Novel materials for organic electroluminescent devices

Abstract

The present invention relates to novel compounds (materials) and organic electroluminescent devices such as OLEDs (organic light emitting diodes) that contain these compounds, for example as electron transport materials and / or matrix materials, optionally combined with another matrix material. The invention also relates to mixtures and formulations that contain these novel compounds.

Description

[0001] New materials for organic electroluminescent devices

[0002] The present invention relates to novel compounds (materials) and organic electronic devices such as OLEDs (organic light-emitting diodes) that contain these compounds, for example as electron-transport materials and / or matrix materials, optionally in combination with another matrix material. Furthermore, the present invention relates to mixtures and formulations containing these novel compounds.

[0003] The construction of organic electroluminescent devices (e.g., OLEDs or OLECs - organic light-emitting electrochemical cells), in which organic semiconductors are used as organic functional materials, is described, for example, in US 4,539,507, US 5,151,629, EP 0676461, and WO 98 / 27136. In addition to fluorescent emitters, organometallic complexes that exhibit phosphorescence are increasingly being used as emitting materials (MA Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6). For quantum mechanical reasons, up to four times the energy and power efficiency is possible using organometallic compounds as phosphorescence emitters. In general, there is still room for improvement, both for OLEDs that exhibit singlet emission and for OLEDs that exhibit triplet emission, particularly 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, hole-transport materials, and electron- or exciton-blocking materials, are also of particular importance. Improvements to these materials can lead to significant improvements in electroluminescent devices.

[0005] In the prior art, heteroaromatic compounds, in particular, are used as electron-transport materials and as matrix materials for phosphorescent compounds. The term "matrix material" is typically used when referring to a host material for phosphorescent emitters. This use of the term "matrix material" is also used for the present invention. However, there is still room for improvement with these compounds, for example for use as matrix materials, particularly with regard to lifetime, but also with regard to the efficiency and operating voltage of the device.

[0006] Compounds containing a 3,3,4,4-tetramethylsuccinimide unit are described by Martin Vysvanl et al. (Inorganica Chimica Acta 362 (2009) 4899-4905). The synthesis and characterization of novel imidophosphines and phosphine oxides containing 3,3,4,4-tetramethylsuccinimide units are discussed in detail. The 3,3,4,4-tetramethylsuccinimide unit is used for substitution reactions with phosphorus halides. The use of these compounds, for example, in electronic devices, is not described.

[0007] The object of the present invention is therefore to provide compounds that are suitable for use in an organic electroluminescent device and that, when used in this device, lead to good device properties, as well as to provide the corresponding organic electroluminescent device. In particular, the object of the present invention is to provide compounds that lead to a long lifetime, good efficiency, and low operating voltage in a phosphorescent or fluorescent, in particular phosphorescent, OLED. The properties of the matrix materials in particular have a significant influence on the lifetime and efficiency of the organic electroluminescent device.

[0008] Furthermore, the compounds should lead to devices with excellent color purity, particularly when used as electron transport materials, matrix materials or hole transport materials in organic electroluminescent devices.

[0009] These tasks are solved by providing compounds according to formula (I): Formula (I) where the symbols used are:

[0010] W is a single bond, -O-, -S- or C(R X )2;

[0011] R xis, on each occurrence, identically or differently, H, D, F, CN, a straight-chain alkyl chain having 1 to 40 C atoms, preferably 1 to 20 C atoms, more preferably 1 to 10 C atoms, a branched or cyclic alkyl chain having 3 to 40 C atoms, preferably 3 to 20 C atoms, more preferably 3 to 10 C atoms, where in the alkyl chains one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, preferably 5 to 24 aromatic ring atoms, more preferably 5 to 18 aromatic ring atoms, each of which is substituted by one or more radicals R 6 can be substituted; two R x form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which, with one or more radicals R 6 can be substituted;

[0012] R is, identically or differently at each occurrence, F, CN, a straight-chain alkyl chain having 1 to 40 C atoms, a branched or cyclic alkyl chain having 3 to 40 C atoms, where in the alkyl chains one or more H atoms may be replaced by D, F or CN, where optionally two geminal or vicinal R form a monocyclic or polycyclic aliphatic ring system which reacts with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted, or two vicinal R represent the following group where

[0013] * represents the attachment points to the respective carbon atom and Y 1 an electron-transporting group Q 1 which is substituted with one or more residues R 7 may be substituted, or a hole-transporting group H1 which is substituted with one or more residues R 8 can be substituted

[0014] L is a single bond, or an aromatic or heteroaromatic ring system with 5 - 40 aromatic ring atoms, which is bonded to one or more residues R 9 can be substituted;

[0015] Y is an electron-transporting group Q which is reacted with one or more residues R 3 may be substituted, or a hole-transporting group H, which may be substituted with one or more residues R 10 can be substituted;

[0016] R 1 , R 6 is, at each occurrence, the same or different: H, D, F, CI, Br, I, -OH, -SH, CN, NO2, N(Ar)2, N(R 2 )2, C(=O)Ar, C(=O)R 2 , P(=O)(Ar)2, P(Ar)2, B(Ar)2, B(R 2 )2, C(Ar)3, C(R 2 )3, Si(Ar)3, Si(R 2)3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, or an alkenyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, with one or more non-adjacent CH2 groups being replaced by -R 2 C=CR 2 -, -C=C-, Si(R 2 )2, C=O, C=S, C=Se, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 2 ), -O-, -S-, SO or SO2 and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 2may be substituted, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms which may be substituted with one or more radicals R 2 may be substituted, or a combination of these systems; two or more, preferably adjacent, radicals R 1 or two adjacent residues R 6 together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which, with one or more radicals R 2 can be substituted;

[0017] R 2 , R 4is, on each occurrence, identically or differently, H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, where in each case one or more H atoms may be replaced by D, F, CI, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, where two or more, preferably adjacent, substituents R 2 or adjacent substituents R 4 form a ring system with each other; is the same or different at each occurrence: H, D, F, CI, Br, I, -OH, -SH, CN, NO2, N(Ar 1 )2, N(R 4 )2, C(=O)Ar 1 , C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, B(R 1 )2, C(Ar 1 )3, C(R 4 )3, Si(Ar 1 )3, Si(R 4)3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, or an alkenyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R 4 may be substituted, with one or more non-adjacent CH2 groups being replaced by -R 4 C=CR 4 -, -C=C-, Si(R 4 )2, C=O, C=S, C=Se, NR 4 , -C(=O)O-, -C(=O)NR 4 -, NR 2 , P(=O)(R 4 ), -O-, -S-, SO or SO2 and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 4 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 4may be substituted, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms which may be substituted with one or more radicals R 4 may be substituted, or a combination of these systems; two or more, preferably adjacent, radicals R 3 , two or more, preferably adjacent, radicals R 7 , two or more, preferably adjacent, radicals R 8 or two or more, preferably adjacent, radicals R 10 together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which, with one or more radicals R 4 may be substituted; or a group of the following formula where the dashed line represents the connection to Q or Q 1 and R has the meaning given above;

[0018] Ar, Ar 1, is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system with 5 - 40 aromatic ring atoms, each substituted by one or more radicals R 5 can be substituted;

[0019] R 5 , R 9 is, at each occurrence, identically or differently, H, D, F, CN, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms in which one or more H atoms may be replaced by D, F, Cl, I, Br or CN or a straight-chain or branched alkyl chain having 1 - 4 C atoms, and the following compounds are excluded: The symbol “D” or “D-atom” stands for deuterium.

[0020] An aryl group within the meaning of this invention contains 6 to 40 ring atoms, preferably C atoms. A heteroaryl group within the meaning of this invention contains 5 to 40 ring atoms, where the ring atoms comprise C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e. phenyl, derived from benzene, or a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene, or a fused aryl or heteroaryl group, for example derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline.An aryl group with 6 to 30 C atoms is therefore preferably phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylenyl, fluoranthenyl, dibenzoanthracenyl, chrysenyl or perylenyl, whereby the attachment of the aryl group as a substituent is not restricted.

[0021] An aromatic ring system within the meaning of this invention contains 6 to 40 C atoms in the ring system, wherein the ring system also comprises the aryl groups described above.

[0022] A heteroaromatic ring system within the meaning of this invention contains 5 to 40 ring atoms and at least one heteroatom. A preferred heteroaromatic ring system has 9 to 40 ring atoms and at least one heteroatom. The heteroaromatic ring system also includes heteroaryl groups, as described above. The heteroatoms in the heteroaromatic ring system are preferably selected from N, O, and / or S.

[0023] An aromatic or heteroaromatic ring system within the meaning of this invention is understood to mean a system that does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be interrupted by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as a C or O atom or a carbonyl group. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diaryl ethers, stilbene, etc. are also to be understood as aromatic or heteroaromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group. Furthermore, systems in which two or more aryl or heteroaryl groups are directly bonded to one another, such asBiphenyl, terphenyl, quaterphenyl or bipyridine, are also included in the definition of the aromatic or heteroaromatic ring system.

[0024] An aromatic or heteroaromatic ring system with 5 - 40 ring atoms, which can be linked to the aromatic or heteroaromatic ring via any position, is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, Isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine,Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1 ,2-Thiazol, 1 ,3- Thiazol, Benzothiazol, Pyridazin, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin,

[0025] 1.5-Diazaanthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1 ,6-Diazapyren, 1 ,8-Diazapyren,

[0026] 4.5-Diazapyren, 4,5,9, 10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Pheno- thiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1 ,2,3- Triazol, 1 ,2,4-Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1 ,2,4-Oxadiazol, 1 ,2,5-Oxadiazol,

[0027] 1.3.4-Oxadiazol, 1 ,2,3-Thiadiazol, 1 ,2,4-Thiadiazol, 1 ,2,5-Thiadiazol, 1 ,3,4-Thiadiazol,

[0028] 1.3.5-Triazin, 1 ,2,4-Triazin, 1 ,2,3-Triazin, Tetrazol, 1 ,2,4,5-Tetrazin, 1 ,2,3,4-Tetrazin,

[0029] 1.2.3.5-Tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0030] Furthermore, a straight-chain alkyl group having 1 to 40 C atoms, preferably 1 to 20 C atoms, more preferably 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 40 C atoms, preferably having 3 to 20 C atoms, more preferably having 3 to 10 C atoms, for example the radicals methyl, ethyl, n-propyl,

[0031] 1-Propyl, Cyclopropyl, n-Butyl, i-Butyl, s-Butyl, t-Butyl, Cyclobutyl, 2-Methylbutyl, n-Pentyl, s-Pentyl, t-Pentyl, 2-Pentyl, neo-Pentyl, Cyclopentyl, n-Hexyl, s-Hexyl, t-Hexyl,

[0032] 2-Hexyl, 3-Hexyl, neo-Hexyl, Cyclohexyl, 1-Methylcyclopentyl, 2-Methylpentyl, n-Heptyl, 2-Heptyl, 3-Heptyl, 4-Heptyl, Cycloheptyl, 1-Methylcyclohexyl, n-Octyl, 2-Ethylhexyl, Cyclooctyl, 1-Bicyclo[2,2,2]octyl, 2-Bicyclo[2,2,2]octyl, 2-(2,6-Dimethyl)- octyl, 3-(3,7-Dimethyl)octyl, Adamantyl, Trifluormethyl, Pentafluorethyl, 2,2,2-Tri- fluorethyl, 1,1-Dimethyl-n-hex-1-yl-, 1 ,1-Dimethyl-n-hept-1-yl-, 1,1-Dimethyl-n-oct-1-yl-,

[0033] 1.1-Dimethyl-n-dec-1-yl-, 1,1-Dimethyl-n-dodec-1-yl-, 1,1-Dimethyl-n-tetradec-1-yl-,

[0034] 1.1-Dimethyl-n-hexadec-1-yl-, 1 ,1-Dimethyl-n-octadec-1-yl-, 1 , 1-Diethyl-n-hex-1 -yl-,

[0035] 1.1-Diethyl-n-hept-1-yl-, 1,1-Diethyl-n-oct-1-yl-, 1,1-Diethyl-n-dec-1-yl-, 1,1-Diethyl-n-dodec-1-yl-, 1,1-Diethyl-n-tetradec-1-yl-, 1,1-Diethyln-n-hexadec-1-yl-, 1, 1-Diethyl-n-octadec-1-yl-, 1-(n-propyl)-cyclohex-1-yl-, 1-(n-butyl)-cyclohex-1-yl-, l-(n-hexyl)-cyclohex-1-yl-, 1-(n-Octyl)-cyclohex-1-yl- and 1-(n-Decyl)-cyclohex-1-yl- understood. The term “cyclic alkyl group” includes a monocyclic, bicyclic or polycyclic group.

[0036] A straight-chain alkyl group having 1-20 C atoms, preferably having 1-10 C atoms, or a branched alkyl group having 3-20 C atoms, preferably having 3-10 C atoms, in which one or more non-adjacent CH2 groups can be replaced by O or S, and in which at least one H atom can be replaced by D, F or CN, is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, thiomethyl, 1-thioethyl, 1-thio-i-propyl, 1-thio-n-propoyl, 1-thio-i-butyl, 1-thio-n-butyl or 1-thio-t-butyl.

[0037] For the purposes of the present invention, adjacent carbon atoms are carbon atoms that are directly linked to one another. Furthermore, "adjacent radicals" in the definition of radicals means that these radicals are bonded to the same carbon atom or to adjacent carbon atoms. These definitions apply accordingly, among other things, to the terms "adjacent groups" and "adjacent substituents."

[0038] The phrase "two or more residues can form a ring system" refers to the formation of an aliphatic, aromatic, or heteroaromatic ring system. For the purposes of this description, it is understood, among other things, that the two residues are linked by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0039] 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:

[0040] The compounds of formula (I) and their preferred embodiments are described below. The preferred embodiments also apply to the mixture and formulation according to the invention, as well as to the organic electronic or electroluminescent device according to the invention.

[0041] In a preferred embodiment of the present invention, L is selected from the group consisting of a single bond, an aromatic ring system having 6 to 30 aromatic ring atoms, more preferably an aromatic ring system having 6 to 18 aromatic ring atoms, or a heteroaromatic ring system having 5 to 24 aromatic ring atoms, more preferably a heteroaromatic ring system having 5 to 18 aromatic ring atoms, even more preferably a heteroaromatic ring system having 5 to 13 aromatic ring atoms, wherein the respective ring system is linked to one or more radicals R 9 can be substituted.

[0042] When L represents an aromatic or heteroaromatic ring system, it is preferably selected from the following formulas (L-1) to (L-60):

[0043] Formula (L-1) Formula (L-2) Formula (L-3)

[0044]

[0045] Formula (L-35) Formula (L-36) Formula (L-37) where the dashed bonds mark the attachment positions, the index k is 0 or 1, the index l is 0, 1 or 2, the index j is 0, 1, 2 or 3 at each occurrence independently of one another; the index h is 0, 1, 2, 3 or 4 at each occurrence independently of one another, the index g is 0, 1, 2, 3, 4 or 5; the symbol Y 2 O, S, BR 1 or NR 1 , preferably O, S or NR 1 , preferred O or NR 1 and the remainder R 9 has the meaning previously given for formula (I).

[0046] The rest R 9 is preferably identical or different and is H, D, F, CN, an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, in which one or more H atoms may be replaced by D, F or CN, or a straight-chain or branched alkyl chain having 1 - 4 C atoms; more preferably, the radical R 9identical or different H, D, F, CN, an aromatic or heteroaromatic ring system with 5 to 13 aromatic ring atoms in which one or more H atoms may be replaced by D, F or CN or a straight-chain or branched alkyl chain with 1 - 4 C atoms.

[0047] In a further preferred embodiment of the present invention, W is a single bond. The corresponding compounds are encompassed by the following formula (Ia):

[0048] Formula (la) where the symbols R, L and Y have the meaning given above.

[0049] In yet another preferred embodiment of the present invention, R is, identically or differently on each occurrence, F, CN, a straight-chain alkyl chain having 1 to 20 C atoms, a branched or cyclic alkyl chain having 3 to 20 C atoms, where in the alkyl chains one or more H atoms may be replaced by D, F or CN, where optionally two geminal or vicinal R form a monocyclic aliphatic ring system which, with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted, or two vicinal R represent the following group where

[0050] * represents the attachment points to the respective carbon atom and Y 1 has the meaning given in claim 1.

[0051] If R represents an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, it is on each occurrence, identically or differently, phenyl, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, triphenylenyl, phenanthrenyl, pyridyl, pyrimidinyl, triazinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, 1-, 2-, 3- or 4-Carbazolyl, , quinazolinyl, quinaxolinyl, indenocarbazolyl, or indolocarbazolyl, each of which is substituted by one or more radicals R 1 can be substituted.

[0052] Preferably, R is, identically or differently on each occurrence, F, CN, a straight-chain alkyl chain having 1 to 10 C atoms, a branched or cyclic alkyl chain having 3 to 10 C atoms, where in the alkyl chains one or more H atoms may be replaced by D, F or CN, where two geminal or vicinal R form a monocyclic aliphatic ring system which, with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system with 5 to 13 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted, or two vicinal R represent the following group where * and Y 1 have the meaning given above.

[0053] Even more preferably, R is, identically or differently at each occurrence, F, CN, a straight-chain alkyl chain having 1 to 6 C atoms, a branched or cyclic alkyl chain having 3 to 10 C atoms, where in the alkyl chains one or more H atoms may be replaced by D, F or CN, where two geminal or vicinal R form a monocyclic aliphatic ring system which, with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system with 5 to 13 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted, or two vicinal R represent the following group where * and Y 1have the meaning given above. Very preferably, R is, identically or differently on each occurrence, F, methyl, ethyl, i-propyl, t-butyl, neo-pentyl, cyclopentyl, cyclohexyl, 1-adamantyl or 1-bicyclo[2.2.2]octanyl, where in each case one or more H atoms may be replaced by D, F or CN, preferably by D, or two geminal or vicinal R form a cyclopentyl or cyclohexyl unit which reacts with one or more radicals R 1 can be substituted, or two vicinal R represent the following group where * and Y 1 have the meaning given above.

[0054] If R is the same or different and is an aromatic or heteroaromatic ring system having 5 to 13 aromatic ring atoms, it is very preferably phenyl, ortho-, meta- or para-biphenyl, 1-, 2-, 3- or 4-fluorenyl, pyridyl, pyrimidinyl, triazinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl or 1-, 2-, 3- or 4-carbazolyl, each of which is substituted by one or more radicals R 1 can be substituted.

[0055] Preferably, the residue R 1 or R 6 at each occurrence, identically or differently, H, D, F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, more preferably having 1 to 10 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, more preferably having 3 to 10 C atoms, or an alkenyl group having 2 to 40 C atoms, more preferably having 2 to 10 C atoms, each of which is substituted by one or more radicals R 2may be substituted, and wherein one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, more preferably having 5 to 18 aromatic ring atoms, each substituted by one or more radicals R 2 can be substituted.

[0056] In yet another preferred embodiment of the present invention, Y or Y 1 an electron-transporting group Q or Q 1 which are, identically or differently, a triazine, pyrimidine, pyridine, quinazoline, quinoxaline, diazadibenzofuran, diazadibenzothiophene, B(Ar)2, P(=O)(Ar)2, P(Ar)2, where Q is substituted with one or more radicals R 3 and Q 1 with one or more residues R 8 can be substituted. Q or Q 1 selected from structures of the following formulas:

[0057] Formula (Q-13) Formula (Q-14) where the dashed line shows the connection to L, Y 3 O or S and the formulas (Q-1) to (Q-14) are each substituted with one or more radicals R 3 or R 8 may be substituted, where R 3 or R 8 have the meaning given above.

[0058] It is further preferred that Q or Q 1 identical or different is a triazine, pyrimidine, quinazoline, diazadibenzofuran or dibenzothiophene, where Q is substituted with one or more radicals R 3 and Q 1 with one or more residues R 8 may be substituted. Particularly preferably, Q or Q1, identical or different, is a triazine, pyrimidine or quinazoline, where Q is substituted with one or more radicals R 3 and Q 1 with one or more residues R 8 can be substituted. Q or Q1 corresponds here to the formulas (Q-1) to (Q-4), (Q-8), (Q-9) and (Q-11) to (Q-14). The radicals R 3or R 8 have the meaning mentioned above.

[0059] Preferably, the residue R 3 or R 8 at each occurrence, identical or different, H, D, F, CN, -OH, -SH, Si(R 4 )4, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or an alkenyl group having 2 to 20 C atoms, each of which is substituted by one or more radicals R 4 may be substituted, where in the alkyl chains one or more H atoms may be replaced by D, F, CI, Br, I or CN, or an aromatic or heteroaromatic ring system with 5 to 25 aromatic ring atoms, each substituted by one or more radicals R 2 may be substituted, or a combination of these systems; two or more, preferably adjacent, radicals R 3together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which, with one or more radicals R 4 may be substituted; or a group of the following formula, where the dashed line represents the connection to Q or Q 1 and R has the meaning given above. The radicals R 2 and R 4 has the meaning given above. Even more preferably, the radical R 3 or R 8identical or different represents an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms and is selected from the group consisting of phenyl, biphenyl, such as ortho-, meta- or para-biphenyl, terphenyl, such as ortho-, meta-, para- or branched terphenyl, quaterphenyl, ortho-, meta-, para- or branched quaterphenyl, fluorene, such as 1-, 2-, 3- or 4-fluorenyl spirobifluorene, such as 1-, 2-, 3- or 4-spirobifluorenyl, naphthalene, such as 1- or 2-naphthyl, indole, benzofuran, benzothiophene, carbazole, such as 1-, 2-, 3- or 4-carbazolyl, dibenzofuran, such as 1-, 2-, 3- or 4-dibenzofuranyl, dibenzothiophene, such as 1-, 2-, 3- or 4-Dibenzothienyl, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which is substituted with one or more radicals R 4 can be substituted. The residue R 4 the meaning given above.

[0060] In yet another preferred embodiment of the present invention, when Y in formula (I) is a hole-transporting group H, this hole-transporting group is a carbazole, biscarbazole, tricarbazole, indenocarbazole, indolocarbazole, benzimidazobenzimidazole or a diarylamine which is reacted with one or more radicals R 10 can be substituted.

[0061] The hole-transporting group H can be chosen from the following formulas (H-1) to

[0062] (H-39) can be selected: Formula (H-4) Formula (H-5)

[0063] Formula (H-15) Formula (H-16)

[0064]

[0065] Formula (H-27) Formula (H-28)

[0066]

[0067] Formula (H-38) Formula (H-39) where the dashed line shows the connection to L,

[0068] Ar 2 , Ar 3 and Ar 4identical or different, an aromatic or heteroaromatic

[0069] Ring system with 5 to 40 aromatic ring atoms, which is independently substituted by one or more radicals R 10 may be substituted, where the radical R 10 has the meaning given above. Preferably, Ar 2 , Ar 3 and Ar 4 identically or differently, an aromatic or heteroaromatic ring system having 5 - 25 aromatic ring atoms, more preferably having 5 to 18 aromatic ring atoms, even more preferably having 5 to 13 aromatic ring atoms, each substituted by one or more radicals R 10can be substituted. The aromatic or heteroaromatic ring systems mentioned can, for example, be selected from the group consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl, in particular branched terphenyl, quaterphenyl, in particular phenyl, ortho-, meta- or para-biphenyl, 1-, 2-, 3- or 4-fluorenyl, in particular 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, 1-, 2-, 3- or 4-carbazolyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl and / or triphenylenyl.

[0070] Examples of suitable compounds according to the invention according to formula (I) are listed below in Table 1:

[0071] Table 1 :

[0072]

[0073]

[0074]

[0075] The compounds of the invention can be prepared by synthetic steps known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc. In the following synthesis scheme, the compounds are shown with a small number of substituents to simplify the structures. This does not exclude the presence of any other substituents in the processes. The processes shown for the synthesis of the compounds of the invention are to be understood as examples. The skilled person can develop alternative synthesis routes within the scope of their general technical knowledge.

[0076] Scheme 1 : SIX^Ar reaction

[0077] The compounds (3) according to the invention can be obtained, on the one hand, by reacting the substituted imides (1) with chloro-heterocycles (2), such as chloro-pyrimidines, triazines, quinoxalines, quinazolinenes, benzofuro[2,3-d]pyrimidines, benzofuro[3,2-d]pyrimidines, etc., in an SN2Ar reaction, in the presence of a base, such as alkyl lithium compounds, alkali hydrides such as NaH, alkali metal carbonates such as K2CO3 or CS2CO3, or amines such as triethylamine or pyridine, in dipolar aprotic solvents such as THF, dioxane, DMSO, DMF, DMAc, NMP, etc. Alternatively, the CN bond formation can be carried out by means of the Buchwald-Hartwig coupling in the presence of a base, e.g. a stoichiometric or superstoichiometric amount of an alkali metal alkoxide, preferably sodium tert-butoxide or an alkali metal carbonate or phosphate, preferably cesium carbonate or tripotassium phosphate, and a catalyst, preferably a combination of an electron-rich phosphine, e.g.Tri-tert-bytlyphosphine, Xanthphos, SPhos, XPhos, AmPhos, RuPhos etc, and a palladium source, e.g. Pd2(dba)3 or Pd(OAc)2.

[0078] On the other hand, the compounds according to the invention can be obtained as shown in Scheme 2 (6) by condensation of cyclic, substituted carboxylic acid anhydrides (4) with aryl / heteroarylamines (5), by heating in the melt or in the presence of a solvent, preferably a high-boiling dipolar aprotic solvent, such as DMSO, DMF, DMAc, NMP, etc.

[0079] Scheme 2: Condensation reaction

[0080] Detailed reaction conditions are known from the state of the art or are described in the examples section.

[0081] For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention or mixtures of compounds of the invention with other functional materials, such as matrix materials, fluorescent emitters, phosphorescent emitters, and / or emitters exhibiting TADF, are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-Dimethylanisol, 3,5-Dimethylanisol, Acetophenon, a- Terpineol, Benzothiazol, Butylbenzoat, Cumol, Cyclohexanol, Cyclohexanon, Cyclohexylbenzol, Decalin, Dodecylbenzol, Ethylbenzoat, Indan, NMP, p-Cymol, Phenetol, 1,4-Diisopropylbenzol, Dibenzylether, Diethylenglycolbutylmethylether, Tri- ethylenglycolbutylmethylether, Diethylenglycoldibutylether, T riethylenglycol- dimethylether, Diethylenglycolmonobutylether, Tripropyleneglycoldimethylether, Tetra- ethylenglycoldimethylether, 2-lsopropylnaphthalin, Pentylbenzol, Hexylbenzol, Heptylbenzol, Octylbenzol, 1,1-Bis(3,4-dimethylphenyl)ethan, 2-Methylbiphenyl, 3-Methylbi- phenyl, 1-Methylnaphthalin, 1-Ethylnaphthalin, Ethyloctanoat, Sebacinsäure- diethylester, Octyloctanoat, Heptylbenzol, Menthyl-isovalerat, Cyclohexylhexanoat oder Mischungen dieser Lösemittel.,

[0082] If the compound according to the invention is used as matrix material or synonymously host material in an emitting layer, it is preferably used in combination with another compound.

[0083] A further subject matter of the invention is therefore a mixture comprising at least one compound of the formula (I) or at least one preferred compound of the formula (Ia), or a compound of Table 1 and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence), electron-injecting materials, hole-transporting materials, hole-injecting materials, electron-blocking materials, and / or a solvent.

[0084] Other suitable matrix materials that can be used in this mixture according to the invention are arylamines, diarylamines, triarylamines, and bridged amines; preferred bridged amines are dihydroacridines, dihydrophenazines, phenoxaziones and phenothiazines, carbazoles, bridged carbazoles, biscarbazoles, triscarbazoles, benzimidazobenzimidazoles, indenocarbazoles, and indolocarbazoles. These matrix materials can be partially or fully deuterated, where the term "partially" means at least the presence of one D. The degree of deuteration of these compounds is preferably at least 50% to 90%, more preferably at least 70% to 100%. Suitable emitters that can be used in this mixture according to the invention are described below.

[0085] The present invention also further provides a formulation comprising at least one compound according to the invention, as described above, or a mixture according to the invention, as described above, and at least one solvent. The solvent can be one of the solvents mentioned above or a mixture of these solvents.

[0086] The present invention further provides an organic electronic device comprising an anode, a cathode and at least one organic layer containing at least one compound of formula (I) or at least one preferred compound of formula (Ia) or a compound of Table 1.

[0087] Preferably, the organic electronic device is an organic electroluminescent device.

[0088] The organic electroluminescent device according to the invention (synonymously referred to as organic electroluminescent device) is, for example, an organic light-emitting transistor (OLET), an organic field quench device (OFQD), an organic light-emitting electrochemical cell (OLEC, LEG, LEEC), an organic laser diode (O-laser), or an organic light-emitting diode (OLED). The organic electroluminescent device according to the invention is, in particular, an organic light-emitting diode or an organic light-emitting electrochemical cell. The device according to the invention is particularly preferably an OLED.

[0089] The organic layer of the device according to the invention preferably contains, in addition to a light-emitting layer (EML), a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), an exciton blocking layer, an electron blocking layer, and / or charge generation layers. The device according to the invention may also contain several layers from this group, preferably selected from EML, HIL, HTL, ETL, EIL, and HBL. Likewise, interlayers may be introduced between two emitting layers, which, for example, have an exciton-blocking function. If several emission layers are present, they preferably have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, i.e.Various emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. A single emitting layer can also contain several fluorescent and / or phosphorescent compounds. Particular preference is given to systems with three emitting layers, each layer exhibiting blue, green, and orange or red emission. As an alternative to the combination described above, an emitting layer can also exhibit yellow emission. Such combinations are known to the person skilled in the art. The organic electroluminescent device according to the invention can also be a tandem electroluminescent device, particularly for white-emitting OLEDs. The device can also contain inorganic materials or layers composed entirely of inorganic materials.

[0090] It is not difficult for a person skilled in the art to draw on a multitude of materials known in the prior art to select suitable materials for use in the layers of the organic electroluminescent device described above. In doing so, the person skilled in the art will consider common considerations regarding the chemical and physical properties of the materials, as they are aware that the materials in an organic electroluminescent device are interrelated. This applies, for example, to the energy positions of the orbitals (HOMO, LIIMO) or the position of triplet and singlet energies, as well as other material properties.

[0091] The compound of the formula (I) according to the invention, as described above or preferably described, can be used in different layers, depending on the precise structure. Preference is given to an organic electroluminescent device comprising a compound of the formula (I) or the preferred embodiments outlined above in an emitting layer as a matrix material for fluorescent emitters, phosphorescent emitters or for emitters which display TADF (thermally activated delayed fluorescence), in particular for phosphorescent emitters. Furthermore, the compound according to the invention can also be used in an electron transport layer and / or in a hole transport layer and / or in an exciton blocking layer and / or in a hole blocking layer. The compound according to the invention is particularly preferably used as a matrix material in an emitting layer or as an electron transport or hole blocking material in an electron transport or hole blocking layer.Hole blocking layer used.

[0092] The present invention further provides an organic electronic device as described above, wherein the organic layer comprises at least one electron-transporting layer, electron-injecting layer, hole-blocking layer, hole-transporting or light-emitting layer, the at least one compound of formula (I) or the at least one preferred compound of formula (Ia) or a compound of Table 1 or a mixture comprising at least one compound of formula (I) or the at least one preferred compound of formula (I) or compound of Table 1.

[0093] Suitable matrix materials, in addition to the above-mentioned matrix materials, which can be used in combination with the compounds according to the invention, are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, biscarbazoles, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole derivatives, bipolar matrix materials, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasilole or tetraazasilole derivatives, diazaphosphole derivatives, bridged carbazole derivatives, triphenylene derivatives, or dibenzofuran derivatives. Likewise, another phosphorescent emitter, which emits at a shorter wavelength than the actual emitter, can be present in the mixture as a co-host, or a compound that does not participate, or does not participate to a significant extent, in charge transport, such as a wide-band-gap compound.

[0094] A wide-band-gap material is understood herein to mean a material within the meaning of the disclosure of US 7,294,849, which is characterized by a band gap of at least 3.5 eV, where the band gap is understood to be the distance between the HOMO and LUMO energy of a material.

[0095] If the at least one further matrix material is a deuterated compound, it is possible that this at least one matrix material is a mixture of deuterated compounds of the same basic chemical structure, which differ only in the degree of deuteration.

[0096] Corresponding deuteration methods are known to the person skilled in the art and are described, for example, in KR2016041014 A, WO2017 / 122988 A1, KR2020052820 A, KR101978651 B1 and WO2018 / 110887 A1 or in Bulletin of the Chemical Society of Japan, 2021, 94(2), 600-605 or Asian Journal of Organic Chemistry, 2017, 6(8), 1063-1071.

[0097] A suitable method for deuterating a compound by exchanging one or more hydrogen atoms for diatoms is to treat the compound to be deuterated in the presence of a platinum or palladium catalyst and a deuterium source. The term "deuterium source" refers to any compound containing one or more diatoms and capable of releasing them under suitable conditions.

[0098] The platinum catalyst is preferably dry platinum on carbon, preferably 5% dry platinum on carbon. The palladium catalyst is preferably dry palladium on carbon, preferably 5% dry palladium on carbon. A suitable deuterium source is DO, benzene-d6, chloroform-d, acetonitrile-d3, acetone-d6, acetic acid^, methanol-d4, or toluene-d8. A preferred deuterium source is DO or a combination of DO and a fully deuterated organic solvent. A particularly preferred deuterium source is the combination of DO with a fully deuterated organic solvent, the fully deuterated solvent not being limited here. Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8. A particularly preferred deuterium source is a combination of DO and toluene-d8.The reaction is preferably carried out with heating, more preferably with heating to temperatures between 100 °C and 200 °C. Furthermore, the reaction is preferably carried out under pressure.

[0099] Examples of suitable further matrix materials for combination with compounds of formula (I), as previously described or preferably described, are the compounds described in W02019 / 229011 A1, Table 3, pages 137 to 203, which may also be partially or fully deuterated.

[0100] Examples of suitable further matrix materials for a combination with compounds of the formula (I) or preferred compounds of the formula (I), as described above or preferably described, are the compounds described in WO2021 / 180625 A1, Table 3, pages 131 to 127 and in Table 4, pages 137 to 139, which may also be partially or fully deuterated. Examples of suitable further matrix materials for a combination with compounds of the formula (I) or preferred compounds of the formula (Ia), as described above or preferably described, are the compounds described in WO2011 / 088877 A1, table on page 30, compounds 1 to 166, which may also be partially or fully deuterated.

[0101] Examples of suitable further matrix materials for a combination with compounds of formula (I) or preferred compounds of formula (Ia), as described above or preferably described, are the compounds 1 to 151 listed in the table on page 23 of WO2011 / 128017 A1, wherein these compounds may also be partially or completely deuterated.

[0102] Examples of suitable further matrix materials for combination with compounds of formula (I) or preferred compounds of formula (Ia), as previously described or preferably described, are the compounds described in KR20230034896 A, on pages 42 to 47, compounds [2-1] to [2-110], or on pages 49 to 51, compounds [3-1] to [3-26]. The following Table 3 lists suitable further matrix materials, which may also be partially or fully deuterated.

[0103] Table 3:

[0104]

[0105] The concentration of the host material of the formula (I), as described above or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 5 wt.% to 90 wt.%, preferably in the range from 10 wt.% to 85 wt.%, more preferably in the range from 20 wt.% to 85 wt.%, even more preferably in the range from 30 wt.% to 80 wt.%, very particularly preferably in the range from 20 wt.% to 60 wt.% and most preferably in the range from 30 wt.% to 50 wt.%, based on the total mixture or based on the total composition of the light-emitting layer.

[0106] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the light-emitting layer contains, in addition to the above-mentioned host materials of the formula (I) and at least one above-mentioned further matrix material, at least one phosphorescent emitter.

[0107] The term "phosphorescent emitters" typically encompasses compounds in which light emission occurs through a spin-forbidden transition from an excited state with higher spin multiplicity, i.e., a spin state > 1, for example, through a transition from a triplet state or a state with an even higher spin quantum number, such as a quintet state. Preferably, this refers to a transition from a triplet state.

[0108] 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.

[0109] 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.

[0110] Preferred phosphorescent emitters according to the present invention Formula (3a), where the symbols and indices for this formula (3a) have the meaning: n+q is 3, n is 1 or 2, q is 2 or 1 ,

[0111] X is the same or different at each occurrence, N or CR,

[0112] R xis, on each occurrence, identically or differently, H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 7 C atoms which may be partially or fully substituted with deuterium or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms which may be partially or fully substituted with deuterium.

[0113] A further subject matter of the invention is accordingly an organic electroluminescent device as described above or preferably described, characterized in that the light-emitting layer contains, in addition to the host materials 1 and 2, at least one phosphorescent emitter which corresponds to the formula (3a), as described above.

[0114] In emitters of formula (3a), n is preferably 1 and q is preferably 2. In emitters of formula (3a), one X is preferably selected from N and the other Xs are CR or all Xs, identically or differently at each occurrence, are CR. In emitters of formula (3a), at least one R is preferably different from H. In emitters of formula (3a), two Rs are preferably different from H and have one of the meanings otherwise previously given for the emitters of formula (3a).

[0115] Preferred phosphorescent emitters according to the present invention correspond to formulas (1), (2), (3), (4) or (5),

[0116] where the symbols and indices for these formulas (1), (2), (3), (4) and (5) have the meaning:

[0117] Ri is H or D, R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium. Preferred phosphorescent emitters according to the present invention correspond to formulas (6), (7) or (8),

[0118] formula

[0119] formula

[0120] formula where the symbols and indices for these formulas (6), (7) and (8) have the meaning: Ri is H or D, R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium.

[0121] Preferred examples of phosphorescent emitters are described in WO2019 / 007867 on pages 120 to 126 in Table 5 and on pages 127 to 129 in Table 6. The emitters are incorporated into the description by this reference. Particularly preferred examples of phosphorescent emitters are listed in Table 4 below.

[0122] Table 4:

[0123] The light-emitting layer in the organic electroluminescent device according to the invention containing at least one phosphorescent emitter is preferably an infrared-emitting, yellow, orange, red, green, blue or ultraviolet-emitting layer, particularly preferably a yellow or green-emitting layer and very particularly preferably a green-emitting layer.

[0124] 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.

[0125] The photoluminescence spectrum of the layer is recorded, for example, using a commercially available photoluminescence spectrometer.

[0126] The photoluminescence spectrum of the selected emitter is usually measured in oxygen-free solution, 10' 5 molar, measured at room temperature, and any solvent in which the selected emitter dissolves at the specified concentration is suitable. Particularly suitable solvents are usually toluene or 2-methyl-THF, but also dichloromethane. The measurement is carried out using a commercially available photoluminescence spectrometer. The triplet energy T1 in eV is determined from the photoluminescence spectra of the emitters. First, the peak maximum Plmax. (in nm) of the photoluminescence spectrum is determined. The peak maximum Plmax. (in nm) is then converted to eV according to: E(T1 in eV) = 1240 / E(T1 in nm) = 1240 / PLmax. (in nm).

[0127] Preferred phosphorescent emitters are therefore yellow emitters, preferably of formula (3a), formulas (1) to (8) or from Table 6, whose triplet energy T-| is preferably between ~2.3 eV and ~2.1 eV.

[0128] Preferred phosphorescent emitters are therefore green emitters, preferably of formula (3a), formulas (1) to (8) or from Table 6, whose triplet energy T-| is preferably between ~2.5 eV and ~2.3 eV.

[0129] Particularly preferred phosphorescent emitters are accordingly green emitters, preferably of formula (3a), formulas (1) to (8) or from Table 6, as previously described, whose triplet energy T-| is preferably between ~2.5 eV and ~2.3 eV.

[0130] Fluorescent emitters can also be present in the light-emitting layer of the device according to the invention or in the mixture according to the invention. Preferred fluorescent emitting compounds are selected from the class of arylamines, wherein preferably at least one of the aromatic or heteroaromatic ring systems of the arylamine is a fused ring system, particularly preferably with at least 14 ring atoms. Preferred examples thereof are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, or aromatic chrysenediamines. An aromatic anthraceneamine is understood to be a compound in which one diarylamino group is bonded directly to one anthracene group, preferably in the 9-position. An aromatic anthracenediamine is understood to be a compound in which two diarylamino groups are bonded directly to one anthracene group, preferably in the 9,10-position.Aromatic pyrenamines, pyrenediamines, chrysenamines, and chrysenediamines are defined analogously, with the diarylamino groups on the pyrene preferably being bonded in the 1-position or 1,6-position. Further preferred emitting compounds are indenofluorenamines or diamines, benzoindenofluorenamines or diamines, and dibenzoindenofluorenamines or diamines, as well as indenofluorene derivatives with fused aryl groups. Pyrenearylamines are also preferred. Also preferred are benzoindenofluoreneamines, benzofluoreneamines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives linked to furan units or thiophene units. Furthermore, the light-emitting device or the mixture according to the invention can also contain materials that exhibit TADF (thermally activated delayed fluorescence).

[0131] According to one embodiment of the present invention, the mixture contains no further components, i.e., functional materials, apart from the constituents of the host material of formula (I) and the further matrix material, as described above or preferably described. These are material mixtures that are used as such to produce the light-emitting layer. These mixtures are also referred to as premix systems, which are used as the sole material source during the vapor deposition of the host materials for the light-emitting layer and which have a constant mixing ratio during vapor deposition. This allows the vapor deposition of a layer with a uniform distribution of the components to be achieved in a simple and rapid manner, without the need for precise control of a large number of material sources.

[0132] According to an alternative embodiment of the present invention, the mixture contains, in addition to the constituents of the host material of formula (I) and the further matrix material, as described above or preferably described, a phosphorescent emitter as described above. With a suitable mixing ratio during vapor deposition, this mixture can also be used as the sole material source.

[0133] The components or constituents of the light-emitting layer of the device according to the invention can thus be processed by vapor deposition or from solution. The material combination of the host materials, as described above or preferably described, optionally with the phosphorescent emitter, as described above or preferably described, is provided for this purpose in a formulation containing at least one solvent. Suitable formulations have been described previously.

[0134] The light-emitting layer in the device according to the invention according to the preferred embodiments and the emitting compound preferably contains between 99.9 and 1 vol.%, more preferably between 99 and 10 vol.%, particularly preferably between 98 and 60 vol.%, most preferably between 97 and 80 vol.% of matrix material composed of at least one compound of formula (I), preferably of formula (Ia), and at least one compound of a further matrix material, based on the total composition of emitter and matrix material. Accordingly, the light-emitting layer in the device according to the invention preferably contains between 0.1 and 99 vol.%, more preferably between 1 and 90 vol.%, particularly preferably between 2 and 40 vol.%, most preferably between 3 and 20 vol.% of the emitter, based on the total composition of the light-emitting layer consisting of emitter and matrix material.If the compounds are processed from solution, the corresponding amounts in wt.% are preferably used instead of the amounts in vol.% given above.

[0135] The present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the organic layer contains a hole injection layer (HIL) and / or a hole transport layer (HTL), whose hole injecting material and hole transporting material belong to the class of arylamines.

[0136] The sequence of layers in the organic electroluminescent device according to the invention is preferably as follows:

[0137] Anode / hole injection layer / hole transport layer / emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0138] It should be noted again that not all of the layers mentioned need to be present and / or that additional layers may be present.

[0139] In addition to the compounds of formula (I) according to the invention, all materials 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 Alqβ, zirconium complexes, for example Zrq4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives.

[0140] Materials that can also be used as electron-transport materials and / or hole-blocking materials are 9,9'-disubstituted fluorene derivatives, including 9,9'-(bistriazinyl)fluorene derivatives (see WO 2009 / 124627 A1) or dibenzofuran derivatives, in which electron-transporting groups such as triazine groups can be bonded directly or via a linker to the dibenzofuran moiety (see WO 2015 / 014434 A1). Further materials for this purpose are the following, which can be prepared according to the processes described in the cited patent applications:

[0141] Suitable cathodes for the device according to the invention include metals with low work functions, metal alloys, or multilayer structures made of different metals, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys made of an alkali or alkaline earth metal and silver, for example, an alloy of magnesium and silver, are also suitable. In multilayer structures, in addition to the metals mentioned, other metals with a relatively high work function, such as Ag or Al, can also be used. Combinations of the metals, such as Ca / Ag, Mg / Ag, or Ba / Ag, are then generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor.Suitable materials for this purpose include alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides or carbonates (e.g., LiF, Ü2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). Lithium quinolinate (LiQ) can also be used. The thickness of this layer is preferably between 0.5 and 5 nm.

[0142] Materials with a high work function are preferred as anodes. The anode preferably has a work function greater than 4.5 eV vs. vacuum. Metals with a high redox potential, such as Ag, Pt, or Au, are suitable for this purpose. Metal / metal oxide electrodes (e.g., Al / Ni / NiO) can also be used. x , AI / PtO x) may be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to enable either the irradiation of the organic material (organic solar cell) or the coupling out of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive, doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of several layers, for example an inner layer made of ITO and an outer layer made of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

[0143] 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.

[0144] 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 vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10'5 mbar, preferably less than 10'0 mbar. However, it is also possible for the initial pressure to be even lower, for example, less than 10' mbar.

[0145] The organic electroluminescent device according to the invention is preferably characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are applied at a pressure between 10'5 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).

[0146] 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 using 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 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.

[0147] 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.

[0148] These methods are generally known to the person skilled in the art and can be applied to organic electroluminescent devices.

[0149] A further subject of the invention is therefore a method for producing the organic electroluminescent device according to the invention, as described above or preferably described, characterized in that the organic layer, preferably the light-emitting layer, the hole injection layer and / or hole transport layer, is applied by vapor phase deposition, in particular with a sublimation process and / or with an OVPD (Organic Vapor Phase Deposition) process and / or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing process.

[0150] When manufactured by vapor deposition, there are basically two ways in which the organic layer according to the invention, preferably the light-emitting layer, can be applied or vapor-deposited onto any substrate or the previous layer. Firstly, the materials used can each be placed in a material source and then evaporated from the various material sources ("co-evaporation"). Secondly, the various materials can be premixed ("premixed" systems) and the mixture placed in a single material source, from which it is then vaporized ("premix evaporation"). This allows for the vapor deposition of the light-emitting layer with a uniform distribution of the components in a simple and rapid manner, without the need for precise control of a large number of material sources.

[0151] The following methods are possible: A method for producing the organic electroluminescent device according to the invention, as described above or preferably described, characterized in that the organic layer, preferably the light-emitting layer, the electron transport layer and / or hole blocking layer, is applied by vapor phase deposition, in particular with a sublimation method and / or with an OVPD (Organic Vapor Phase Deposition) method and / or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing method.

[0152] 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 of the organic layer is applied by gas phase deposition, wherein the at least one compound of formula (I), in particular of formula (Ia), together with the further materials forming the light-emitting layer, are deposited successively or simultaneously from at least two material sources from the gas phase.

[0153] A method for producing the device according to the invention, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of formula (I), in particular of formula (Ia) together with at least one further matrix material as a premix, is deposited from the gas phase successively or simultaneously with the light-emitting materials selected from the group of phosphorescent emitters, fluorescent emitters and / or emitters which exhibit TADF (thermally activated delayed fluorescence).

[0154] The electronic devices according to the invention, in particular organic electroluminescent devices, are characterized by one or more of the following surprising advantages over the prior art:

[0155] 1. Electronic devices, in particular organic electroluminescent devices comprising compounds of the formula (I) or the preferred embodiments set out above and below, in particular as matrix material or as electron-conducting materials, have a very long lifetime. In this case, these compounds bring about a low roll-off, i.e. a low drop in the power efficiency of the device at high luminances. 2. Electronic devices, in particular organic electroluminescent devices comprising compounds of the formula (I) or the preferred embodiments set out above and below as electron-conducting materials, and / or matrix materials, have an excellent efficiency. In this case, compounds of the formula (I) orthe preferred embodiments set out above and below have a low operating voltage when used in electronic devices.

[0156] 3. The compounds according to the invention according to formula (I) or the preferred embodiments described above and below show a very high stability and lifetime.

[0157] 4. Using compounds according to formula (I) or the preferred embodiments described above and below, the formation of optical loss channels can be avoided in electronic devices, particularly organic electroluminescent devices. As a result, these devices are characterized by high PL and thus high EL efficiency of emitters and excellent energy transfer from the matrices to dopants.

[0158] 5. The use of compounds according to formula (I) or the preferred embodiments described above and below in layers of electronic devices, in particular organic electroluminescent devices, leads to a high mobility of the electron conductor structures.

[0159] 6. Compounds according to formula (I) or the preferred embodiments described above and below have excellent glass film formation.

[0160] 7. Compounds according to formula (I) or the preferred embodiments described above and below form very good films from solutions.

[0161] 8. The compounds according to formula (I) or the preferred embodiments described above and below have a deep triplet level Ti, which can be, for example, in the range from 2.50 eV to 2.90 eV.

[0162] These above-mentioned advantages are not accompanied by an excessively high deterioration of the other electronic properties. The present invention further relates to the use of a compound according to formula (I), in particular formula (Ia), or a mixture according to the invention or a formulation according to the invention in an organic electroluminescent device. The compound according to the invention according to formula (I), in particular formula (Ia), or a mixture according to the invention or a formulation according to the invention is preferably used as an electron-transporting material, electron-injecting material, matrix material, hole-transporting and / or hole-blocking material, more preferably as an electron-transporting material, matrix material, hole-transporting material and / or hole-blocking material.

[0163] 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.

[0164] 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).

[0165] The teaching of technical action disclosed in the present invention can be abstracted and combined with other examples.

[0166] The invention is further illustrated by the following examples, without intending to limit it. Examples

[0167] Unless otherwise stated, the following syntheses were carried out under a protective gas atmosphere in dried solvents. Solvents and reagents can be purchased from Sigma-ALDRICH or ABCR, for example. The respective information in square brackets or the numbers given for individual compounds refer to the CAS numbers of the known compounds. For compounds that can exhibit multiple enantiomeric, diastereomeric, or tautomeric forms, one form is shown as a representative example.

[0168] A) Synthons known from literature: B) Synthesis of compounds B:

[0169] Example B1: Variant 1

[0170] A well-stirred suspension of 15.5 g (105 mmol) of LS1 in 400 mL of tetrahydrofuran (THF), cooled to -78 °C, was treated dropwise with 65.6 mL (105 mmol) of n-BuLi, 1.6 N in hexane. Stirring was continued for 1 h, and then a solution of 26.8 g (100 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine [3842-55-5] in 250 mL of THF was added dropwise. The mixture is stirred for 1 h, then allowed to warm to room temperature overnight. 800 ml of ice water is added dropwise. The precipitated solid is filtered off with suction, washed once with 200 ml of water, once with 150 ml of water / ethanol (EtOH) (1:1 vv), and three times with 100 ml of EtOH, and dried in vacuo. The crude product is purified by chromatography (Torrent column system from A. Semrau) and / or repeated hot extraction crystallization (common organic solvents or combinations thereof, preferably acetonitrile / DCM, 1:3 to 3:1 vv), as well as fractional sublimation or annealing under high vacuum. Yield: 30.4 g (78 mmol) 78%;

[0171] Purity: approx. 99.9% according to HPLC.

[0172] Example B1: Variant 2

[0173] A well-stirred mixture of 15.5 g (105 mmol) LS1, 26.8 g (100 mmol) 2-chloro-4,6-diphenyl-1,3,5-triazine [3842-55-5], 65.2 g (200 mmol) cesium carbonate, 2.3 g (4 mmol) XanthPhos, 449 mg (2 mmol) palladium(II) acetate, 100 g (glass beads, 3 mm diameter) and 600 ml toluene is heated under reflux for 18 h. The mixture is filtered with suction while still hot through a bed of Celite pre-slurried with toluene, the filtrate is evaporated to dryness, the residue is taken up in 300 ml of water / ethanol (EtOH) (1:1 vv), the solid is stirred, filtered with suction, washed three times with 100 ml of EtOH each time, and dried in vacuo. Further purification is carried out as described under variant 1. Yield: 32.1 g (82 mmol) 82%; Purity: approximately 99.9% by HPLC.

[0174] The following compounds can be prepared analogously, adjusting the respective stoichiometries of the reactants. When various amides (LS1 to LS30) are reacted with di- or trichloroheterocycles in a mixture or by consecutive reaction, mixed products with respect to the LS are obtained.

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181] Example 600:

[0182] A mixture of 17.3 g (50 mmol) of 9,9'-spirobi[9H-fluorene]-2,2'-diamine [67665-45-6], 16.4 g (105 mmol) of LS100, and 100 ml of dimethylacetamide is heated to 160 °C for 16 h. After cooling, the reaction mixture is poured into 500 ml of ice-water with vigorous stirring, the precipitated solid is filtered off with suction, washed three times with 100 ml of water each time, three times with 50 ml of ethanol each time, and dried in vacuo.

[0183] Alternatively, extraction with dichloromethane (DOM) can be used.

[0184] Purification of the crude product is carried out by chromatography (Torrent column machine from A. Semrau) and / or repeated hot extraction crystallization (usual organic solvents or their combinations, preferably acetonitrile-DCM, 1:3 to 3:1 vv) as well as fractional sublimation or annealing in

[0185] High vacuum. Yield: 20.1 g (32 mmol) 64%; Purity: approximately 99.9% by HPLC. The following compounds can be prepared analogously, adjusting the respective stoichiometries of the reactants. When various anhydrides (LS100 to LS109 and LS200) are reacted with di- or tri-amino aromatics / heteroaromatics in a mixture or by consecutive reaction, mixed products with respect to the LS are obtained.

[0186]

[0187]

[0188]

[0189] Production of OLEDs

[0190] The production of OLEDs according to the invention as well as OLEDs according to the prior art is carried out according to a general process according to WO 2004 / 058911 , which is adapted to the conditions described here (layer thickness variation, materials used).

[0191] The following examples present the results of various OLEDs. Cleaned glass plates (cleaned in a Miele laboratory dishwasher, using Merck Extran cleaner) coated with 50 nm thick structured ITO (indium tin oxide) are pretreated with UV ozone for 25 minutes (UV ozone generator PR-100, UVP). These coated glass plates form the substrates onto which the OLEDs are applied. a) Blue fluorescent OLED devices - BF:

[0192] The compounds B according to the invention can be used in the hole-blocking layer (HBL) and the electron-transport layer (ETL). All materials are thermally vapor-deposited in a vacuum chamber. The emission layer (EML) always consists of at least one matrix material (host material) SMB (see Table 1) and an emitting dopant (emitter) D, which is admixed to the matrix material(s) by co-evaporation in a specific volume fraction. A value such as SMB:D (97%:3%) means that the SMB material is present in the layer in a volume fraction of 97% and the dopant D in a volume fraction of 3%. Analogously, the electron-transport layer can also consist of a mixture of two materials, see Table 1. The materials used to produce the OLEDs are shown in Table 5.

[0193] The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, current efficiency (measured in cd / A), power efficiency (measured in λ / W), and external quantum efficiency (EQE, measured in percent) are determined as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming a Lambertian radiation pattern. The EQE is expressed in (%) and the voltage in (V) at a luminance of 1000 cd / m². 2 .

[0194] The OLEDs have the following layer structure:

[0195] Substrat

[0196] Hole injection layer (HIL) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0197] Hole transport layer (HTL), made of HTM1, 180 nm

[0198] Electron blocking layer (EBL), see Table 1

[0199] Emission layer (EML), see Table 1

[0200] Hole blocking layer (HBL), see Table 1

[0201] Electron transport layer (ETL), see Table 1

[0202] Electron injection layer (EIL) made of ETM2, 1 nm

[0203] Cathode made of aluminum, 100 nm Table 4: Structure of blue fluorescent OLED components

[0204] Table 5: Results of blue fluorescent OLED devices b) Phosphorescent OLED components:

[0205] The compounds B according to the invention can be used in the hole-blocking layer (HBL), the electron-transport layer (ETL), and in the emission layer (EML) as electron-conducting matrix material (host material) (eTMM). For this purpose, all materials are thermally vapor-deposited in a vacuum chamber. The emission layer always consists of at least one or more matrix materials M and a phosphorescent dopant Ir, which is admixed to the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as M1:M2:Ir (55%:35%:10%) means that the material M1 is present in the layer in a volume fraction of 55%, M2 in a volume fraction of 35%, and Ir in a volume fraction of 10%. Analogously, the electron-transport layer can also consist of a mixture of two materials. The exact structure of the OLEDs can be found in Table 3.The materials used to manufacture the OLEDs are shown in Table 5. The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, current efficiency (measured in cd / A), power efficiency (measured in λm / W), and external quantum efficiency (EQE, measured in percent) are determined as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming a Lambertian radiation pattern. The EQE (%) and the voltage (V) are expressed at a luminance of 1000 cd / m². 2 .

[0206] The OLEDs have the following layer structure:

[0207] Substrat

[0208] Hole injection layer (HIL) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0209] Hole transport layer (HTL) made of HTM1, 180 nm for blue, 50 nm for green, yellow and red

[0210] Electron blocking layer (EBL), see Table 3

[0211] Emission layer (EML), see Table 3

[0212] Hole blocking layer (HBL), see Table 3

[0213] Electron transport layer (ETL), see Table 3

[0214] Electron injection layer (EIL) made of ETM2, 1 nm

[0215] Cathode made of aluminum, 100 nm

[0216] Table 6: Structure of phosphorescent OLED components

[0217] Table 7: Results of phosphorescent OLED devices

[0218] Table 8: Structural formulas of the materials used

Claims

Patent claims 1. Compound according to formula (I) Formula (I) where the symbols used are: W is a single bond, -O-, -S- or C(R X )2; R x is, identically or differently at each occurrence, H, D, F, CN, a straight-chain alkyl chain having 1 to 40 C atoms, a branched or cyclic alkyl chain having 3 to 40 C atoms, where in the alkyl chains one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 6 can be substituted; two R x form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which, with one or more radicals R 6 can be substituted; R is, identically or differently at each occurrence, F, CN, a straight-chain alkyl chain having 1 to 40 C atoms, a branched or cyclic alkyl chain having 3 to 40 C atoms, where in the alkyl chains one or more H atoms may be replaced by D, F or CN, where optionally two geminal or vicinal R form a monocyclic or polycyclic aliphatic ring system which reacts with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted, or two vicinal R represent the following group where represents the attachment points to the respective carbon atom and Y 1 an electron-transporting group Q 1 which is substituted with one or more residues R 7 may be substituted, or a hole-transporting group H 1which is substituted with one or more residues R 8 can be substituted L is a single bond, or an aromatic or heteroaromatic ring system with 5 - 40 aromatic ring atoms, which is linked to one or more radicals R 9 can be substituted; Y is an electron-transporting group Q which is reacted with one or more residues R 3 may be substituted, or a hole-transporting group H, which may be substituted with one or more residues R 10 can be substituted; R 1 , R 6 is, at each occurrence, the same or different: H, D, F, CI, Br, I, -OH, -SH, CN, NO2, N(Ar)2, N(R 2 )2, C(=O)Ar, C(=O)R 2 , P(=O)(Ar)2, P(Ar)2, B(Ar)2, B(R 2 )2, C(Ar)3, C(R 2 )3, Si(Ar)3, Si(R 2)3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, or an alkenyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, with one or more non-adjacent CH2 groups being replaced by -R 2 C=CR 2 -, -C=C-, Si(R 2 )2, C=O, C=S, C=Se, C=NR 2 , -C(=O)O-, -C(=O)NR 2 -, NR 2 , P(=O)(R 2 ), -O-, -S-, SO or SO2 and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 2may be substituted, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms which may be substituted with one or more radicals R 2 may be substituted, or a combination of these systems; two or more, preferably adjacent, radicals R 1 or two adjacent residues R 6 together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which, with one or more radicals R 2 can be substituted; R 2 , R 4is, on each occurrence, identically or differently, H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, where in each case one or more H atoms may be replaced by D, F, CI, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, where two or more, preferably adjacent, substituents R 2 or adjacent substituents R 4 form a ring system with each other; R 3 , R 7 , R 8 , R 10 is the same or different at each occurrence: H, D, F, CI, Br, I, -OH, -SH, CN, NO2, N(Ar 1 )2, N(R 4 )2, C(=O)Ar 1 , C(=O)R 4 , P(=O)(Ar 1 )2, P(Ar 1 )2, B(Ar 1 )2, B(R 1 )2, C(Ar 1 )a, C(R 4 )3, Si(Ar 1 )3, Si(R 4)s, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, or an alkenyl group having 2 to 40 C atoms, each of which is substituted by one or more radicals R 4 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R 4 C=CR 4 -, -C=C-, Si(R 4 )2, C=O, C=S, C=Se, NR 4 , -C(=O)O-, -C(=O)NR 4 -, NR 2 , P(=O)(R 4 ), -O-, -S-, SO or SO2 and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 4 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 4may be substituted, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms which may be substituted with one or more radicals R 4 may be substituted, or a combination of these systems; two or more, preferably adjacent, radicals R 3 together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which, with one or more radicals R 4 may be substituted; or a group of the following formula, where the dashed line represents the connection to Q or Q 1 and R has the meaning given above; Ar, Ar 1 , is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system with 5 - 40 aromatic ring atoms, each substituted by one or more radicals R 5 can be substituted; R 5 , R 9is, at each occurrence, identically or differently, H, D, F, CN, an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms in which one or more H atoms may be replaced by D, F, Cl, I, Br or CN or a straight-chain or branched alkyl chain with 1 - 4 C atoms and the following compounds are excluded:

2. A compound according to claim 1, wherein L is a single bond, or an aromatic ring system having 6 to 30 aromatic ring atoms or a heteroaromatic ring system having 5 to 24 aromatic ring atoms, wherein the respective ring system is linked to one or more radicals R 9 can be substituted.

3. A compound according to claim 1 or 2, wherein W is a single bond.

4. A compound according to one or more of claims 1 to 3, wherein R on each occurrence, identically or differently, is F, CN, a straight-chain alkyl chain having 1 to 20 C atoms, a branched or cyclic alkyl chain having 3 to 20 C atoms, wherein in the alkyl chains one or more H atoms may be replaced by D, F or CN, wherein optionally two geminal or vicinal R form a monocyclic aliphatic ring system which reacts with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted, or two vicinal R represent the following group where * represents the attachment points to the respective carbon atom and Y 1 has the meaning given in claim 1.

5. A compound according to one or more of claims 1 to 4, wherein Q or Q1 identical or different are a triazine, pyrimidine, pyridine, quinazoline, quinoxaline, diazadibenzofuran, diazadibenzothiophene, B(Ar)2, P(=O)(Ar)2, P(Ar)2, where Q is substituted with one or more radicals R 3 and Q 1 with one or more residues R 8 can be substituted.

6. A compound according to claim 5, wherein Q or Q 1 identical or different is a triazine, pyrimidine, quinazoline, diazadibenzofuran or dibenzothiophene, where Q is substituted with one or more radicals R 3 and Q 1 with one or more residues R 8 can be substituted.

7. A compound according to one or more of claims 1 to 6, wherein R 3 or R 8 at each occurrence, identically or differently, H, D, F, CN, -OH, -SH, Si(R 4)4, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or an alkenyl group having 2 to 20 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, where in the alkyl chains one or more H atoms may be replaced by D, F, CI, Br, I or CN, or an aromatic or heteroaromatic ring system with 5 to 25 aromatic ring atoms, each substituted by one or more radicals R 2 may be substituted, or a combination of these systems; two or more, preferably adjacent, radicals R 3 together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which, with one or more radicals R 4 may be substituted; or a group of the following formula, where the dashed line represents the connection to Q or Q 1 and R has the meaning given in claim 1.

8. A compound according to one or more of claims 1 to 7, wherein R 3 or R 8 independently of one another represents an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms and is selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, which are each substituted with one or more radicals R 4 can be substituted.

9. A compound according to one or more of claims 1 to 5, wherein the hole-transporting group H is a carbazole, biscarbazole, triscarbazole, indenocarbazole, indolocarbazole, benzimidazobenzimidazole or diarylamine, which is reacted with one or more radicals R 10 can be substituted.

10. A mixture comprising at least one compound according to one or more of claims 1 to 9 and at least one further compound selected from the group of matrix materials, phosphorescent emitters, fluorescent emitters and / or emitters exhibiting TADF (thermally activated delayed fluorescence), electron-transporting materials, electron-injecting materials, hole-transporting materials, hole-injecting materials, electron-blocking materials, and / or a solvent.

11. An organic electronic device comprising an anode, a cathode and at least one organic layer containing at least one compound according to one or more of claims 1 to 9 or a mixture according to claim 10.

12. The organic electronic device of claim 10, wherein the device is an organic electroluminescent device.

13. The organic electronic device according to claim 11 or 12, wherein the organic layer comprises at least one electron-transporting layer, electron-injecting layer, hole-blocking layer, hole-transporting or light-emitting layer containing the compound according to one or more of claims 1 to 9 or the mixture according to claim 10.

14. The organic electronic device according to claim 12 or 13, which is an electroluminescent device selected from the group consisting of organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers), and organic light-emitting diodes (OLEDs).

15. Use of a compound according to one or more of claims 1 to 9 or a mixture according to claim 10 in an organic electroluminescent device.

16. Use according to claim 15 as electron-transporting material, electron-injecting material, matrix material, hole-transporting and / or hole-blocking material.

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