MATERIALS FOR ORGANIC ELECTROLUMINESCENTS

Description

[0001] The present invention relates to materials for use in electronic devices, in particular in organic electroluminescent devices, and to electronic devices, in particular organic electroluminescent devices, containing these materials.

[0002] In organic electroluminescent devices (OLEDs), phosphorescent organometallic complexes are often used as emitting materials. In general, OLEDs, especially those exhibiting triplet emission (phosphorescence), still have room for improvement, for example, with regard to efficiency, operating voltage, and lifetime. The properties of phosphorescent OLEDs are determined not only by the triplet emitters used. The other materials used, such as matrix materials, are also of particular importance. Improvements to these materials can therefore also lead to improvements in OLED properties.

[0003] The object of the present invention is to provide compounds which are suitable for use in an OLED, in particular as matrix material for phosphorescent emitters, as electron transport material, as hole blocking material or also as hole transport or electron blocking material and which lead to good properties there.

[0004] CN112625032 A, CN112062772 A and WO2012048781 A1 describe bridged triphenylene compounds suitable for use in electronic devices.

[0005] Surprisingly, it has been found that certain compounds, described in more detail below, solve this problem and are well suited for use in OLEDs. In particular, the OLEDs exhibit a long lifetime, high efficiency, and a lower operating voltage. These compounds and electronic devices, in particular organic electroluminescent devices containing these compounds, are therefore the subject of the present invention. The present invention relates to a compound according to formula (1), where the symbols used are: X is the same or different on each occurrence and is CR or N, with the proviso that a maximum of two X groups per cycle are N and that two adjacent X groups which are part of the cycle with three X groups are C, which form an aromatic or heteroaromatic ring system fused to the cycle via the bonds marked *; Y is C(R) 2 , O or S; Y 1< is C(R) 2 ; Q is the same or different on each occurrence and is CR or N, with the proviso that a maximum of two Q groups per cycle are N. R is, identically or differently at each occurrence, H, D, F, Cl, Br, I, N(Ar') 2 , N(R 1< ) 2 , OAr', SAr', B(OR 1< ) 2 , CHO, C(=O)R 1< , CR 1< =C(R 1< ) 2 , CN, C(=O)OR 1< , C(=O)NR 1< , Si(R 1< ) 3 , NO 2 , P(=O)(R 1< ) 2 , OSO 2 R 1< , OR 1< , S(=O)R 1< , S(=O) 2 R 1< , SR 1< , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms,where the alkyl, alkenyl or alkynyl group may each be substituted by one or more radicals R 1<, where one or more non-adjacent CH 2 groups may be replaced by -R 1< C=CR 1< -, -C≡C-, Si(R 1< ) 2 , NR 1< , CONR 1< , C=O, C=S, -C(=O)O-, P(=O)(R 1< ), -O-, -S-, SO or SO 2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may each be substituted by one or more radicals R 1<, where two or more radicals R bonded to the same ring may together form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system which may be substituted with one or more radicals R 1<, and where two radicals R bonded to the same carbon, silicon, germanium or tin atom can form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system with each other,which may be substituted by one or more radicals R 1<; Ar' is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 1<; R 1< is, identically or differently on each occurrence, H, D, F, I, B(OR 2< ) 2 , N(R 2< )2, CHO, C(=O)R 2< , CR 2< =C(R 2< )2, CN, C(=O)OR 2< , Si(R 2< )3, NO 2 , P(=O)(R 2< ) 2 , OSO 2 R 2< , SR 2< , OR 2< , S(=O)R 2< , S(=O) 2 R 2< , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or Alkynyl group may be substituted by one or more radicals R 2< and wherein one or more CH 2 groups in the above-mentioned groups are substituted by -R 2< C=CR 2< -, -C=C-, Si(R 2< ) 2 , C=O, C=S, -C(=O)O-, NR 2< , CONR 2< , P(=O)(R 2< ), -O-, -S-,SO or SO 2 can be replaced and where one or more H atoms in the above-mentioned groups can be replaced by D, F, Cl, Br, I, CN or NO 2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R 2<, where two or more radicals R 1< can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R 2< is, identical or different at each occurrence, H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms can also be replaced by D or F; two or more substituents R 2< can be linked to one another and form a ring.

[0006] An aryl group within the meaning of this invention contains 6 to 40 C atoms; a heteroaryl group within the meaning of this invention contains 2 to 40 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc., or a condensed (fused) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatics linked to one another by a single bond, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as an aromatic ring system.

[0007] An aromatic ring system within the meaning of this invention contains 6 to 60 C atoms, preferably 6 to 40 C atoms in the ring system. A heteroaromatic ring system within the meaning of this invention contains 2 to 60 C atoms, preferably 2 to 40 C atoms and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system within the meaning of this invention is to be understood as a system which does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be connected by a non-aromatic unit, such as a C, N or O atom. This is also to be understood as meaning systems in which two or more aryl or heteroaryl groups are directly linked to one another, such as, for example, a C, N or O atom. B. biphenyl, terphenyl, bipyridine or phenylpyridine.For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ethers, stilbene, etc., are also to be understood as aromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are linked, for example, by a short alkyl group. Preferred aromatic or heteroaromatic ring systems are simple aryl or heteroaryl groups, as well as groups in which two or more aryl or heteroaryl groups are directly linked to one another, for example, biphenyl or bipyridine, as well as fluorene or spirobifluorene.

[0008] An electron-rich heteroaromatic ring system is characterized by the fact that it is a heteroaromatic ring system that contains no electron-deficient heteroaryl groups. An electron-deficient heteroaryl group is a six-membered ring heteroaryl group with at least one nitrogen atom or a five-membered ring heteroaryl group with at least two heteroatoms, one of which is a nitrogen atom and the other oxygen, sulfur, or a substituted nitrogen atom, to which further aryl or heteroaryl groups may be fused. In contrast, electron-rich heteroaryl groups are five-membered ring heteroaryl groups with exactly one heteroatom selected from oxygen, sulfur, or substituted nitrogen, to which further aryl groups and / or further electron-rich five-membered ring heteroaryl groups may be fused.Examples of electron-rich heteroaryl groups include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, and indenocarbazole. An electron-rich heteroaryl group is also called an electron-rich heteroaromatic radical.

[0009] An electron-poor heteroaromatic ring system is characterized in that it contains at least one electron-poor heteroaryl group, and particularly preferably no electron-rich heteroaryl groups.

[0010] In the context of the present invention, the term "alkyl group" is used as a generic term for both linear or branched alkyl groups and cyclic alkyl groups. Analogously, the terms "alkenyl group" and "alkynyl group" are used as generic terms for both linear or branched alkenyl or alkynyl groups, as well as for cyclic alkenyl or alkynyl groups.

[0011] In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which may contain 1 to 40 C atoms and in which individual H atoms or CH 2 groups may be substituted by the abovementioned groups, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neo-pentyl, cyclopentyl, n-hexyl, neo-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, Cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentinyl, hexynyl, heptynyl or octynyl.Unter einer Alkoxygruppe OR 1< mit 1 bis 40 C-Atomen werden bevorzugt Methoxy, Trifluormethoxy, Ethoxy, n-Propoxy, i-Propoxy, n-Butoxy, i-Butoxy, s-Butoxy, t-Butoxy, n-Pentoxy, s-Pentoxy, 2-Methylbutoxy, n-Hexoxy, Cyclohexyloxy, n-Heptoxy, Cycloheptyloxy, n-Octyloxy, Cyclooctyloxy, 2-Ethylhexyloxy, Pentafluorethoxy und 2,2,2-Trifluorethoxy verstanden.Unter einer Thioalkylgruppe SR 1< mit 1 bis 40 C-Atomen werden insbesondere Methylthio, Ethylthio, n-Propylthio, i-Propylthio, n-Butylthio, i-Butylthio, s-Butylthio, t-Butylthio, n-Pentylthio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclooctylthio, 2-Ethylhexylthio, Trifluormethylthio, Pentafluorethylthio, 2,2,2-Trifluorethylthio, Ethenylthio, Propenylthio, Butenylthio, Pentenylthio, Cyclopentenylthio, Hexenylthio, Cyclohexenylthio, Heptenylthio, Cycloheptenylthio, Octenylthio, Cyclooctenylthio, Ethinylthio, Propinylthio, Butinylthio, Pentinylthio, Hexinylthio, Heptinylthio oder Octinylthio verstanden.In general, alkyl, alkoxy, or thioalkyl groups according to the present invention may be straight-chain, branched, or cyclic, wherein one or more non-adjacent CH 2 groups may be replaced by the above-mentioned groups; furthermore, one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO 2 , preferably F, Cl, or CN, particularly preferably F or CN.

[0012] An aromatic or heteroaromatic ring system with 5 - 60 aromatic ring atoms, which may also be substituted by the above-mentioned radicals R 2< or a hydrocarbon radical and which may be linked to the aromatic or heteroaromatic ring via any position, is understood to mean in particular groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, Thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,Benzo-7,8-chinolin, Phenothiazin, Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1,2-Thiazol, 1,3-Thiazol, Benzothiazol, Pyridazin, Hexaazatriphenylen, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1,5-Diazaanthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1,6-Diazapyren, 1,8-Diazapyren, 4,5-Diazapyren, 4,5,9,10-Tetraazaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1,2,3-Triazol, 1,2,4-Triazol, Benzotriazol, 1,2,3-Oxadiazol, 1,2,4-Oxadiazol, 1,2,5-Oxadiazol, 1,3,4-Oxadiazol, 1,2,3-Thiadiazol, 1,2,4-Thiadiazol, 1,2,5-Thiadiazol, 1,3,4-Thiadiazol, 1,3,5-Triazin, 1,2,4-Triazin, 1,2,3-Triazin, Tetrazol, 1,2,4,5-Tetrazin, 1,2,3,4-Tetrazin, 1,2,3,5-Tetrazin, Purin, Pteridin, Indolizin und Benzothiadiazol oder Gruppen,which are derived from combination of these systems.,

[0013] For the purposes of this description, the phrase "two or more residues can form a ring system" is understood to mean, 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:

[0014] 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:

[0015] Further preferred embodiments are shown by the following formulas (2-1) to (2-4): where the symbols used have the meanings given above for formula (1).

[0016] In a preferred embodiment, at least one radical R of the symbols Y, Y 1< , X or Q in one of the formulas (1) or (2-1) to (2-4) represents an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R 1<.

[0017] In a preferred embodiment of the invention, a maximum of one symbol X per cycle represents N. In a further preferred embodiment of the invention, a maximum of one symbol Q represents N.

[0018] In a particularly preferred embodiment of the invention, X and Q are CR.

[0019] In a preferred embodiment of the invention, the compound has only one fused ring system, which is fused via the bonds marked with *.

[0020] Preferably, the compound of formula (1) has only one fused ring system, which is fused via the bonds marked with *, and only up to one further fused ring system, in which two adjacent radicals R form an aromatic or heteroaromatic ring system having 4 to 8 ring atoms, which is fused to the cycle and can be substituted by one or more radicals R.

[0021] Preferred embodiments of the compounds of formulas (2-1) to (2-4) are the following compounds of formulas (3-1) to (3-4): where the symbols, if present, have the meanings given for formulas (2-1) to (2-4).

[0022] Preferred embodiments of the compounds of formulas (3-1) to (3-4) are the following compounds of formulas (3-1a) to (3-4a): where the symbols, if present, have the meanings given for formulas (2-1) to (2-4).

[0023] In a preferred embodiment of the invention, a maximum of 5 groups R in the formulas (2-1) to (2-4), in the formulas (3-1) to (3-4) and in the formulas (3-1a) to (3-4a) do not represent H, CN or D, particularly preferably a maximum of three groups R, very particularly preferably a maximum of two groups R and especially preferably a maximum of one group R.

[0024] Preferred substituents R, Ar', R 1<, and R 2< are described below. In a particularly preferred embodiment of the invention, the following preferences for R, Ar', R 1<, and R 2< occur simultaneously and apply to the structures of formula (1) as well as to all preferred embodiments listed above.

[0025] In a preferred embodiment of the invention, R is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, OR 1< , a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl or alkenyl group may in each case be substituted by one or more radicals R 1<, but is preferably unsubstituted, and where one or more non-adjacent CH 2 groups may be replaced by O, or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 1<; two radicals R can also form an aliphatic, aromatic or heteroaromatic ring system with one another.Particularly preferably, R is selected, identically or differently at each occurrence, from the group consisting of H, D, a straight-chain alkyl group having 1 to 6 C atoms, in particular having 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group having 3 to 6 C atoms, where the alkyl group may in each case be substituted by one or more radicals R 1<, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R 1<, preferably non-aromatic radicals R 1<. Very particularly preferably, R is selected, identically or differently at each occurrence, from the group consisting of H or D or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2< , preferably non-aromatic radicals R 1< .

[0026] Suitable aromatic or heteroaromatic ring systems R are selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which can be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which can be linked via the 1-, 2-, 3- or 4-position, naphthalene, which can be linked via the 1- or 2-position, indole, benzofuran, benzothiophene, which can be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, carbazole, which can be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, which can be linked via the 1-, 2-, 3- or 4-position can, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, quinoxaline, benzimidazole, phenanthrene, triphenylene or a combination of two or three of these groups,which may each be substituted by one or more radicals R 1<. If R represents a heteroaryl group, in particular triazine, pyrimidine, quinoxaline, or quinazoline, aromatic or heteroaromatic radicals R 1< on this heteroaryl group may also be preferred.

[0027] The groups R, when they represent an aromatic or heteroaromatic ring system, are preferably selected from the groups of the following formulas R-1 to R-83, where R 1< has the meanings given above, the dashed bond represents the bond to a carbon atom of the basic structure in formula (1) or in the preferred embodiments and furthermore: Ar 3< is, on each occurrence, identical or different, a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, each of which may be substituted by one or more radicals R 1<; A 1< is, on each occurrence, identical or different, C(R 1<) 2, NR 1<, O or S, preferably O or S; p is 0 or 1, where p = 0 means that the group Ar 3< is not present and that the corresponding aromatic or heteroaromatic group is directly bonded to a carbon atom of the basic structure in formula (1); r is 0 or 1, where r = 0 means that no group A 1< is bonded at this position and instead radicals R 1< are bonded to the corresponding carbon atoms.

[0028] In a preferred embodiment, Ar 3< comprises bivalent aromatic or heteroaromatic ring systems based on the groups R-1 to R-83, where m is 0 and the dashed bond and an R 1< represents the bond to the aromatic or heteroaromatic group after R-1 to R-83.

[0029] If the above-mentioned groups R-1 to R-83 have multiple A 1< groups for R, all combinations from the definition of A 1< are possible. Preferred embodiments are then those in which one A 1< group represents O or S and the other A 1< group represents C(R 1< ) 2 , or in which both A 1< groups represent S or O, or in which both A 1< groups represent O or S.

[0030] When A 1< stands for NR 1<, the substituent R 1< which is bonded to the nitrogen atom preferably stands for an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more radicals R 2<. In a particularly preferred embodiment, this substituent R 1<, identical or different on each occurrence, stands for an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, which does not have any fused aryl groups or heteroaryl groups in which two or more aromatic or heteroaromatic 6-membered ring groups are directly fused to one another, and which may in each case also be substituted by one or more radicals R 2<.Particularly preferred are phenyl, biphenyl, terphenyl and quaterphenyl with linkage patterns as listed above for R-1 to R-11, where these structures may be substituted by one or more radicals R 1<, but are preferably unsubstituted.

[0031] When A 1< stands for C(R 1< ) 2, the substituents R 1< which are bonded to this carbon atom are preferably identical or different on each occurrence and are a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more radicals R 2<. Very particularly preferably, R 1< stands for a methyl group or a phenyl group. The radicals R 1< can also form a ring system with one another, resulting in a spiro system.

[0032] If Y and / or Y 1< stands for C(R) 2, the substituents R which are bonded to this carbon atom are preferably identical or different on each occurrence and are a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or electron-deficient heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be substituted by one or more radicals R 1<. These substituents R very particularly preferably stand for a methyl group or a phenyl group. The radicals R can also form a ring system with one another, resulting in a spiro system.

[0033] In one embodiment of the invention, at least one radical R represents an electron-rich heteroaromatic ring system. The electron-rich heteroaromatic ring system is preferably selected from the groups R-13 to R-42 depicted above, where in the groups R-13 to R-16, R-18 to R-20, R-22 to R-24, R-27 to R-29, R-31 to R-33, and R-35 to R-37, at least one group A 1< represents NR 1<, where R 1< preferably represents an aromatic or heteroaromatic ring system, in particular an aromatic ring system.

[0034] In another particularly preferred embodiment of the invention, at least one R radical represents an electron-poor heteroaromatic ring system. The electron-poor heteroaromatic ring system is preferably selected from the groups R-47 to R-50, R-57, R-58, R-76; R-79, R-80, R-81, and R-82 depicted above.

[0035] In a further preferred embodiment of the invention, R 1< is selected, identically or differently on each occurrence, from the group consisting of H, D, F, CN, OR 2< , a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl or alkenyl group may in each case be substituted by one or more radicals R 2< and where one or more non-adjacent CH 2 groups may be replaced by O, or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2<; two or more radicals R 1< may here form an aliphatic ring system with one another.In a particularly preferred embodiment of the invention, R 1< is selected, identically or differently on each occurrence, from the group consisting of H, D, a straight-chain alkyl group having 1 to 6 C atoms, in particular having 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group having 3 to 6 C atoms, where the alkyl group may be substituted by one or more radicals R 2<, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R 2<, but is preferably unsubstituted.

[0036] In a further preferred embodiment of the invention, R 2< is identical or different on each occurrence and is H, D, F, an alkyl group having 1 to 4 C atoms or an aryl group having 6 to 10 C atoms, which may be substituted by an alkyl group having 1 to 4 C atoms, but is preferably unsubstituted.

[0037] In a further preferred embodiment of the invention, all radicals R 1< , insofar as they represent an aromatic or heteroaromatic ring system, or R 2< , insofar as they represent aromatic or heteroaromatic groups, are selected from the groups R-1 to R-83, which, however, are then each substituted accordingly with R 2< , or the groups mentioned under R 2<.

[0038] In a preferred embodiment, the radicals R do not form any further aromatic or heteroaromatic groups fused to the basic structure of formula (1).

[0039] The alkyl groups in compounds according to the invention that are processed by vacuum evaporation preferably have no more than five carbon atoms, more preferably no more than four carbon atoms, and most preferably no more than one carbon atom. For compounds that are processed from solution, compounds that are substituted with alkyl groups, in particular branched alkyl groups, having up to 10 carbon atoms, or that are substituted with oligoarylene groups, for example ortho-, meta-, para-, or branched terphenyl or quaterphenyl groups, are also suitable.

[0040] When the compounds of formula (1) or the preferred embodiments are used as matrix material for a phosphorescent emitter or in a layer directly adjacent to a phosphorescent layer, it is further preferred if the compound does not contain any condensed aryl or heteroaryl groups in which more than two six-membered rings are directly fused to one another. In particular, it is preferred that the radicals Ar', R, R 1<, and R 2< do not contain any condensed aryl or heteroaryl groups in which two or more six-membered rings are directly fused to one another. Exceptions to this are phenanthrene, triphenylene, quinoxaline, and quinazoline, which may be preferred due to their high triplet energy despite the presence of condensed aromatic six-membered rings.

[0041] The above-mentioned preferred embodiments can be combined with each other as desired within the limitations defined in claim 1. In a particularly preferred embodiment of the invention, the above-mentioned advantages occur simultaneously.

[0042] Examples of preferred compounds according to the embodiments listed above are the compounds listed in the following table.

[0043] The compounds according to the invention can be prepared by synthesis steps known to the person skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Heck reaction, Hartwig-Buchwald coupling, etc.

[0044] A further object of the present invention is therefore a process for preparing the compounds according to the invention, characterized by the following steps: (A) Synthesis of the basic structure according to formula (1); (B) condensation of the aromatic or heteroaromatic ring system to form the bonds marked * according to formula (1) by coupling and ring closure reaction.

[0045] The synthesis of the basic framework can be carried out, for example, via a combination of Ullmann coupling, Suzuki coupling and an intramolecular Heck reaction, as shown in the following Scheme 1 or Scheme 2:

[0046] The condensation of the aromatic or heteroaromatic ring system can then be carried out by appropriate coupling and ring closure reactions, as shown in the following Schemes 3 or 5.

[0047] 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 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-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, Decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenetol,1,4-Diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents.

[0048] The present invention therefore further provides a formulation comprising at least one compound according to the invention and at least one further compound. The further compound can, for example, be a solvent, in particular one of the abovementioned solvents or a mixture of these solvents. However, the further compound can also be at least one further organic or inorganic compound that is also used in the electronic device, for example an emitting compound and / or a further matrix material. Suitable emitting compounds and further matrix materials are listed below in connection with the organic electroluminescent device. This further compound can also be polymeric.

[0049] The compounds according to the invention are suitable for use in an electronic device, in particular in an organic electroluminescent device.

[0050] A further object of the present invention is therefore the use of a compound according to the invention in an electronic device, in particular in an organic electroluminescent device.

[0051] A further subject of the present invention is an electronic device comprising at least one compound according to the invention.

[0052] An electronic device within the meaning of the present invention is a device that contains at least one layer containing at least one organic compound. The component may also contain inorganic materials or layers composed entirely of inorganic materials.

[0053] The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), dye-sensitized organic solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), and organic plasmon emitting devices, but preferably organic electroluminescent devices (OLEDs), particularly preferably phosphorescent OLEDs.

[0054] The organic electroluminescent device contains a cathode, an anode, and at least one emitting layer. In addition to these layers, it may contain further layers, for example, one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers, and / or charge-generation layers. Interlayers, which, for example, have an exciton-blocking function, may also be inserted between two emitting layers. It should be noted, however, that not all of these layers are necessarily present. The organic electroluminescent device may contain one emitting layer or it may contain multiple emitting layers.If multiple emission layers are present, they preferably have a total of several emission maxima between 380 nm and 750 nm, resulting in overall white emission. This means that different emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. Systems with three emitting layers are particularly preferred, with the three layers exhibiting blue, green, and orange or red emission. The organic electroluminescent device according to the invention can also be a tandem OLED, particularly for white-emitting OLEDs.

[0055] The compound according to the invention according to the embodiments listed above can be used in different layers, depending on the precise structure. An organic electroluminescent device comprising a compound according to formula (1) or the preferred embodiments listed above in an emitting layer is preferred as a matrix material for phosphorescent emitters, for fluorescent emitters, or for emitters exhibiting TADF (thermally activated delayed fluorescence), in particular for phosphorescent emitters. The organic electroluminescent device can contain one emitting layer or it can contain several emitting layers, with at least one emitting layer containing at least one compound according to the invention as a matrix material.Furthermore, the compound according to the invention can also be used in an electron transport layer and / or in a hole blocking layer and / or in a hole transport layer and / or in an exciton blocking layer.

[0056] When the compound according to the invention is used as a matrix material for a phosphorescent compound in an emitting layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). Phosphorescence, within the meaning of this invention, refers to luminescence from an excited state with higher spin multiplicity, i.e., a spin state > 1, in particular from an excited triplet state. For the purposes of this application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum, and copper complexes, are to be considered phosphorescent compounds.

[0057] The mixture of the compound according to the invention and the emitting compound contains between 99 and 1 vol.%, preferably between 98 and 10 vol.%, particularly preferably between 97 and 60 vol.%, in particular between 95 and 80 vol.% of the compound according to the invention, based on the total mixture of emitter and matrix material. Accordingly, the mixture contains between 1 and 99 vol.%, preferably between 2 and 90 vol.%, particularly preferably between 3 and 40 vol.%, in particular between 5 and 20 vol.% of the emitter, based on the total mixture of emitter and matrix material.

[0058] A further preferred embodiment of the present invention is the use of the compound according to the invention as a matrix material for a phosphorescent emitter in combination with another matrix material. Suitable matrix materials that can be used in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g., according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627, or WO 2010 / 006680, triarylamines, carbazole derivatives, e.g., B. CBP (N,N-biscarbazolylbiphenyl) or WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176, indolocarbazole derivatives, e.g. according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, e.g. according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776, azacarbazole derivatives, e.g. B. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, e.g.according to WO 2007 / 137725, silanes, e.g. according to WO 2005 / 111172, azaboroles or boronate esters, e.g. according to WO 2006 / 117052, triazine derivatives, e.g. according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, diazasilole or tetraazasilole derivatives, e.g. according to WO 2010 / 054729, diazaphosphole derivatives, e.g. B. according to WO 2010 / 054730, bridged carbazole derivatives, e.g. according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080, triphenylene derivatives, e.g. according to WO 2012 / 048781, or dibenzofuran derivatives, e.g. according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565.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, as described, for example, in WO 2010 / 108579.

[0059] In a preferred embodiment of the invention, the materials are used in combination with another matrix material. Preferred co-matrix materials, especially when the compound according to the invention is substituted with an electron-deficient heteroaromatic ring system, are selected from the group of biscarbazoles, bridged carbazoles, triarylamines, dibenzofuran-carbazole derivatives or dibenzofuran-amine derivatives, and carbazolamines.

[0060] Preferred biscarbazoles are the structures of the following formulas (4) and (5), where for Ar, R and A 1< the following applies: A 1< is, identically or differently on each occurrence, NAr, O, S or C(R) 2 ; Ar is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R; R is at each occurrence, identically or differently, H, D, F, Cl, Br, I, B(OR 1< ) 2 , CHO, C(=O)R', CR 1< =C(R 1< ) 2 , CN, C(=O)OR 1< , C(=O)N(R 1< ) 2 , Si(R 1< ) 3 , N(R 1< ) 2 , NO 2 , P(=O)(R 1< ) 2 , OSO 2 R 1< , OR 1< , S(=O)R 1< , S(=O) 2 R 1< , SR 1< , a straight-chain alkylalkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group may each be substituted by one or more radicals R 1<, where one or more non-adjacent CH 2 groups are substituted by -R 1< C=CR 1< -, -C=C-, Si(R 1< ) 2 , C=O, C=S, C=NR 1< , -C(=O)O-, -C(=O)NR 1< -, NR 1< ,P(=O)(R 1< ), -O-, -S-, SO or SO 2 , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R 1<, where two or more radicals R may be linked to one another and form a ring; ,

[0061] In a preferred embodiment of the invention, A 1< is CR 2 .

[0062] Preferably, Ar in the case of formula (4) and (5) represents an aromatic or heteroaromatic ring system, preferably selected on each occurrence, identically or differently, from the groups of the following formulae Ar-1 to Ar-76, where the dashed line represents the bond to the backbone and furthermore: Ar 3< is, identical or different on each occurrence, a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, each of which may be substituted by one or more R radicals; Ar 2< is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more R radicals; A 1< is, identical or different on each occurrence, NAr 2< , O, S or C(R) 2 ; n is 0 or 1, where n = 0 means that no A 1< group is bonded at this position and R radicals are bonded to the corresponding carbon atoms instead; m is 0 or 1, where m = 0 means that the Ar 3< group is not present and that the corresponding aromatic or heteroaromatic group is bonded directly to the nitrogen atom.

[0063] Preferred embodiments of the compounds of formulas (4) and (5) are the compounds of the following formulas (4a) and (5a), where the symbols used have the meanings given above according to formula (4) and formula (5).

[0064] Examples of suitable compounds according to formula (4) or (5) are the compounds shown below.

[0065] Preferred bridged carbazoles are the structures of the following formula (6), where A 1< and R have the meanings given above according to formulas (4) and (5) and A 1< is preferably selected, identically or differently on each occurrence, from the group consisting of NAr and CR 2 .

[0066] Preferred dibenzofuran derivatives are the compounds of the following formula (7), where the oxygen can also be replaced by sulfur to form a dibenzothiophene, L represents a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which can also be substituted by one or more R radicals, and R and Ar have the meanings given above. The two Ar groups, which bond to the same nitrogen atom, or an Ar group and an L group, which bond to the same nitrogen atom, can also be bonded to one another, for example to form a carbazole.

[0067] Examples of suitable dibenzofuran derivatives are the compounds shown below.

[0068] Preferred carbazolamines are the structures of the following formulas (8), (9) and (10), where L represents an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R, and R and Ar have the abovementioned meanings according to formula (4) or formula (5).

[0069] Examples of suitable carbazolamine derivatives are the compounds shown below.

[0070] Further particularly preferred co-matrix materials, in particular hole-transporting co-hosts, especially when the compound according to the invention is substituted with an electron-deficient heteroaromatic ring system, are shown in the following table:

[0071] Preferred co-matrix materials, especially when the compound according to the invention is substituted with an electron-rich heteroaromatic ring system, for example a carbazole group, are further selected from the group consisting of triazine derivatives, pyrimidine derivatives, quinazoline derivatives, and quinoxaline derivatives. Preferred triazine, quinazoline, quinoxaline, or pyrimidine derivatives, which can be used as a mixture together with the compounds according to the invention, are the compounds of the following formulas (11), (12), (13), and (14): where Ar and R have the abovementioned meanings according to formulas (4) and (5).

[0072] Particularly preferred are the triazine derivatives of formula (11) and the quinazoline derivatives of formula (13), in particular the triazine derivatives of formula (11).

[0073] In a preferred embodiment of the invention, Ar in formulas (11), (12), (13) and (14) is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, in particular having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R. Suitable aromatic or heteroaromatic ring systems Ar are the same as those set out above as embodiments for Ar, in particular the structures Ar-1 to Ar-76.

[0074] Examples of suitable triazine compounds which can be used as matrix materials together with the compounds according to the invention are the compounds shown in the following table.

[0075] Examples of suitable quinazoline compounds are those shown in the following table:

[0076] Particularly suitable phosphorescent compounds (= 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. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are preferably used as phosphorescent emitters, in particular compounds containing iridium or platinum.

[0077] Examples of the emitters described above can be found in the applications WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626, WO 2011 / 066898, WO 2011 / 157339, WO 2012 / 007086, WO 2014 / 008982, WO 2014 / 023377, WO 2014 / 094961, WO 2014 / 094960, WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO 2016 / 015815, WO 2016 / 124304, WO 2017 / 032439, WO 2018 / 011186, WO 2018 / 041769, WO 2019 / 020538, WO 2018 / 178001, WO 2019 / 115423, and WO 2019 / 158453. 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 electroluminescence are suitable, and the person skilled in the art can use further phosphorescent complexes without inventive step.

[0078] Examples of phosphorescent dopants are listed below.

[0079] In the further layers of the organic electroluminescent device according to the invention, all materials can be used as they are usually used according to the prior art.

[0080] Also preferred is an organic electroluminescent device characterized in that one or more layers are coated using a sublimation process. The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10 -5 mbar, preferably less than 10 -6 mbar. However, it is also possible for the initial pressure to be even lower, for example, less than 10 -7 mbar.

[0081] Also preferred is an organic electroluminescent device, 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 patterned.

[0082] Also preferred is an organic electroluminescent device characterized in that one or more layers are produced from solution, such as by spin coating, or by any printing process, such as screen printing, flexographic printing, offset printing, LITI (Light Induced Thermal Imaging, thermal transfer printing), inkjet printing, or nozzle printing. Soluble compounds are required for this, which are obtained, for example, by suitable substitution.

[0083] 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.

[0084] These processes are known and can be applied to organic electroluminescent devices containing the compounds of the invention.

[0085] The compounds according to the invention and the organic electroluminescent devices according to the invention are characterized by one or more of the following properties: 1. The compounds of the invention, used as matrix material for phosphorescent emitters, lead to long lifetimes. 2. The compounds of the invention lead to high efficiencies, in particular a high EQE. This applies particularly when the compounds are used as matrix material for a phosphorescent emitter. 3. The compounds of the invention lead to low operating voltages. This applies particularly when the compounds are used as matrix material for a phosphorescent emitter.

[0086] The invention is explained in more detail by the following examples. Examples

[0087] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. Solvents and reagents can be purchased from Sigma-ALDRICH or ABCR, for example. The corresponding CAS numbers are also given for the compounds known from the literature. S1a:

[0088]

[0089] Under an inert atmosphere, DMSO (50 mL), K 3 PO 4 (53.08 g, 250 mmol), pyridine-2-carboxylic acid (1.53 g, 12.44 mmol), and Cul (1.19 g, 6.22 mmol) are initially charged. 3-chlorophenol (19.20 g, 150 mmol) [108-43-0] and 3-bromo-1-chlorobenzene (23.93 g, 125 mmol) [108-37-2] are then slowly added successively, and the reaction mixture is stirred at 85 °C for 16 h. After cooling, the reaction mixture is extracted with aqueous ammonia solution and methyl tert-butyl ether. The organic phase is washed five times with water and twice with saturated NaCl solution, the combined phases are dried over Na 2 SO 4 , and the solvent is removed using a rotary evaporator. The crude product is further purified by fractional distillation. Yield: 26.88 g (106 mmol), 85%; purity: 96% according to 1< H NMR.

[0090] The following compounds can be prepared analogously. In addition to distillation, column chromatography can be used for purification, and other common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be used for recrystallization. Educt 1 Educt 2 product yield 779198-52-6 108-37-2 S2a 80% 108-37-2 S3a 86% 108-37-2 S4a 74% 3743-23-5 108-37-2 S5a 75% 210346-76-2 108-37-2 S6a 68% S1b:

[0091]

[0092] S1a (23.90 g, 100 mmol) is initially charged in THF (150 mL) under an inert atmosphere and cooled to -75 °C. N-butyllithium (2.5 mol / L in hexane, 80 mL, 200 mol) is then slowly added dropwise at a rate such that the internal temperature does not exceed -65 °C. Stirring is continued at -75 °C for 4 h, and then bromine (5.6 mL, 109.3 mmol) is added dropwise at a rate such that the internal temperature does not exceed -65 °C. After the addition is complete, the mixture is stirred at -75 °C for 1 h, then slowly warmed to 10 °C over the course of 1 h and stirred at 10 °C for 1 h. The mixture is then cooled to 0 °C and carefully quenched with saturated Na 2 SO 3 solution (50 mL). The mixture is extracted with toluene and water, the combined organic phases are washed three times with water and once with saturated NaCl solution, dried over Na 2 SO 4 , and the solvent is removed on a rotary evaporator. The crude product is extracted twice with 2-propanol under reflux. Yield: 24.21 g (86 mmol, 86%); purity 97% according to 1< H-NMR.

[0093] The following compounds can be prepared analogously. Purification can be carried out by trituration, distillation, or column chromatography, while other common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc., can be used for recrystallization. Educt 1 product yield S2a S2b 70% S3a S3b 79% S4a S4b 79% S5a S5b 74% S6a S6b 53% S1c:

[0094]

[0095] S1b (39.19 g, 140.0 mmol), phenylboronic acid (18.29 g, 150.0 mmol) [5720-07-0], and K2CO3 (38.70 g, 280.0 mmol) are initially charged in THF (100 mL) and water (170 mL) and rendered inert for 30 min. Tetrakis(triphenylphosphine)palladium [14221-01-3] (1.78 g, 1.54 mmol) is then added, and the reaction mixture is stirred under reflux for 20 h. The reaction mixture is extracted with toluene and water, the combined organic phases are washed with water and saturated NaCl solution, dried over Na2SO4, and the solvent is removed on a rotary evaporator. The crude product is recrystallized from ethanol. Yield: 30.1 g (108 mmol, 72%); purity 97% according to 1< H-NMR.

[0096] The following compounds can be prepared analogously. Purification can be achieved by column chromatography, while other common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be used for recrystallization. Educt 1 Educt 2 product yield S2b 98-80-6 S2c 64% S3b 98-80-6 S3c 69% S5b 98-80-6 S4c 59% S6b 98-80-6 S5c 51% S1d:

[0097]

[0098] S1c (27.87 g, 100 mmol) and K 2 CO 3 (41.46 g, 300 mmol) are placed under an inert atmosphere, treated with DMAc (400 mL), and rendered inert for 30 min. Subsequently, Pd(OAc) 2 (447 mg, 1.99 mmol) and 1,3-bis-(2,6-diisopropylphenyl)3- H-imidazol-1-ium chloride (1.69 g, 3.98 mmol) was added, and the reaction mixture was stirred at 140 °C for 18 h. After cooling, the reaction mixture was poured into ethanol / water (1:1, 500 mL) and stirred for 30 min. The precipitated solid was filtered off with suction and washed five times with water and three times with ethanol. The crude product was stirred with 2-propanol under reflux, and the solid was filtered off with suction after cooling. Yield: 22.9 g (84 mmol, 84%), 98% purity according to 1< H NMR.

[0099] The following compounds can be prepared analogously. In addition to 1,3-bis-(2,6-diisopropyl-phenyl)3- H-imidazol-1-ium chloride, tritert-butylphosphine or tricyclohexylphosphine can also be used, or as a Pd source, in addition to Pd(OAc) 2 , Pd 2 (dba) 3 . Column chromatography can be used for purification, and other common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be used for recrystallization. Educt 1 product yield S2c S2d 75% S3c S3d 73% S4c S4d 80% S5c S5d 63% S1r S6d 75% S1e:

[0100]

[0101] S3d (27.23 g, 100 mmol) is initially dissolved in dichloromethane (600 mL) and cooled to 0 °C in an ice bath. BBr 3 (6.0 mL, 63.2 mmol) is then carefully added dropwise. After the addition is complete, the reaction mixture is allowed to warm to room temperature. Once the reaction is complete, the reaction mixture is cooled again to 0 °C and carefully quenched with MeOH (150 mL). The solvent is removed on a rotary evaporator. The reaction mixture is then treated three times with 300 mL of MeOH, which is then removed on a rotary evaporator. A further 200 mL of MeOH is added, and the solid is filtered off with suction. The crude product is dried and used in the next step without further purification. Yield: 15.8 g (61 mmol, 61%).

[0102] The following compounds can be prepared analogously. Column chromatography can be used for purification, and other common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be used for recrystallization. Educt 1 product yield S2d S2e 64% S5d S3e 71% S4d S4e 63% S1f:

[0103]

[0104] S1e (12.91 g, 50.0 mmol) and triethylamine (20.8 mL, 150 mmol) are initially dissolved in dichloromethane (700 mL) and cooled to 0 °C in an ice bath. Trifluoromethanesulfonic anhydride (10.9 mL, 65.0 mmol) is then slowly added dropwise. After the addition is complete, the reaction mixture is allowed to warm to room temperature. After the reaction is complete, the reaction mixture is extracted with dichloromethane and water, the combined organic phases are dried over Na 2 SO 4 , and the solvent is removed using a rotary evaporator. The residue is taken up in 300 mL of cyclohexane and stirred at room temperature for 30 min. The solid is filtered off with suction and dried in a VTS. Yield: 11.8 g (30.1 mmol, 60%).

[0105] The following compounds can be prepared analogously. Purification can be achieved by column chromatography, while other common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be used for recrystallization. Educt 1 product yield S2e S2f 73% S4e S4f 64% S1g:

[0106]

[0107] S4d (24.23 g, 100 mmol) is initially dissolved in 300 mL of THF and cooled to -75 °C. Hexyllithium (44.0 mL, c=2.5 mol / L, 110 mmol) is then added dropwise at a rate such that the temperature does not rise above -65 °C. After the addition is complete, the reaction mixture is stirred at -75 °C for 1 h. The reaction mixture is then slowly warmed to room temperature, stirred at room temperature for 1 h, cooled again to -75 °C, and trimethyl borate (15.59 g, 150.0 mmol) is added dropwise at a rate such that the temperature does not rise above -65 °C. The reaction mixture is warmed to room temperature overnight and carefully quenched the next day with HCl (c=5 mol / L, 50 mL). The reaction mixture is extracted with water, and the organic phase is washed three times with water. The THF is evaporated down to 50 mL, then 150 mL of n-heptane is added, and the precipitated solid is filtered off with suction and washed with n-heptane. Yield: 24.03 g (84.2 mmol, 84%), 96% pure according to 1< H NMR. S1h:

[0108]

[0109] S1f (12.88 g, 33.0 mmol), bis(pinacolato)diboron (10.34 g, 39.9 mmol), and KOAc (9.79 g, 99.75 mmol) are initially charged in 1,4-dioxane (250 mL) and inertized with argon for 30 min. Pd(dppf)Cl 2 (740 mg, 0.91 mmol) is then added, and the mixture is stirred under reflux for 20 h. After cooling, the solvent is removed using a rotary evaporator, and the residue is extracted with dichloromethane and water. The combined organic phases are dried over Na 2 SO 4 , ethanol (180 mL) is added, and the dichloromethane is removed using a rotary evaporator. The precipitated solid is filtered off with suction and dried in a vacuum drying oven. The crude product is used in the next step without further purification. Yield: 9.11 g (24.75 mmol, 75%), purity 95% according to 1< H-NMR.

[0110] The following compounds can be prepared analogously. Alternatively, Pd(PCy 3 ) 2 Cl 2 or Pd 2 (dba) 3 with S-Phos (1:3) can be used as a catalyst system. In addition to column chromatography, hot extraction can be used for purification. Other common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane can be used for recrystallization or hot extraction. High boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be used for recrystallization. Educt 1 product yield S2f S2h 85% S4f S3h 70% S2r S4h 68% S3r S5h 73% S4r S6h 42% S5r S7h 80% S6r S8h 36% S1i:

[0111]

[0112] S1h (36.82 g, 100 mmol), ethyl 2-bromobenzoate (22.91 g, 100 mmol) [CAS-4688-76-0], and sodium carbonate (21.2 g, 200 mmol) are initially dissolved in toluene (650 mL) and water (150 mL) under an inert atmosphere. Tetrakis(triphenylphosphine)palladium(0) (2.32 g, 2.00 mmol) is then added, and the reaction mixture is stirred under reflux for 24 h. After cooling, the reaction mixture is packed over a frit, filtered with toluene and Celite, and then extracted with toluene and water. The organic phase is washed with water (200 mL) and saturated NaCl solution (100 mL), dried over Na 2 SO 4 , and the solvent is removed on a rotary evaporator. The crude product was further purified by column chromatography. Yield: 25.0 g (64 mmol, 64%), purity 97% according to 1< H NMR. S1l:

[0113]

[0114] S1g (12.02 g, 42.0 mmol), 1-bromo-2-iodo-benzene (9.27 g, 42.8 mmol), and K2CO3 (11.61 g, 84.0 mmol) are placed in toluene:ethanol:water (200 mL:50 mL:100 mL) and rendered inert with argon for 30 min. Pd(dppf)Cl2 (118 mg, 168 µmol) is then added, and the mixture is stirred under reflux for 16 h. The mixture is extracted with toluene / water. The combined organic phases are dried over Na2SO4, and the solvent is removed on a rotary evaporator. The crude product is recrystallized from a mixture of 2-propanol and toluene. Yield: 15.18 g (38.2 mmol, 91%), purity 98% according to 1< H-NMR. S1m:

[0115]

[0116] S1l (13.98 g, 35.2 mmol) is placed in 250 mL of THF and cooled to -75 °C. n-BuLi (16.0 mL, c=2.5 mol / L, 40.0 mmol) is then added dropwise at a rate such that the temperature does not rise above -65 °C. After the addition is complete, the mixture is stirred at -75 °C for 1 h. A solution of fluoren-9-one (6.48 g, 36.0 mmol) in THF (50 mL) is added dropwise at a rate such that the temperature does not rise above -65 °C. The mixture is warmed to room temperature overnight, then water (100 mL) is added dropwise. The phases are separated, the organic phase is dried over Na2SO4, and the solvent is removed using a rotary evaporator. The crude product is used in the next step without further purification. Yield: quantitative. S1n:

[0117]

[0118] S1m (49.86 g, 100 mmol) is dissolved in concentrated HCl (37%, 41.4 mL, 500 mmol) and glacial acetic acid (450 mL) and stirred under reflux for 20 h. The precipitated solid is filtered off with suction and washed five times with water and five times with ethanol. The crude product is extracted twice with 2-propanol under reflux. Yield: 39.0 g (81.2 mmol, 81%), purity 98% according to 1< H NMR. S1o:

[0119]

[0120] S1n (32.02 g, 66.7 mmol) is initially dissolved in THF (500 mL) under an inert atmosphere and cooled to -20 °C. Sec-BuLi (95.3 mL, 133.4 mmol, 1.4 mol / L in cyclohexane) is then slowly added dropwise, and the mixture is stirred for 1 h. Trimethyl borate (9.30 g, 89.5 mmol) is then added dropwise over 10 min, the mixture is allowed to warm to room temperature, and the mixture is stirred at room temperature for 12 h. 50 mL of HCl is slowly added dropwise, and the mixture is extracted with water. The solvent is removed on a rotary evaporator, and the crude product is used in the next step without further purification. Yield: 30.78 g (58.7 mmol, 88%), 95% purity according to 1< H NMR.

[0121] The following compounds can be prepared analogously. In addition to column chromatography, hot extraction can be used for purification. Other common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or high-boiling solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc., can be used for recrystallization or hot extraction. Educt 1 product yield S1q S2o 41% S6d S3o + S4o S3o 26% + S4o 28% S1p:

[0122]

[0123] Dry CeCl 3 (50.53 g, 205 mmol) is initially charged in THF (250 mL dried) and stirred at room temperature for 30 min. S6i (39.04 g, 100 mmol) is then dissolved in 500 mL THF and added to the CeCl 3 suspension at 0 °C. The mixture is then stirred at room temperature for 30 min. The reaction mixture is cooled to 0 °C, and MeMgCl (100 mL, 3 mol / L in THF, 300 mmol) is slowly added dropwise. After the addition is complete, the reaction mixture is stirred at room temperature for 2 h and then carefully quenched with NH 4 Cl solution (100 mL). The reaction mixture is extracted with dichloromethane and water, the combined organic phases are washed with water and saturated NaCl solution, and the solvent is removed on a rotary evaporator. The crude product is used in the next step without further purification. Yield: quantitative, approximately 90% according to 1H NMR. S1q + S2q:

[0124]

[0125] Methanesulfonic acid (48.05 g, 500 mmol) and polyphosphoric acid (75 g) are placed in 250 mL of a reaction vessel and cooled to 0 °C. S1p (37.65 g, 100 mmol) is then dissolved in dichloromethane (250 mL) and added dropwise to the methanesulfonic acid / polyphosphoric acid mixture at 0 °C. The reaction mixture is stirred at RT for 1 h. 400 mL of water and 200 mL of EtOH are added, and the mixture is stirred at room temperature for 1 h. The organic phase is separated, washed with water and saturated NaCl solution, and filtered through a bed of silica gel (pre-slurried with dichloromethane). n-Heptane (300 mL) is added to the filtrate, and the dichloromethane is removed on a rotary evaporator. The precipitated solid is filtered off with suction and washed with n-heptane. The isomer mixture is separated chromatographically. Purity of S1q and S2q is approximately 95% according to 1H NMR. S1r:

[0126]

[0127] S4e (12.91 g, 50.0 mmol), 1-bromo-2-fluorobenzene (9.63 g, 55.0 mmol), and potassium carbonate (17.27 g, 125.0 mmol) were initially charged in DMAC (300 mL) under an inert atmosphere and stirred at 120 °C for 30 h. After cooling, the DMAC was largely removed on a rotary evaporator, and the crude product was extracted with dichloromethane and water. The combined organic phases were washed with water (3 x 150 mL) and saturated NaCl solution (100 mL), dried over Na 2 SO 4 , and the solvent was removed on a rotary evaporator. The crude product was boiled with refluxing ethanol. Yield: 14.1 g (34.2 mmol, 68%), 95% pure according to 1H NMR.

[0128] The following compounds can be prepared analogously: In addition to column chromatography, hot extraction can also be used for purification; for recrystallization or hot extraction, other common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane or for recrystallization, high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be used. Educt 1 Educt 2 product yield S1e 60811-18-9 S2r 58% S4e 60811-18-9 S3r 60% S2e 144584-65-6 S4r 41% S3e 60811-21-4 S5r 68% S3e 60811-18-9 S6r 37% S1s:

[0129]

[0130] S5h (49.48 g, 100.0 mmol), 2-[1,1'-biphenyl]-4-yl-4-chloro-6-phenyl-1,3,5-triazine [CAS-1472062-94-4] (37.82 g, 110.0 mmol) [5720-07-0], and K2CO3 (38.70 g, 280.0 mmol) were initially charged in THF (700 mL) and water (250 mL) and rendered inert for 30 min. Tetrakis(triphenylphosphine)palladium [14221-01-3] (3.56 g, 3.08 mmol) was then added, and the reaction mixture was stirred under reflux for 20 h. The mixture is extracted with toluene and water, the combined organic phases are washed with water and saturated NaCl solution, dried over Na 2 SO 4 , and the solvent is removed on a rotary evaporator. The crude product is recrystallized from n-butyl acetate. Yield: 52.7 g (78 mmol, 78%), purity 98% according to 1< H NMR.

[0131] The following compounds can be prepared analogously. Purification can be achieved by column chromatography, while other common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be used for recrystallization. Educt 1 Educt 2 product yield S4h CAS-160892-07-9 S2s 79% S4h CAS-1800220-86-7 S3s 61% S5h CAS-2375066-17-2 S4s 60% CAS-2915-16-4 S5s 84% S6h CAS-1614244-83-5 S6s 65% S6h S7s 28% S6h CAS-1943719-88-7 S8s 48% S7h CAS-1428551-28-3 S9s 65% S10s 75% S8h 2260561 -80-4 S11s 45% S8h 1955546-91-4 S12s 56% S8h S13s 40% P1a + P2a not according to the invention

[0132]

[0133] S1s (67.51 g, 100 mmol) and K 2 CO 3 (41.46 g, 300 mmol) are placed under an inert atmosphere, treated with DMAc (700 mL), and rendered inert for 30 min. Subsequently, Pd(OAc) 2 (447 mg, 1.99 mmol) and 1,3-bis-(2,6-diisopropylphenyl)3- H-imidazol-1-ium chloride (1.69 g, 3.98 mmol) was added, and the reaction mixture was stirred at 150 °C for 22 h. After cooling, the reaction mixture was poured into ethanol / water (1:1, 600 mL) and stirred for a further 30 min. The precipitated solid was filtered off with suction and washed five times with water and three times with ethanol. The crude product mixture was separated by chromatography and then further purified by hot extraction. P1a was hot-extracted three times with o-xylene over Alox, and P2a was hot-extracted four times with toluene over Alox. Both materials were then sublimated under high vacuum. Yield: P1a: 11.5 g (18.0 mmol, 18%); purity >99.9% according to HPLC; P2a: 14.5 g (22.7 mmol, 23%); Purity >99.9% by HPLC.

[0134] The following compounds can be prepared analogously. In addition to 1,3-bis-(2,6-diisopropyl-phenyl)3- HIn addition to imidazol-1-ium chloride, tritert-butylphosphine or tricyclohexylphosphine can also be used as a ligand, or Pd2(dba)3 can be used as a Pd source in addition to Pd(OAc)2. Purification can be achieved by column chromatography, hot extraction, or recrystallization. Common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc., can be used for recrystallization. Educt 1 product yield S2s P3a* + P4a* P3a* 14% + P4a* 11% S3s P5a* + P6a* P5a* 20% + P6a* 13% S4s P7a* 43% S5s P8a* 38% S6s P9a* + P10a* P9a* 12% + P10a* 17% S7s P11a* + P12a* P11a* 15% P12a* 16% S8s P13a* + P14a* P13a* 9% + P14a* 14% S9s P15a* 55% S10s P16a* 61% S11s P17a* 49% S12s P18a* 40% S13s P19a* 34% *not according to the invention P1b:

[0135]

[0136] S1o (52.44 g, 100 mmol), bis-biphenyl-4-yl-(4-bromophenyl)amine (47.64 g, 100 mmol), and K3PO4 (63.79 g, 300 mmol) are initially charged in THF (1200 mL) and water (300 mL) and inertized with argon for 30 min. Pd(OAc)2 (448 mg, 2.00 mmol) and X-Phos (1.99 g, 4.00 mmol) are then added successively, and the mixture is stirred under reflux for 16 h. After cooling, the precipitated solid is filtered off with suction and washed with water and ethanol. The crude product is subjected to four hot extractions with o-xylene over Alox and finally sublimed under high vacuum. Yield: 54.58 g (62.3 mmol, 62%); purity >99.9% by HPLC.

[0137] The following compounds can be prepared analogously. S-Phos or P(o-tol) 3 or P(tBu 3 ) with Pd 2 (dba) 3 or Pd(OAc) 2 can also be used as a catalyst system, or the catalyst systems Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2 can be used for purification. Column chromatography, hot extraction, or recrystallization can be used. Common solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane can be used for recrystallization or hot extraction, or high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be used for recrystallization. Educt 1 Educt 2 product yield S2o CAS-160892-07-9 P2b 57% S2o CAS-1800220-86-7 P3b 42% S1o CAS-1428551-28-3 P4b 51% S2o CAS-2375066-17-2 P5b 36% S2o P6b 58% S1o CAS-2142681-84-1 P7b 49% P8b* + P9b* Chromatographic separation 13% P8b* + 17% P9b* *not according to the invention Production of OLEDs

[0138] In the following examples (see Tables 1 to 5), the use of the compounds according to the invention in OLEDs is presented in comparison to materials from the prior art. Pretreatment for examples V1 to V6 and E1a to E6h:

[0139] Glass plates coated with 50 nm thick, structured ITO (indium tin oxide) are first treated with an oxygen plasma, followed by an argon plasma, before coating. These plasma-treated glass plates form the substrates onto which the OLEDs are applied.

[0140] OLEDs generally have the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emission layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL), and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of the OLEDs can be found in Tables 1 and 3. The materials required for OLED production, unless already described, are shown in Table 7. The device data of the OLEDs are listed in Tables 2 and 4.

[0141] All materials are thermally evaporated in a vacuum chamber. The emission layer always consists of at least two matrix materials and an emissive dopant (dopant, emitter), which is mixed with the matrix material(s) by co-evaporation in a specific volume fraction. A specification such as P1a:H1:TE2 (32%:60%:8%) means that the material P1a is present in the layer at a volume fraction of 32%, H1 at a volume fraction of 60%, and TE2 at a volume fraction of 8%. Similarly, the electron-transport layer can also consist of a mixture of two materials.

[0142] The electroluminescence spectra are determined at a luminance of 1000 cd / m², and the CIE 1931 x and y color coordinates are calculated from this. The value U10 in Tables 2 and 6 refers to the voltage required for a current density of 10 mA / cm². EQE10 refers to the external quantum efficiency achieved at 10 mA / cm². The lifetime LD is defined as the time after which the luminance, measured in cd / m² in the forward direction, drops from the starting luminance to a certain fraction L1 when operated at a constant current density j0. A value of L1=80% in Table 2 means that the lifetime given in column LD corresponds to the time after which the luminance in cd / m² drops to 80% of its initial value.

[0143] The value U1000 in Table 4 refers to the voltage required for a luminance of 1000 cd / m2. EQE1000 refers to the external quantum efficiency achieved at 1000 cd / m2. The lifetime LD is defined as the time after which the luminance drops from the initial luminance to a certain fraction L1 when operated at a constant current density j0. A value of L1=95% in Table 4 means that the lifetime specified in column LD corresponds to the time after which the luminance drops to 95% of its initial value. Use of compounds according to the invention in OLEDs

[0144] The materials according to the invention are used in Examples E1c, E2f, E6g, and E6i as matrix materials in the emission layer of green and red phosphorescent OLEDs, respectively. As a comparison from the prior art, the materials SdT1, SdT2, and SdT3 are used in combination with the host materials H1, H2, and H3, or with the host materials E1 and E2, in Comparative Examples C1 to C6. Comparing the examples according to the invention with the corresponding comparative examples, it is clearly evident that the examples according to the invention each demonstrate a significant advantage in the lifetime of the OLED. Table 1: Structure of the OLEDs for green Example HIL thickness HTL thickness EBL thickness EML thickness HBL thickness ETL thickness EIL thickness V1 SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm E2:SdT1:TE1 (22%:70%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E1a* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm E2:P15a:TE1 (22%:70%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E1b* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm E2:P19a:TE1 (22%:70%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E1c SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm E2:P4b:TE1 (22%:70%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm V2 SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm SdT2:H1:TE2 (32%:60%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E2a* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm P1a:H1:TE2 (32%:60%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E2b* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm P2a:H1:TE2 (32%:60%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E2c* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm P3a:H1:TE2 (32%:60%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E2d* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm P7a:H1:TE2 (32%:60%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E2e* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm P8a:H1:TE2 (32%:60%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E2f SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm P7b:H1:TE2 (32%:60%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E2g* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm P8b:H1:TE2 (32%:60%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm V3 SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm SdT3:H2:TE1 (38%:50%:12%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E3a* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm P17a:H2:TE1 (38%:50%:12%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E3b* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm P9b:H2:TE1 (38%:50%:12%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E3c* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm P18a:H2:TE1 (38%:50%:12%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm V4 SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm E1:SdT1:TE2 (32%:60%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E4a* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm E2:P16a:TE1 (22%:70%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm V5 SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm SpMA2 20nm E1:H1:TE2 (32%:60%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E5a* SpMA1:PD1 (95%:5%) 20nm SpMA1 200nm P19a 20nm E1:H1:TE2 (32%:60%:8%) 40nm ST2 5nm ST2:LiQ (50%:50%) 30nm LiQ 1nm *nicht erfindungsgemäß Table 2: OLED data for green Bsp. U10 (V) EQE10 (%) CIE x / y bei 1000 cd / m 2< j 0 (mA / cm 2< ) L1 (%) LD (h) V1 5.2 17.8 0.34 / 0.62 40 80 190 E1a* 5.4 18.7 0.34 / 0.62 40 80 590 E1b* 5.2 18.2 0.34 / 0.63 40 80 440 E1c 5.4 18.5 0.34 / 0.63 40 80 665 V2 4.4 20.5 0.34 / 0.63 40 80 200 E2a* 4.1 20.4 0.35 / 0.63 40 80 370 E2b* 4.2 20.0 0.35 / 0.63 40 80 440 E2c* 4.3 21.9 0.34 / 0.63 40 80 315 E2d* 4.4 22.2 0.35 / 0.63 40 80 690 E2e* 4.2 22.9 0.34 / 0.63 40 80 570 E2f 4.1 21.8 0.35 / 0.63 40 80 555 E2g* 4.2 22.3 0.34 / 0.63 40 80 710 V3 5.3 16.6 0.34 / 0.62 40 80 450 E3a* 5.2 17.0 0.33 / 0.63 40 80 990 E3b* 4.9 17.5 0.34 / 0.62 40 80 590 E3c* 5.0 17.4 0.33 / 0.62 40 80 915 V4 4.5 21.2 0.34 / 0.63 40 80 220 E4a* 4.9 21.2 0.34 / 0.63 40 80 550 V5 4.4 22.2 0.34 / 0.63 40 80 760 E5a* 4.2 22.7 0.33 / 0.63 40 80 1120 *nicht erfindungsgemäß Table 3: Structure of the OLEDs for red Bsp HIL Dicke HTL Dicke EBL Dicke EML Dicke HBL Dicke ETL Dicke EIL Dicke V6 SpMA1:PD1 (95%:5%) 20nm SpMA1 110nm SpMA2 10nm SdT2:H3:TER1 (57%:40%:3%) 35nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E6a* SpMA1:PD1 (95%:5%) 20nm SpMA1 110nm SpMA2 10nm P5a:H3:TER1 (57%:40%:3%) 35nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E6b* SpMA1:PD1 (95%:5%) 20nm SpMA1 110nm SpMA2 10nm P6a:H3:TER1 (57%:40%:3%) 35nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E6c* SpMA1:PD1 (95%:5%) 20nm SpMA1 110nm SpMA2 10nm P9a:H3:TER1 (57%:40%:3%) 35nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E6d* SpMA1:PD1 (95%:5%) 20nm SpMA1 110nm SpMA2 10nm P10a:H3:TER1 (57%:40%:3%) 35nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E6e* SpMA1:PD1 (95%:5%) 20nm SpMA1 110nm SpMA2 10nm P11a:H3:TER1 (57%:40%:3%) 35nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E6f* SpMA1:PD1 (95%:5%) 20nm SpMA1 110nm SpMA2 10nm P12a:H3:TER1 (57%:40%:3%) 35nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E6g SpMA1:PD1 (95%:5%) 20nm SpMA1 110nm SpMA2 10nm P6b:H3:TER1 (57%:40%:3%) 35nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E6h* SpMA1:PD1 (95%:5%) 20nm SpMA1 110nm SpMA2 10nm P13a:H3:TER1 (57%:40%:3%) 35nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm E6i SpMA1:PD1 (95%:5%) 20nm SpMA1 110nm SpMA2 10nm SdT1:P1b:TER1 (57%:40%:3%) 35nm ST2 10nm ST2:LiQ (50%:50%) 30nm LiQ 1nm *nicht erfindungsgemäß Table 4: OLED data for red Bsp. U100 0 (V) EQE 1000 (%) CIE x / y bei 1000 cd / m 2< j 0 (mA / cm 2< ) L1 (%) LD (h) V6 3.7 24.1 0.66 / 0.33 60 95 12 E6a* 3.5 25.4 0.67 / 0.33 60 95 66 E6b* 3.4 26.5 0.67 / 0.33 60 95 74 E6c* 3.8 25.8 0.67 / 0.33 60 95 105 E6d* 3.8 25.7 0.67 / 0.33 60 95 112 E6e* 3.3 26.3 0.66 / 0.33 60 95 84 E6f* 3.4 26.6 0.66 / 0.33 60 95 80 E6g 3.5 26.8 0.66 / 0.33 60 95 35 E6h* 3.3 25.5 0.66 / 0.33 60 95 21 E6i 3.4 24.7 0.66 / 0.33 60 95 17 *nicht erfindungsgemäß Table 5: Structural formulas of the materials used in OLEDs, unless previously described: PD1 (CAS Reg. No. 1224447-88-4) SpMA1 SpMA2 ST2 LiQ TE1 TE2 TER1 H1 H2 H3 E1 E2 SdT1 SdT2 (WO 2012 / 048781) SdT3 (WO 2012 / 048781)

Claims

1. Compound of the formula (1), where the following applies to the symbols used: X is, identically or differently on each occurrence, CR or N, with the proviso that a maximum of two groups X per ring stand for N and that two adjacent groups X that are part of the ring having three groups X stand for C and form, via the bonds denoted by *, an aromatic or heteroaromatic ring system which is condensed onto the ring; Y is C(R)2, O or S; Y1 is C(R)2; Q is, identically or differently on each occurrence, CR or N, with the proviso that a maximum of two groups Q per ring stand for N; R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(Ar')2, N(R1)2, OAr', SAr', B(OR1)2, CHO, C(=O)R1, CR1=C(R1)2, CN, C(=O)OR1, C(=O)NR1, Si(R1)3, NO2, P(=O)(R1)2, OSO2R1, OR1, S(=O)R1, S(=O)2R1, SR1, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more radicals R1, where one or more non-adjacent CH2 groups may be replaced by -R1C=CR1-, -C≡C-, Si(R1)2, NR1, CONR1, C=O, C=S, -C(=O)O-, P(=O)(R1), -O-, -S-, SO or SO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R1, where two or more radicals R bonded to the same ring may form with one another an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R1, and where two radicals R bonded to the same carbon, silicon, germanium or tin atom may form with one another a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R1; Ar' is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R1; R1 is on each occurrence, identically or differently, H, D, F, I, B(OR2)2, N(R2)2, CHO, C(=O)R2, CR2=C(R2)2, CN, C(=O)OR2, Si(R2)3, NO2, P(=O)(R2)2, OSO2R2, SR2, OR2, S(=O)R2, S(=O)2R2, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more radicals R2 and where one or more CH2 groups in the above-mentioned groups may be replaced by -R2C=CR2-, -C=C-, Si(R2)2, C=O, C=S, -C(=O)O-, NR2, CONR2, P(=O)(R2), -O-, -S-, SO or SO2 and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R2, where two or more radicals R1 may form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system with one another; R2 is on each occurrence, identically or differently, H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by D or F; two or more substituents R2 may be linked to one another and form a ring.

2. Compound according to Claim 1, selected from the compounds of the formulae (2-1) to (2-4), where the symbols used have the meanings given in Claim 1.

3. Compound according to Claim 1 or 2, selected from the compounds of the formulae (3-1) to (3-4), where the symbols used have the meanings given in Claim 1.

4. Compound according to one or more of Claims 1 to 3, selected from the compounds of the formulae (3-1a) to (3-4a), where the symbols used have the meanings given in Claim 1.

5. Compound according to one or more of Claims 1 to 4, selected from the following compounds P1b P2b P3b P4b P6b P7b.

6. Process for the preparation of a compound according to Claim 1, characterised by the following steps: (A) synthesis of the basic structure of the formula (1); (B) condensation-on of the aromatic or heteroaromatic ring system with formation of the bonds denoted by * in formula (1) by a coupling and ring-closure reaction.

7. Formulation comprising at least one compound according to one or more of Claims 1 to 5 and at least one further compound and / or at least one solvent.

8. Use of a compound according to one or more of Claims 1 to 5 and / or a formulation according to Claim 7 in an electronic device.

9. Electronic device containing at least one compound according to one or more of Claims 1 to 5 and / or a formulation according to Claim 7.

10. Electronic device according to Claim 9, which is an organic electroluminescent device, characterised in that the compound according to one or more of Claims 1 to 5 is employed in an emitting layer as matrix material for phosphorescent or fluorescent emitters or for emitters which exhibit TADF (thermally activated delayed fluorescence), and / or in an electron-transport layer and / or in a hole-blocking layer and / or in a hole-transport layer and / or in an electron-blocking layer.

11. Electronic device according to Claim 10, where the emitting layer comprises the compound according to one or more of Claims 1 to 5 in combination with one or more phosphorescent materials.

12. Electronic device according to Claim 10, where the emitting layer comprises the compound according to one or more of Claims 1 to 5 in combination with a further matrix material.

13. Electronic device according to Claim 12, where the further matrix material is selected from the group of the biscarbazoles, the bridged carbazoles, the triarylamines, the dibenzofurancarbazoles, the di-benzofuranamines and the carbazolamines.

14. Electronic device according to Claim 12, where the further matrix material is selected from the group of the triazines, pyrimidines, quinazolines or quinoxalines.