2) or (3), preferably as host material 1 and host material 2 in the light-emitting layer, as described above, leads in particular to an increase in the service life of the devices, with otherwise comparable performance data of the devices.

[0259] It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Any feature disclosed in the present invention may, unless explicitly excluded, be replaced by alternative features serving the same, equivalent, or similar purpose. Thus, unless otherwise stated, any feature disclosed in the present invention is to be considered an example of a generic series or an equivalent or similar feature.

[0260] All features of the present invention may be combined with each other in any way, unless certain features and / or steps are mutually exclusive. This applies in particular to preferred features of the present invention. Likewise, features of non-essential combinations may be used separately (and not in combination).

[0261] The teachings on technical practice disclosed by the present invention can be abstracted and combined with other examples. The invention is explained in more detail by the following examples, without intending to limit it.

[0262] Production of OLEDs

[0263] The following examples (see Table 7) demonstrate the use of the material combinations according to the invention in OLEDs.

[0264] Pretreatment for examples V1a to E7e: Glass plates coated with 50 nm thick patterned ITO (indium tin oxide) are first treated with an oxygen plasma followed by an argon plasma prior to coating. These plasma-treated glass plates form the substrates onto which the OLEDs are applied.

[0265] The OLEDs essentially have the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emission layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL), and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of the OLEDs can be found in Table 7. The materials required to manufacture the OLEDs are shown in Table 9. The device data of the OLEDs are listed in Table 8. Examples V1a-V1b, V2a-V2d, V3a-V3b, V4a, V5a, V6a, and V7a are comparative examples with an electron-transporting host according to the state of the art listed in Table 9. Examples E1a-E1r, E2a-E2j, E3a-E3g, E4a-E4c, E5a-E5c, E6a, E7a-E7e show data from OLEDs according to the invention.

[0266] All materials are thermally vapor-deposited in a vacuum chamber. The emission layer always consists of at least one matrix material (host material), in the context of the invention, at least two matrix materials, and an emitting dopant (dopant, emitter), which is mixed with the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as SdT-1:H5:TEG3 (32%:61%:7%) means that the material SdT-1 is present in the layer in a volume fraction of 32%, the compound H5 as co-host in a fraction of 61%, and TEG3 in a fraction of 7%. Analogously, the electron-transport layer can also consist of a mixture of two materials.

[0267] The electroluminescence spectra are measured at a luminance of 1000 cd / m 2and calculated the CIE 1931 x and y color coordinates. The value U10 in Table 8 refers to the voltage that is required for a current density of 10 mA / cm 2 EQE10 is the external quantum efficiency, which is required at 10 mA / cm 2 is reached. The lifetime LD is defined as the time after which the luminance measured in cd / m 2 in the forward direction, when operated at constant current density jo, from the starting luminance to a certain proportion L1. A value of L1=80% in Table 8 means that the lifetime given in column LD corresponds to the time after which the luminance in cd / m 2 drops to 80% of its initial value.

[0268] Use of mixtures according to the invention in OLEDs

[0269] The materials according to the invention are used in Examples E1a-E1r, E2a-E2j, E3a-E3g, E4a-E4c, E5a-E5c, E6a, and E7a-E7e as matrix materials in the emission layer of green phosphorescent OLEDs. As a comparison from the prior art, the materials SdT-1 to SdT-12 are used in combination with the host materials H1, H2, H5, H6, H14, and H23 in Comparative Examples V1a to V7a. Comparing the examples according to the invention with the corresponding comparative examples, it is clearly evident that the examples according to the invention each demonstrate a significant advantage in the lifetime of the OLED, with otherwise comparable OLED performance data.

[0270] Table 7:

[0271] Table 8: OLED data

[0272]

[0273] Table 9: Structural formulas of the materials in the OLEDs

[0274] In examples V2c, V2d, and V3b, the device does not display the emitter spectrum because the T1 level of the compounds SdT-5, SdT-6, and SdT-11 is not sufficiently high for a green phosphorescent device. Therefore, no device lifetime was measured.

[0275] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. Solvents and reagents can be purchased from Sigma-ALDRICH or ABCR, for example. The respective information in square brackets or the numbers given for individual compounds refer to the CAS numbers of the known compounds.

[0276] Preparation of the compounds a) 2-phenyl-4H-naphtho[1,2,3,4-def]carbazole

[0277] [2209069-43-0]

[0278] 25.6 g (210 mmol; 1.00 eq.) phenylboronic acid-4], 81 g (255 mmol; 1.21 eq.) 2-phenyl-4H-naphtho[1,2,3,4-def]carbazole and 44.5 g (420 mmol, 2.00 eq.) sodium carbonate [CAS 497-19-8] are suspended in a mixture of 1000 mL dioxane [CAS 123-91-1], 1000 mL toluene [CAS 108-88-3] and 400 mL water. To this suspension, 4.85 g (4.20 mmol; 0.02 eq.) of tetrakis(triphenylphosphine)palladium(0) [CAS 14221-01-3] are added, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated, filtered through silica gel, washed three times with 200 mL of water, and then evaporated to dryness. The yield is 38 g (121 mmol; 79% of theory).

[0279] The following compounds can be obtained analogously: b) 2-(1-dibenzofuranyl)-4-(7-fluoro-1-dibenzofuranyl)-6-phenyl-1,3,5-triazine

[0280] 58 g (210 mmol; 1.00 eq.) 1-Boronyl-8-chloro-dibenzofuran [CAS 162667-19-4], 90.2 g (252 mmol; 1.20 eq.) 2-chloro-4-{8-oxatricyclo[7.4.0.0 2 ' 7 ]trideca-

[0281] 1 (9), 2 (7), 3, 5, 10, 12-hexaen-3-yl}-6-phenyl-1,3,5-triazine [CAS 1883265-32-4] and 44.5 g (420 mmol, 2.00 eq.) of sodium carbonate [CAS 497-19-8] were suspended in a mixture of 1000 mL of dioxane [CAS 123-91-1], 1000 mL of toluene [CAS 108-88-3], and 400 mL of water. 4.85 g (4.20 mmol; 0.02 eq.) of tetrakis(triphenylphosphine)palladium(0) [CAS 14221-01-3] were added to this suspension, and the reaction mixture was heated under reflux for 16 h. After cooling, the organic phase is separated, filtered through silica gel, washed three times with 200 mL of water, and then evaporated to dryness. The yield is 79.1 g (151 mmol; 72% of theory).

[0282] The following compounds can be obtained analogously: c) 3-Biphenyl-3-yl-9-[9-(4,6-diphenyl-[1,3,5]triazin-2-yl)-dibenzofuran-2-yl]-4H-Naphtho[1, 2, 3, 4-def]carbazole - compound E1 (c)

[0283] Route A for bromides:

[0284] 21.4 g (42.7 mmol; 1.00 eg.) 2-(1-dibenzofuranyl)-4-(7-fluoro-1-dibenzofuranyl)-6-phenyl-1 ,3,5-triazine, 9.6 g (40.7 mmol; 1.10 eg.) 4H-naphtho[1 , 2,3,4- def]carbazole and 7.82 g (81.4 mmol; 2.00 eg.) sodium terf-butoxide [CAS 865-47-4] are suspended in 500 mL orf / 7o-xylene [CAS 95-47-6]. To this suspension, 1.50 g (3.66 mmol; 9 mol%) of dicyclohexyl-(2',6'-dimethoxy-biphenyl-2-yl)-phosphane (SPhos) [CAS 657408-07-6] and 1.12 g (1.22 mmol, 3 mol%) of tris(dibenzylideneacetone)dipalladium [CAS 51364-51-3] were added, and the reaction mixture was heated under reflux for 16 h. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The resulting solid was washed with 300 mL of ethanol and recrystallized several times from a mixture of heptane and xylene. After hot filtration through Alox and final sublimation under high vacuum, the purified product was obtained as a colorless solid (20.5 g; 32 mmol; 71%).

[0285] Route B for chlorides: Pd-cBRIDP cat

[0286] MeMgCl Xylene / THF

[0287] [2173554-85-1]

[0288] Under nitrogen, 16.0 g (66.0 mmol) of 4 / 7-naphtho[1,2,3,4-def]carbazole are treated with 60 ml of xylene and 6 ml of THF and cooled to 5°C. A THF solution of MeMgCl (3.22 mol / l, 20.0 ml, 64.4 mmol) and 18 ml of THF is slowly added dropwise to the carbazole solution in a dropping funnel over a period of 10 min, ensuring that the temperature does not exceed 25°C. A solution of 27.2 g (63.0 mmol) of 2-(8-chloro-1-dibenzofuranyl)-4,6-diphenyl-1,3,5-triazine and 14 ml of Pd-cBRIDP catalyst solution (prepared from PdCl(allyl)]2 (5.8 mg, 0.025 mol%) and cBRIDP (22.2 mg, 0.1 mol%) in 3 ml of THF and 11 ml of xylene) was then added to this solution. The mixture was heated to reflux under nitrogen for 3 hours, then the reaction mixture was allowed to cool to room temperature. 25 ml of water and 1.7 g of NH4Cl (31.8 mmol) were added and the mixture was stirred at room temperature for 5 min. The organic phase was separated, and the solution was concentrated and purified by chromatography (n-hexane, toluene 3 / 1).After three hot extractions over Alox and subsequent sublimation under high vacuum, the purified product is obtained as a colorless solid 16.7 g (26 mmol; 71%).

[0289] Analogously, the following compounds can be obtained either via route A or route B. Other common solvents and purification methods can also be used for workup and purification.

[0290]

Claims

Patent claims 1. Composition comprising at least one compound of the formula (1) and at least one combination of formula (2) or formula (3), the following applies to the symbols and indices used: R* is a group of the following formula (1a), Formula (1a) where the dashed bond represents the bond to the N atom of formula (1); X is the same or different in each occurrence N or CR C , provided that at least one group X represents N and in the case that X represents CR C This does not include a ring with Ar a or Ar b forms; L is, in each occurrence, either the same or different, an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each separated by one or more R groups 1L can be substituted with a remainder R or remainder R a can also form an aliphatic, heteroaliphatic or heteroaromatic ring system, or L is a group of the formula --L 1 -QL 2 -- where L 2 binds to the heteroaryl group of formula (1a) and L 1 to the N atom of the basic body of formula (1); Q is a group of formula (4), where the dashed lines represent the connection to L 1 or L 2 represent and L 1 and L 2 in each occurrence they can be bonded to either the same or different phenyl rings of the group of formula (4), with the proviso that the sum of aromatic ring atoms including all heteroatoms of the groups L 1 , L 2 and Q 13 to 40 is; G is the same or different O or S in each occurrence; L 1 , L 2Each occurrence is independent of the other and may be the same or different: a single bond, or an aryl group with 6 to 24 aromatic ring atoms, or a heteroaryl group with 5 to 24 aromatic ring atoms, each separated by one or more R groups. 1 may be substituted; Ar a , Ar b Each occurrence is independent of the other and may be the same or different: an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each separated by one or more R groups. 1 may be substituted; Ar c , Ar d Each occurrence is independent of the other and may be the same or different: an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each separated by one or more R groups. dmay be substituted; Y is selected from O, S or C(R) in each instance, either the same or different. g )2; Ar 1 , Ar 2 Each occurrence is independent of the other and may be the same or different: an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each separated by one or more R groups. 1 may be substituted; R, R a , R b are each independently of each other, the same or different at every occurrence: H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2,OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group with 1 to 20 carbon atoms, or an alkenyl or alkynyl group with 2 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group is each linked to one or more R groups 1 can be substituted, where one or more non-adjacent CH2 groups are replaced by -R 1 C=CR 1 - , -C=C-, Si(R 1 )2, CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), may be replaced by O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each replaced by one or more R groups 1 can be substituted, with two or more residues R and / or R bound to the same cycle a and / or R b together they can form an aliphatic or heteroaliphatic ring system, which is connected to one or more R residues. 1can be substituted, wherein two residues R and / or R' bonded to the same carbon, silicon, germanium or tin atom a and / or R b can form a monocyclic or polycyclic, aliphatic or aromatic ring system with one or more R residues 1 may be substituted; R c , R e , R f , R g , R h , R' are each independently of each other, the same or different at every occurrence H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2, OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group with 1 to 20 carbon atoms, or an alkenyl or alkynyl group with 2 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or Alkynyl group, each with one or more R residues 1 can be substituted, whereby one or more non-adjacent CH2 groups are replaced by -R 1 C=CR 1 -, -C=C-, Si(R 1 )2, NR 1 , CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), may be replaced by O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each replaced by one or more R groups 1 It can be substituted, with two or more residues R bound to the same cycle. c , R e , R f , R g , R hor R' can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system with one or more R residues 1 can be substituted, and wherein two substituents R bonded to the same carbon, silicon, germanium or tin atom c , R e , R f , R g , R h or R' can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one or more R residues 1 may be substituted; R d is the same or different in each occurrence H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2, OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group with 1 to 20 carbon atoms, or an alkenyl or alkynyl group with 2 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group is each linked to one or more R groups 1 can be substituted, whereby one or more non-adjacent CH2 groups are replaced by -R 1 C=CR 1 -, -C=C-, Si(R 1 )2, NR 1 , CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), may be replaced by O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each replaced by one or more R groups 1 It can be substituted, with two or more residues R bound to the same cycle. d together they can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system, which is joined with one or more R residues 1can be substituted, and wherein two substituents R bonded to the same carbon, silicon, germanium or tin atom d a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system together they can form a system with one or more residues R 1 may be substituted; R x is H, D or (L x ) y -Ar x ; L x In each occurrence, it is either a single bond, or an aromatic ring system with 6 to 40 aromatic ring atoms, or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which is separated by one or more R groups. 1 may be substituted; Ar x is the same or different in each occurrence an unsubstituted or substituted 9-Ar d -carbazolyl or an unsubstituted or substituted carbazol-9-yl containing one or more R groups1 can be substituted and wherein independently one or more times two residues R 1 or a remainder R 1 together with a remainder of Ar d or R f can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring, or for y=0 two adjacent R f and Ar x together form a ring of formula (5), where the positions marked with * represent the bonds to the phenyl ring of formula (2), and the other R f are the same or different in each occurrence H or a substituent as defined above; Formula (5) Ar' is, in each occurrence, either the same or different, an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is interrupted by one or more R groups. 1 may be substituted; R 1is the same or different in each occurrence D, F, I, B(OR) 2 )2, N(R 2 )2, CHO, C(=O)R 2 , CR 2 =C(R 2 )2, CN, C(=O)OR 2 , Si(R 2 )3, NO2, P(=O)(R 2 )2, OSO2R 2 , SR 2 , OR 2 , S(=O)R 2 , S(=O)2R 2 , a straight-chain alkyl group with 1 to 20 carbon atoms or an alkenyl or alkynyl group with 2 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group is each linked to one or more R groups 2 can be substituted and where one or more CH2 groups in the above-mentioned groups are replaced by -R 2 C=CR 2 - , -0=0-, Si(R 2 )2, 0=0, C=S, -C(=O)O-, NR 2 , CONR 2 , P(=O)(R 2), O, S, SO or SO2 may be replaced and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is replaced by one or more R groups 2 can be substituted, with two or more residues R 1 together they can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R 2 The compound is the same or different D, F, CN, or an aliphatic, aromatic, or heteroaromatic organic residue with 1 to 20 C atoms, in which one or more H atoms may also be replaced by D or F; two or more substituents R may be present. 2 be linked together and form a ring; I, m, p, q are either the same or different 0, 1, 2 or 3 independently of each other for each occurrence; n, o, r, z, s, t are either the same or different 0, 1, 2, 3 or 4 independently of each other for each occurrence; y is either 0 or 1 for each occurrence.

2. Composition according to claim 1 , characterized in that the compounds of formula (1) are selected from compounds of formulas (1 -1 a) to (1-11), Formula (1 -1 p) Formula (1-1m) Formula (1-1n) Formula (1-1o) Formula (1-1q) Formula (1-1r) Formula (1-1s) Formula (1-1t) where R* represents a group of the following formulas (1b), (1c) or (1d), Formula (1b), Formula (1c), Formula (1d), and the dashed bond represents the attachment of the group of formula (1b), (1c), or (1d) to the N atom of the basic framework of formulas (1-1a) to (1-11), and where the symbols used are R, R a , R b , R c , L, Ara and Ar b the meaning mentioned in claim 1. . Composition according to claim 1 or 2, characterized in that compounds of formula (2) are selected from compounds of formulas (2-1), (2-2) or (2-3), where the symbols and indices used are Ar c , R e , R f , L x , Ar x , o, y and p have the meaning specified in claim 1. . Composition according to one or more of claims 1 to 3 characterized in that the compounds of formula (2) are selected from compounds of formulas (2-1 a) to (2-1 f) or (2-2 a) to (2-2 e), where the symbols and indices used are Ar c , Ar d , R d , R e , R f , Ar' and R 1 the meaning mentioned in claim 1 and wherein: L x1In each occurrence, it is either the same or different: an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each separated by one or more R groups. 1 may be substituted; V is C(R) at every occurrence 1 )2, NAr', O or S; U is, in each occurrence independently of each other, either a single bond, O, S, NAr' or C(R) . 1 )2 a, b, c, d are, independently of each other, either the same or different 0 or 1, with the proviso that the sum a+b = 1 and the sum c+d = 0 or 1, or that the sum c+d = 1 and the sum a+b = 0; o1 , z1 are either the same or different 0, 1 , 2, 3 or 4 independently of each other for each occurrence; p1 is either the same or different 0, 1 , 2 or 3 independently of each other for each occurrence; p2 is either the same or different 0, 1 or 2 independently of each other for each occurrence.

5. Composition according to one or more of claims 1 to 4, characterized in that the compounds of formula (2) are selected from compounds of formulas (2-1 a-1 ) to (2-1a-3) or (2-1 b-1) to (2-1 b-3) or (2-1c-1) to (2-1c-19) or (2-1 d-1) to (2-1 d-4) or (2-1 e-1) to (2-1e-9) or (2-1f-1) to (2-1f-6) or (2-2a-1) to (2-2a-5) or (2-2b-1) to (2-2b-3) or (2-2c-1) to (2-2c-5) or (2-2d-1) to (2-2d-2) or (2-2e-1) to (2-2e-19), Formula (2-1 c-1 ) Formula (2-1 c-2) Formula (2-1 c-3) Formula (2-1 c-4) Formula (2-1 c-5) Formula (2-1 d-1) Formula (2-1f-4) Formula (2-1f-5) Formula (2-1f-6) Formula (2-2e-1 ) Formula (2-2e-2) Formula (2-2e-3) Formula (2-1e-10) Formula (2-1e-11) Formula (2-2e-18) Formula (2-2e-19) where the symbols used are Ar c , Ar d , V, Ar' and U which are under claim The meanings mentioned in claims 1 and 4, where W represents O, S, or NAr, and the H atoms in the basic structure of the compounds may be wholly or partially replaced by deuterium. Use of a composition according to one or more of claims 1 to 5 in an organic electronic device.

7. Organic electronic device comprising at least one composition according to one or more of claims 1 to 5 in at least one organic layer.

8. Device according to claim 7, characterized in that it is selected from the group consisting of organic integrated circuits (OlCs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-Lasers), or organic light-emitting diodes (OLEDs).

9. Device according to one or more of claims 7 or 8, characterized in that it contains the composition according to one or more of claims 1 to 5 in an emission layer (EML), in an electron transport layer (ETL), in an electron injection layer (EIL) and / or in a hole blocking layer (HBL).

10. Device according to one or more of claims 7 to 9, characterized in that it contains the composition according to one or more of claims 1 to 5 in the emission layer together with a phosphorescent emitter.

11. Method for manufacturing a device according to one or more of claims 7 to 10, characterized in that at least one organic layer containing a composition according to one or more of claims 1 to 5 is applied by vapor deposition or from solution.

12. Method according to claim 11 characterized in that the composition containing at least one compound of formula (1) and at least one compound of formula (2) or formula (3), as described in any one of claims 1 to 5, is deposited successively or simultaneously from at least two material sources, optionally with further materials, from the gas phase will and form the organic layer.

13. Method according to claim 11, characterized in that the composition containing at least one compound of formula (1) and at least one compound of formula (2) or (3), as described in one of claims 1 to 5, is deposited successively or simultaneously from a material source, having at least one phosphorescent emitter, from the gas phase and forms the light-emitting layer.

14. Compounds of formula (1), the following applies to the symbols and indices used: R* is a group of the following formula (1a), Formula (1a) where the dashed bond represents the bond to the N atom of formula (1); X is the same or different in each occurrence N or CR C , provided that at least one group X represents N and in the case that X represents CR C This does not include a ring with Ara or Ar b forms; L is, in each occurrence, either the same or different, an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each separated by one or more R groups 1 L can be substituted with a remainder R or remainder R a can also form an aliphatic, heteroaliphatic or heteroaromatic ring system, or L is a group of the formula -L 1 -Q- L 2 - where L 2 binds to the heteroaryl group of formula (1a) and L 1 to the N atom of the basic body of formula (1); Q is a group of formula (4), where the dashed lines represent the connection to L 1 or L 2 represent and L 1 and L 2in each occurrence they can be bonded to either the same or different phenyl rings of the group of formula (4), with the proviso that the sum of aromatic ring atoms including all heteroatoms of the groups L 1 , L 2 and Q 13 to 40 is; G is the same or different O or S in each occurrence; L 1 , L 2 Each occurrence is independent of the other and may be the same or different: a single bond, an aryl group with 6 to 24 aromatic ring atoms, or a heteroaryl group with 5 to 24 aromatic ring atoms, each separated by one or more R groups. 1 may be substituted; Ar a , Ar b are each independent of each other in every case The occurrence of an aromatic ring system with 6 to 40 aromatic ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, each separated by one or more R groups, may be the same or different. 1 may be substituted; R, R a , R b are each independently of each other, the same or different at every occurrence: H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2,OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1 , a straight-chain alkyl group with 1 to 20 carbon atoms or a an alkenyl or alkynyl group with 2 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group is each linked to one or more R groups 1 can be substituted, where one or more non-adjacent CH2 groups are replaced by -R 1 C=CR 1 -, -C=C-, Si(R 1 )2, CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), may be replaced by O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each replaced by one or more R groups 1 can be substituted, with two or more residues R and / or R bound to the same cycle a and / or R b together they can form an aliphatic or heteroaliphatic ring system, which is connected to one or more R residues. 1can be substituted, and wherein two residues R and / or R' bonded to the same carbon, silicon, germanium or tin atom a and / or R b can form a monocyclic or polycyclic, aliphatic or aromatic ring system with one or more R residues 1 may be substituted; R c is the same or different in each occurrence H, D, F, CI, Br, I, N(Ar')2, N(R 1 )2, OAr', SAr', B(OR 1 )2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group with 1 to 20 carbon atoms, or an alkenyl or alkynyl group with 2 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group is each linked to one or more R groups 1 can be substituted, whereby one or more non-adjacent CH2 groups are replaced by -R 1 C=CR 1 -, -C=C-, Si(R 1 )2, NR 1 , CONR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), may be replaced by O, S, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each replaced by one or more R groups 1 It can be substituted, with two or more residues R bound to the same cycle. c together they can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system, which is joined with one or more R residues 1 can be substituted, and wherein two substituents R bonded to the same carbon, silicon, germanium or tin atom c can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one or more R residues 1 may be substituted; R 1 is the same or different in each occurrence D, F, I, B(OR) 2 )2, N(R 2 )2, CHO, C(=O)R 2 , CR 2 =C(R 2 )2, CN, C(=O)OR 2 , Si(R 2 )3, NO2, P(=O)(R 2 )2, OSO2R 2 , SR 2 , OR 2 , S(=O)R 2 , S(=O)2R 2 , a straight-chain alkyl group with 1 to 20 carbon atoms, or an alkenyl or alkynyl group with 2 to 20 carbon atoms, or a branched or cyclic alkyl group with 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group is each linked to one or more R groups 2can be substituted and where one or more CH2 groups in the above-mentioned groups are replaced by -R 2 C=CR 2 -, -C=C-, Si(R 2 )2, C=O, C=S, -C(=O)O-, NR 2 , CONR 2 , P(=O)(R 2 ), O, S, SO or SO2 may be replaced and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is replaced by one or more R groups 2 can be substituted, with two or more residues R 1 together they can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R 2The compound is the same or different D, F, CN, or an aliphatic, aromatic, or heteroaromatic organic residue with 1 to 20 C atoms, in which one or more H atoms may also be replaced by D or F; two or more substituents R may be present. 2 be linked together and form a ring; s,t are either the same or different 0, 1, 2, 3 or 4 independently of each other in each occurrence; I, m are either the same or different 0, 1, 2 or 3 independently of each other for each occurrence; n is either the same or different 0, 1, 2, 3 or 4 independently of each other for each occurrence. Compounds according to claim 14, characterized in that the compounds are selected from the group of compounds of formulas (1-2) and formula (1-3), where the symbols used are X, Ar a , Ar b , L 1 , L 2 , Q, R, R a , R band indices I, m and n have the meaning mentioned in claim 14 and wherein: L 3 In each occurrence, it is the same or different, an aromatic ring system with 6 to 24 aromatic ring atoms, each separated by one or more R groups. 1 can be substituted, where L 3 with a remainder R or remainder R a can also form an aliphatic, heteroaliphatic, or heteroaromatic ring system. Compounds according to claim 14 or 15, characterized in that the compounds of formula (1) or of formulas (1-2) and (1-3) are selected from compounds of formulas (1-2a), (1-2b), (1-2c), (1-2d), (1-2e), (1-2f), (1-2g), (1-2h), (1-2i), (1-2j), (1-2k), (1-21), (1-2m), (1-2n), (1-2o), (1-3a), (1-3b), (1-3c), or (1-3d). Formula (1-2d) Formula (1-2e) Formula (1-20) where the symbols and indices used are X, Ar a , Ar b , L 1 , L 2 , R, R a , R b , R 1 , 1, m, n, s and t have the meanings mentioned in claim 15, wherein the hydrogen atoms of the compounds may be wholly or partially replaced by deuterium and wherein: u is, independently of each occurrence, the same or different 0, 1 or 2; v is, independently of each occurrence, the same or different 0, 1, 2 or 3; w is, independently of each occurrence, the same or different 0, 1 or 2.

17. Compounds according to one or more of claims 14 to 16, characterized in that the compounds are selected from the group of compounds of formulas (1-2a-1) to (1-2a-3), (1-2b-1), (1-2c-1), (1-2d-1) to (1-2d-3), (1-2j-1) to (1-2j-5), (1-2k-1) to (1-2k-2), (1-2n-1) to (1-2n-2), (1-2o-1) to (1-2o-3), (1-3a-1) to (1-3a-6), formulas (1- 3b-1) to (1-3b-17), formulas (1-3c-1) to (1-3c-6) and formulas (1-3d-1) to (1-3d-17), Formula (1-2n-1) Formula (1-2n-2) Formula (1-3a-2) Formula (1-3a-3) Formula (1-3a-4) Formula (1-3b-3) Formula (1-3b-4) Formula (1-3a-16) Formula (1 -3b-17) Formula (1-3d-16) Formula (1-3d-17) where the symbols used are R 1 , R, R a , R b , Ar a , Ar b and X and the indices I, m, n, s, t, v, w have the meanings mentioned in claim 14, claim 15 or claim 16 and wherein the hydrogen atoms of the compounds may be wholly or partially replaced by deuterium.

Images