Oxygen-containing heterocycles for organic electroluminescent devices

Abstract

The present invention relates to oxygen-containing heterocycles which are suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing these heterocycles.

Description

[0001] Oxygen-containing heterocycles for organic electroluminescent devices

[0002] The present invention relates to oxygen-containing heterocycles for use in electronic devices, in particular in organic electroluminescent devices, and to electronic devices, in particular organic electroluminescent devices, containing these materials.

[0003] In organic electroluminescent devices, phosphorescent organometallic complexes are often used as emitting materials. For quantum mechanical reasons, up to four times the energy and power efficiency is possible when using organometallic compounds as phosphorescence emitters. In general, there is still room for improvement in electroluminescent devices, especially in electroluminescent devices that exhibit triplet emission (phosphorescence). The properties of phosphorescent electroluminescent devices are not only determined 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 significant improvements in the properties of the electroluminescent devices.

[0004] In addition to an emission layer, many electroluminescent devices comprise additional layers, such as 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. These layers have a significant impact on the performance of electroluminescent devices.

[0005] In addition, electroluminescent devices that use fluorescent emitters or emitters that exhibit TADF also face similar challenges.

[0006] In general, there is still room for improvement in these materials, 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.

[0007] The object of the present invention is therefore to provide compounds which are suitable for use in an organic electronic device, in particular in an organic electroluminescent device, and which, when used in this device, lead to good device properties, as well as to provide the corresponding electronic device.

[0008] In particular, the object of the present invention is to provide compounds that result in a long lifetime, good efficiency, and low operating voltage. In addition to the emitters, hole-conducting materials, hole-injection materials, electron-blocking materials, electron-injection materials, electron-transport materials, and hole-blocking materials contribute to these properties. Furthermore, the properties of the matrix materials, also referred to herein as host materials, also have a significant influence on the lifetime and efficiency of the organic electroluminescent device.

[0009] Furthermore, it is the object of the present invention to provide compounds which are characterized by a low refractive index (RI).

[0010] A further object of the present invention can be seen in providing compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, in particular as matrix materials. In particular, it is an object of the present invention to provide matrix materials suitable for green or blue phosphorescent electroluminescent devices and, optionally, also for red or yellow phosphorescent electroluminescent devices.

[0011] Furthermore, the compounds, particularly when used as emitter, host material, hole conductor material, hole injection material, electron blocking material, electron injection material, electron transport material or hole blocking material in organic electroluminescent devices, should lead to devices having excellent color purity.

[0012] Another task can be seen in providing electronic devices with excellent performance as cost-effectively as possible and in consistent quality

[0013] Furthermore, the electronic devices should be able to be used or adapted for a variety of purposes. In particular, the performance of the electronic devices should be maintained over a wide temperature range.

[0014] Surprisingly, it has been found that certain compounds, described in more detail below, solve this problem, are well suited for use in electroluminescent devices, and lead to organic electroluminescent devices that exhibit very good properties, particularly with regard to lifetime, color purity, efficiency, operating voltage, and refractive index. These compounds, as well as electronic devices, in particular organic electroluminescent devices, containing such compounds, are therefore the subject of the present invention.

[0015] The present invention relates to a compound comprising at least one structure of formula (Ia) or (Ib), preferably a compound according to formula (Ia) or (Ib),

[0016] where the symbols are:

[0017] Z stands for a group -(CR b2)n-, where n is an integer in the range of 1 to 6, preferably 1 to 4;

[0018] W stands for a group -(CR b 2)m-, where m is an integer in the range from 1 to 6, preferably 1 to 4, where the group W can be bridged to the group Z via one or more groups V, where V on each occurrence, identically or differently, represents a single bond or an alkylene group having 1 to 40 C atoms which reacts with one or more radicals R 2 may be substituted and wherein one or more non-adjacent CH2 groups are substituted by - R 2 C=CR 2 -, -CEC-, 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, wherein the group V preferably represents a single bond, a group -(CR c 2)o-, where o represents an integer in the range from 1 to 5, preferably 1 to 3, or a group -(CR c 2) P -C=C-, -(CR c 2) P C=C(CR c 2) P - where p represents an integer in the range from 1 to 4, preferably 1 to 3;

[0019] Ar is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms which may be substituted by one or more radicals R, preferably Ar is, identically or differently on each occurrence, an aryl or heteroaryl group having 6 to 40 aromatic ring atoms which may be substituted by one or more radicals R or, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms which may be substituted by one or more radicals R, where the radical Ar may be coordinated to a transition metal;

[0020] R a is at each occurrence, identically or differently, H, D, F, a straight-chain alkyl group having 1 to 40 C atoms, a branched or cyclic alkyl group having 3 to 40 C atoms, each of which is substituted by one or more radicals R bmay be substituted, or an aromatic or heteroaromatic ring system with 5 to 60, each substituted with one or more radicals R 1 may be substituted, preferably a straight-chain alkyl group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms or a phenyl group, where two radicals R a form a ring system with each other;

[0021] R b is at each occurrence, identically or differently, H, D, F, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, preferably H, D, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 15 C atoms, particularly preferably H or D, where two or more radicals R b form a ring system with each other;

[0022] Rc is at each occurrence, identically or differently, H, D, F, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, each of which is substituted by one or more radicals R 2 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by - R 2 C=CR 2 -, -CEC-, 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; preferably H, D, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 15 C atoms, particularly preferably H or D, where two or more radicals R c form a ring system with each other;

[0023] R is, at each occurrence, the same or different, H, D, OH, F, CI, Br, I, CN, NO2, N(Ar')2, N(R 1 )2, C(=O)N(Ar')2, C(=O)N(R 1 )2, C(Ar')3, C(R1 )3, Si(Ar')3, Si(R 1 )3, B(Ar')2, B(R 1 )2, C(=O)Ar', C(=O)R 1 , P(=O)(Ar')2, P(=O)(R 1 )2, P(Ar')2, P(R 1 )2, S(=O)Ar', S(=O)R 1 , S(=O)2Ar', S(=O)2R 1 , OSO2Ar', OSO2R 1 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 1 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R 1 C=CR 1 , C^C, Si(R 1 )2, C=O, C=S, C=Se, C=NR 1 , -C(=O)O-, -C(=O)NR 1 -, NR 1 , P(=O)(R 1), -O-, -S-, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 can be substituted, two radicals R can also be substituted with each other or a radical R can be substituted with another group, in particular a radical R b form a ring system, whereby the radical R can be coordinated to a transition metal;

[0024] Ar' is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is substituted with one or more radicals R 1 may be substituted, whereby two radicals Ar' which bind to the same C-atom, Si-atom, N-atom, P-atom or B-atom may also be connected by a single bond or a bridge selected from B(R1 ), C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, O, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 , are bridged to each other, whereby the residue Ar' can be coordinated to a transition metal;

[0025] R 1 is, at each occurrence, the same or different: H, D, F, CI, Br, I, 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 where one or more H atoms can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2 may be substituted, or an aralkyl or heteroaralkyl group having 5 to 60 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 form a ring system, whereby one or more residues R 1form a ring system with another part of the compound, whereby the residue R 1 be coordinated to a transition metal;

[0026] Ar” is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is substituted by one or more radicals R 2 may be substituted, whereby two radicals Ar” which bind to the same C-atom, Si-atom, N-atom, P-atom or B-atom may also be linked by a single bond or a bridge selected from B(R 2 ), C(R 2 )2, Si(R 2 )2, C=O, C=NR 2 , C=C(R 2 )2, O, S, S=O, SO2, N(R 2 ), P(R 2 ) and P(=O)R 2 , are bridged to each other, whereby the residue Ar" can be coordinated to a transition metal;

[0027] R 2is selected, identically or differently at each occurrence, from the group consisting of 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, in which 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 form a ring system with each other.

[0028] 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 3 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 cycle, i.e. benzene, or a simple heteroaromatic cycle, 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.

[0029] An electron-deficient heteroaryl group within the meaning of the present invention is a heteroaryl group that has at least one heteroaromatic six-membered ring with at least one nitrogen atom. Further aromatic or heteroaromatic five-membered rings or six-membered rings can be fused to this six-membered ring. Examples of electron-deficient heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, or quinoxaline. An aromatic ring system within the meaning of this invention contains 6 to 60 C atoms in the ring system, preferably 6 to 40 C atoms in the ring system. A heteroaromatic ring system within the meaning of this invention contains 3 to 60 C atoms, 3 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 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 connected by a non-aromatic unit, such as a C, N, or O atom. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are also understood to be aromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are connected, for example, by a short alkyl group. The aromatic ring system is preferably selected from fluorene, 9,9'-spirobifluorene, 9,9-diarylamine, or groups in which two or more aryl and / or heteroaryl groups are linked to one another by single bonds.

[0030] In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which may contain 1 to 20 C atoms and in which individual H atoms or CH2 groups may be substituted by the above-mentioned groups, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neo-pentyl, cyclopentyl, n-hexyl, neo-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, Cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentinyl, hexynyl, heptynyl or octynyl.Unter einer Alkoxygruppe mit 1 bis 40 C-Atomen werden bevor- zugt 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, Cyclo- octyloxy, 2-Ethylhexyloxy, Pentafluorethoxy und 2,2,2-Trifluorethoxy ver- standen. Unter einer Thioalkylgruppe mit 1 bis 40 C-Atomen werden ins- besondere Methylthio, Ethylthio, n-Propylthio, i-Propylthio, n-Butylthio,.

[0031] 1-Butylthio, s-Butylthio, t-Butylthio, n-Pentylthio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptylthio, n-Octylthio, Cyclooctylthio,

[0032] 2-Ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio, or octynylthio. In general, alkyl, alkoxy, or thioalkyl groups according to the present invention can be straight-chain, branched, or cyclic, where one or more non-adjacent CH2 groups can be replaced by the above-mentioned groups; Furthermore, one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2, preferably F, Cl or CN, more preferably F or CN, particularly preferably CN.

[0033] An aromatic or heteroaromatic ring system with 5 - 60 or 5 to 40 aromatic ring atoms, which may also be substituted with the above-mentioned radicals 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, iso- benzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, iso-quinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-chinolin, Phenothiazin, Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazin- imidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1 ,2-Thiazol, 1 ,3-Thiazol, Benzo- thiazol, Pyridazin, Hexaazatriphenylen, Benzopyridazin, Pyrimidin, Benz- pyrimidin, Chinoxalin, 1 ,5-Diazaanthracen, 2,7-Diazapyren, 2,3-Diaza- pyren, 1 ,6-Diazapyren, 1 ,8-Diazapyren, 4,5-Diazapyren, 4,5,9, 10-Tetra- azaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1 ,2,3-Triazol, 1 ,2,4-Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1 ,2,4-Oxadiazol, 1 ,2,5-Oxa- diazol, 1 ,3,4-Oxadiazol, 1 ,2,3-Thiadiazol, 1 ,2,4-Thiadiazol, 1 ,2,5-Thiadi- azol, 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 combinations of these systems.,

[0034] For the purposes of this description, the phrase "two or more residues can form a ring" 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.

[0035] Ring formation of the residues R

[0036] 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:

[0037] Ring formation of the residues R

[0038] Preferably, it can be provided that the group Ar is selected, identically or differently on each occurrence, from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, triphenylamine, diphenyl ether, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, which may each be substituted by one or more radicals R, preferably phenyl, biphenyl, fluorene, dibenzofuran, triphenylene, indolocarbazole.

[0039] Furthermore, in particular in structures of the formulas (Ia) and / or (Ib) and the structures related thereto, it can be provided that the sum of the indices m and n is 3 to 6 and / or the sum of the indices p, o, m, and n is preferably 3 to 8.

[0040] The group Ar, together with the C atoms to which the group Ar is bonded and the oxygen atom bonded to the same C atoms, can preferably form a ring with 5, 6, 7, 8, 9 or 10 atoms, preferably with 5, 6, 7, 8 or 9 atoms, particularly preferably with 5, 6, 7 or 8 atoms.

[0041] In a preferred embodiment, the compounds according to the invention can preferably comprise at least one structure of the formulas (Ia-1) to (Ib-7), and are particularly preferably selected from the compounds of the formulas (Ia-1) to (Ib-7),

[0042] Formula (1-1) Formula (I-2) where the symbols R, R a , R b , W and Z have the meanings given above, in particular for formulas (Ia) and (Ib) and the following applies to the other symbols:

[0043] Y is, identically or differently at each occurrence, O, S, NR, Si(R)2, C(R)2 or an ortho-linked phenylene group which may be substituted by one or more radicals R, preferably O or NR, particularly preferably NR;

[0044] Y 1 is, identically or differently at each occurrence, C(R)2, Si(R)2, C=O, P(O)R, P(R), O, S, NR or BR, preferably NR or BR, particularly preferably NR; and

[0045] X is, at each occurrence, the same or different, CR or N, preferably CR.

[0046] Structures / compounds of the formulas Ia-1, Ia-2, Ia-5, Ia-6, Ib-1 and I-2 are preferred and structures / compounds of the formulas Ia-1 and Ib-1 are particularly preferred.

[0047] Preferably, in particular in structures / compounds of the formulas (Ia-1) to (Ib-7), it can be provided that at most two groups X per ring stand for N, preferably all X stand for CR, preferably at least one, particularly preferably at least two of the groups X per ring are selected from CH and CD.

[0048] Furthermore, it can be particularly preferred, in particular in structures / compounds of the formulas (Ia-1) to (Ib-7), that no more than four, preferably no more than two groups X stand for N, particularly preferably all groups X stand for CR, where preferably at most 4, particularly preferably at most 3 and especially preferably at most 2 of the groups CR, which X stands for, are not equal to the group CH or CD.

[0049] In a further preferred embodiment, it can be provided that the compounds according to the invention comprise a structure of the formulas (IIa-1) to (IIb-7), wherein the compounds according to the invention can particularly preferably be selected from the compounds of the formulas (IIa-1) to (IIb-7),

[0050] where the symbols R, R a , R b , W, and Z have the meanings given above, in particular for formulas (Ia) and (Ib), the symbols Y and Y 1 have the meanings given above, in particular for formulas (Ia-1) to (Ib-7), and the following applies to the further symbols: j is, at each occurrence, independently 0, 1, 2 or 3, preferably 0, 1 or 2; h is, at each occurrence, independently 0, 1, 2, 3 or 4, preferably 0, 1 or 2; and g is, at each occurrence, independently 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2.

[0051] Structures / compounds of the formulas IIa-1, IIa-2, IIa-5, IIa-6, IIb-1 and IIb-2 are preferred and structures / compounds of the formulas IIa-1 and IIb-1 are particularly preferred.

[0052] Preferably, in particular in structures / compounds of the formulas (IIa-1) to (IIb-7), it can be provided that the sum of the indices j, h and g is at most 6, preferably at most 4, and particularly preferably at most 2.

[0053] In a further preferred embodiment, it can be provided that the compounds according to the invention comprise a structure of the formulas (III-1) to (III-4), wherein the compounds according to the invention can particularly preferably be selected from the compounds of the formulas (III-1) to (III-4), where the symbols R, R a , R b , W, and Z have the meanings given above, in particular for formulas (la) and (lb) and the following applies to the other symbols:

[0054] Y 2is the same or different at each occurrence B(R 1 ), C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, 0, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 , preferably B(R 1 ), C=O or P(=O)R 1 , particularly preferably B(R 1 );

[0055] Y 3 is the same or different at each occurrence B(R 1 ), C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, 0, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 , preferably 0, N(R 1 ) or P(R 1 ), particularly preferably O or N(R 1 ) and most preferably N(R 1 ); and j is independently 0, 1, 2 or 3 at each occurrence, preferably 0, 1 or 2.

[0056] Furthermore, in particular in structures / compounds of the formulas (III-1) to (III-4), the sum of the indices j may be at most 8, preferably at most 6, particularly preferably at most 5 and particularly preferably at most 3.

[0057] In a preferred embodiment of the present invention, it can be provided that the radicals Z and W are substituted with the CR b -groups or the CR b -Group and the CR b 2 group and the C atom to which the CR b - group binds, forming a partial structure of the formulas (RC-1 ) to (RC-10)

[0058] where R bhas the meaning set out above, in particular for formulas (Ia) and (Ib), the dashed bonds represent the bonds to the oxygen atom and the group Ar, and the further symbols have the following meaning: r is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3, or 4, particularly preferably 0, 1 or 2; s is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3, or 4, particularly preferably 0, 1 or 2; t is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, preferably 0, 1, 2, 3, or 4, particularly preferably 0, 1 or 2; v is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2;

[0059] Structures of the formulas (RC-4), (RC-6), (RC-8) and (RC-9) are preferred.

[0060] In a further preferred embodiment, it can be provided that the compounds according to the invention comprise a structure of the formulas (IV-1) to (IV-16), wherein the compounds according to the invention can particularly preferably be selected from the compounds of the formulas (IV-1) to (IV-16),

[0061] where the symbols R, R a and R b have the meanings given above, in particular for formulas (Ia) and (Ib), the symbols Y and Y 1have the meanings given above, in particular for formulas (Ia-1) to (Ib-7) and the following applies to the further symbols: j is at each occurrence independently 0, 1, 2 or 3, preferably 0, 1 or 2; h is at each occurrence independently 0, 1, 2, 3 or 4, preferably 0, 1 or 2; r is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2; and v is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2. Structures / compounds of the formulas IV-2, IV-3, IV-4, IV-6, IV-7, IV-8, IV-15 and IV-16 are preferred and structures / compounds of the formulas IV-2, IV-7 and IV-15 are particularly preferred.

[0062] Furthermore, in particular in structures / compounds of the formulas (Ia) and (Ib) and the structures / compounds related thereto, for example (Ia-1) to (Ib-7), (IIa-1) to (IIb-7), (III-1) to (III-4) and (IV-1) to (IV-16), it can be provided that the two radicals R a form a partial structure of the formulas (RC-1) to (RC-10), preferably a partial structure of the formula (RC-4), (RC-6), (RC-8) or (RC-9).

[0063] In a further preferred embodiment, it can be provided that the compounds according to the invention comprise a structure of the formulas (V-1) to (V-5), wherein the compounds according to the invention can particularly preferably be selected from the compounds of the formulas (V-1) to (V-5),

[0064] where the symbols R and R b have the meanings given above, in particular for formulas (la) and (lb), the symbols Y and Y 1have the meanings given above, in particular for formulas (Ia-1) to (Ib-7), and the following applies to the further symbols: h is independently 0, 1, 2, 3 or 4 at each occurrence, preferably 0, 1 or 2; r is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2; and v is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 0, 1, 2, 3, or 4, particularly preferably 0, 1 or 2. In a preferred development of the present invention, it can be provided that at least two, preferably adjacent radicals R form a condensed ring with the further groups to which the two radicals R bind, wherein the two radicals R form at least one structure of the formulas (RA-1) to (RA-12) where R 1 has the meaning set out above, the dashed bonds represent the attachment points to the atoms of the groups to which the two radicals R bind, and the other symbols have the following meaning:

[0065] Y 4 is the same or different at each occurrence C(R 1 )2, (R 1 )2C-C(R 1 )2, (R 1 )C=C(R 1 ), NR 1 , NAr', 0 or S, preferably C(R 1 )2, (R 1 )2C-C(R 1 )2, (R 1 )C=C(R 1 ), 0 or S;

[0066] R d is, identically or differently at each occurrence, F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 2 may be substituted, wherein one or more non-adjacent CH2 groups are substituted 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 -, NR2 , P(=O)(R 2 ), -O-, -S-, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2 can be substituted; two radicals R d also with each other or a residue R d with a remainder R 1 or form a ring system with another group, where R 2has the meaning given above, in particular for formulas (Ia) and (Ib); s is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2; t is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2; v is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2.

[0067] Structures of the formulas RA-1, RA-3, RA-4 and RA-5 are preferred, and structures of the formulas RA-4 and RA-5 are particularly preferred. In a preferred embodiment of the invention, at least two, preferably adjacent, radicals R form a condensed ring with the other groups to which the two radicals R are bonded, wherein the two radicals R of the structures of the formulas (RA-1a) to (RA-4f) form where the dashed bonds represent the attachment points to the atoms of the groups to which the two radicals R are bonded, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2 and the symbols R 1 , R 2 , R d and the indices s and t have the meaning set out above, in particular for formulas (la) and (lb) respectively and / or formulas (RA-1) to (RA-12).

[0068] Structures of the formula RA-4f are preferred.

[0069] Furthermore, it can be provided that the at least two radicals R which form structures of the formulas (RA-1) to (RA-12) and / or (RA-1 a) to (RA-4f) and form a condensed ring, represent radicals R from adjacent groups X or represent radicals R which are each bonded to adjacent C atoms, wherein these C atoms are preferably connected via a bond.

[0070] In a further preferred embodiment, preferably at least two, preferably adjacent, radicals R form a condensed ring with the further groups to which the two radicals R bind, wherein the two radicals R form structures of the formula (RB) where R 1 has the meaning given above, in particular for formulas (la) or (lb), the dashed bonds represent the bonding sites via which the two radicals R bind, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y 5 C(R 1 )2, NR 1 , NAr', BR 1 , BAr', 0 or S, preferably C(R 1 )2, NAr' or 0, particularly preferably C(R 1 )2 or 0, where Ar' has the meaning given above, in particular for formulas (la) or (lb).

[0071] Furthermore, it can be provided that the at least two radicals R which form structures of the formula (RB) and form a condensed ring represent radicals R from adjacent groups X or represent radicals R which are each bonded to adjacent C atoms, wherein these C atoms are preferably connected via a bond.

[0072] Particularly preferably, the compounds comprise at least one structure of the formulas (VI-1) to (VI-12), particularly preferably the compounds are selected from compounds of the formulas (VI-1) to (VI-12), wherein the compounds have at least one condensed ring,

[0073] where the symbols R, R a and R bhave the meanings given above, in particular for formulas (Ia) and (Ib), the symbol o stands for the condensation sites of the at least one condensed ring and the following applies to the further indices used: i is, independently at each occurrence, 0, 1 or 2, preferably 0 or 1; r is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2; and v is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2.

[0074] Furthermore, in particular for structures / compounds of the formulas (VI-1) to (VI-12), it can be provided that the condensed ring is formed by structures of the formulas (RA-1) to (RA-12), (RA-1 a) to (RA-4f) and / or (RB), as previously shown, preferably by structures of the formulas (RB).

[0075] Furthermore, in structures / compounds of the formulas (VI-1) to (VI-12) it can be provided that the sum of the indices i, r and v is at most 10, preferably at most 8, particularly preferably at most 6 and particularly preferably at most 4.

[0076] Preferably, the compounds may have at least two condensed rings, wherein at least one condensed ring is formed by structures of the formulas (RA-1) to (RA-12) and / or (RA-1 a) to (RA-4f) and a further ring is formed by structures of the formulas (RA-1) to (RA-12), (RA-1 a) to (RA-4f) or (RB).

[0077] Furthermore, it can be provided that the substituents R and R 1 according to the above formulas with the ring atoms of the ring system to which the substituents R and R 1bind, do not form a fused aromatic or heteroaromatic ring system. This excludes the formation of a fused aromatic or heteroaromatic ring system with possible substituents R 1 and R 2 which are bound to the substituents R and R 1 may be bound.

[0078] The residues R a , R b , R c preferably do not form a ring system with other groups. If substituents R a form a ring system, this ring is preferably composed of exactly two residues R a which are bonded to a C atom. If the compound according to the invention is reacted with aromatic or heteroaromatic groups R, R 1 or R 2is substituted, it is preferred in one embodiment if these do not contain any aryl or heteroaryl groups with more than two directly fused aromatic six-membered rings. Particularly preferably, the substituents do not contain any aryl or heteroaryl groups with directly fused aromatic six-membered rings. This preference is due to the low triplet energy of such structures. Condensed aryl groups with more than two directly fused aromatic six-membered rings that are nevertheless also suitable according to the invention are phenanthrene and triphenylene, since these also have a high triplet level.

[0079] Furthermore, it can be provided that the remainder R, R 1 or R 2does not comprise an aromatic or heteroaromatic ring system having three linearly condensed aromatic 6-rings, wherein preferably none of the radicals R comprises an aromatic or heteroaromatic ring system having three linearly condensed aromatic 6-rings.

[0080] Furthermore, it can be provided that the substituents R and R 1 according to the above formulas, do not form a condensed aromatic or heteroaromatic ring system with the ring atoms of the ring system, preferably not a condensed ring system. This excludes the formation of a condensed ring system with possible substituents R 1 and R 2 which are bound to the residues R, R 1 may be bound.

[0081] When two residues, which can be selected in particular from R, R 1 and / or R 2, form a ring system with each other, this can be mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic. The radicals forming a ring system can be adjacent, ie these radicals are bonded to the same carbon atom or to carbon atoms that are directly bonded to each other, or they can be further apart. Furthermore, the radicals bonded to the substituents R, R 1 and / or R 2 provided ring systems can also be connected to each other via a bond, so that a ring closure can be achieved.

[0082] Furthermore, it can be provided that at least two of the radicals R either form a condensed ring, preferably according to the structures of the formulas (RA-1) to (RA-12) or (RB) or at least one radical R is selected, identically or differently on each occurrence, from the group consisting of an aromatic or heteroaromatic ring system selected from the groups of the following formulas Ar-1 to Ar-76, and / or the group Ar' is selected, identically or differently on each occurrence, from the groups of the following formulas Ar-1 to Ar-76,

[0083] where R 1 has the meanings given above, the dashed bond represents the bond to the corresponding group and furthermore:

[0084] Ar 1is at each occurrence, identically or differently, a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, each of which is substituted by one or more radicals R 1 can be substituted; A is the same or different at each occurrence C(R 1 )2, NR 1 , 0 or S; p is 0 or 1 , where p = 0 means that the group Ar 1 is not present and that the corresponding aromatic or heteroaromatic group is directly bonded to the corresponding residue; q is 0 or 1, where q = 0 means that no group A is bonded to this position and that the corresponding carbon atoms are bonded instead to residues R 1 are bound.

[0085] The previously presented structures of the formulas (Ar-1) to (Ar-76) represent preferred embodiments of the radicals Ar, as defined, for example, for structures of the formula (Ia) or (Ib), in which case the substituents R1 in formulas (Ar-1) to (Ar-76) are to be replaced by R, where R has the meaning defined above, in particular for formulas (Ia) or (Ib). Furthermore, the radical Ar comprises a further attachment point, where in formulas (Ar-1) to (Ar-76) a radical R 1 can represent a binding site.

[0086] Structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-40), (Ar-41), (Ar-42), (Ar-43), (Ar-44), (Ar-45), (Ar-46), (Ar-69), (Ar-70), (Ar-76) are preferred and structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16) are particularly preferred.

[0087] If the above-mentioned groups for structures of the formulas (Ar-1) to (Ar-76) have several groups A, all combinations from the definition of A are possible. Preferred embodiments are then those in which a group A represents NR 1and the other group A for C(R 1 )2 or in which both groups A for NR 1 or in which both groups A stand for 0.

[0088] If A for NR 1 the substituent R 1 which is bonded to the nitrogen atom, preferably represents an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 2 In a particularly preferred embodiment, this substituent R 1identical or different on each occurrence for an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 18 aromatic ring atoms, which has no condensed aryl groups and which has no condensed heteroaryl groups in which two or more aromatic or heteroaromatic 6-ring groups are directly fused to one another, and which in each case also by one or more radicals R 2 may be substituted. Phenyl, biphenyl, terphenyl and quaterphenyl are preferred. Triazine, pyrimidine and quinazoline are also preferred, as listed above for Ar-47 to Ar-50, Ar-57 and Ar-58, where these structures are substituted by R 1 by one or more residues R 2 can be substituted.

[0089] If A for C(R 1 )2, the substituents R 1which are bonded to this carbon atom, preferably identically or differently on each occurrence, represent 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 can also be substituted by one or more radicals R 2 R is particularly preferably 1 represents a methyl group or a phenyl group. The radicals R 1 also form a ring system with each other, which leads to a spiro system.

[0090] Preferred substituents R and R d described.

[0091] Preferably, it can be provided that for the symbols used in particular in formulas (la), (Ib), (la-1) to (lb-7), etc., the following applies:

[0092] R is the same or different at each occurrence and is H, D, N(Ar')2, N(R 1)2, C(Ar')3, C(R 1 )3, Si(Ar')3, Si(R 1 )s, B(Ar')2, B(R 1 )2, a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R 1 C=CR 1 , C=C, Si(R 1 )2, C=O, C=S, C=Se, C=NR 1 , -C(=O)O-, -C(=O)NR 1 -, NR 1 , P(=O)(R 1 ), -O-, -S-, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted; two radicals R may also be substituted with each other or a radical R may be substituted with another group, in particular a radical R b form a ring system.

[0093] In a preferred embodiment of the invention, R is the same or different on each occurrence and is selected from the group consisting of H, D, F, CN, NO2, Si(R 1 )s, B(OR 1 )2, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted.

[0094] In a further preferred embodiment of the invention, substituent R is the same or different on each occurrence and is selected from the group consisting of H, D, F, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1 can be substituted.

[0095] Furthermore, it can be provided that at least one radical R, preferably a substituent R, is selected, identically or differently on each occurrence, from the group consisting of H, D, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which is substituted with one or more radicals R 1may be substituted, or a group N(Ar')2, particularly preferably at least one substituent R, R d is selected, identically or differently on each occurrence, from the group consisting of an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which is substituted with one or more radicals R 1 may be substituted, or a group N(Ar')2. Especially preferably, at least one substituent R is selected, identically or differently on each occurrence, from the group consisting of an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which is substituted with one or more radicals R 1may be substituted. In a further preferred embodiment of the invention, the substituents R either form a ring according to the structures of the formulas (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB) or the substituent R is, identically or differently on each occurrence, selected from the group consisting of H, D, an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which is substituted with one or more radicals R 1 may be substituted, or a group N(Ar')2. Particularly preferably, the radical R is preferably the substituent R, identical or different on each occurrence, selected from the group consisting of H, D or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, particularly preferably having 6 to 13 aromatic ring atoms, which in each case is substituted with one or more radicals R 1 can be substituted.

[0096] Furthermore, it can be provided that at least one radical R represents an aromatic or heteroaromatic ring system having 5 to 13 aromatic ring atoms, which with one or more radicals R 1 can be substituted.

[0097] Preferably, it can be provided that at least one radical, preferably a substituent R, identically or differently on each occurrence, is selected from 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 1 can be substituted.

[0098] Here, the term substituent means in particular that R is not H. Furthermore, the substituents R may be the same or different if two or more substituents are present which are selected from the aromatic or heteroaromatic group mentioned.

[0099] Furthermore, it can be provided that the groups R bonded to a C atom a are equal.

[0100] Furthermore, it can be provided that the groups R bonded to different C atoms a are equal.

[0101] In a particularly preferred embodiment, it can be provided that the two radicals R bonded to a C atom a form the same structure as the groups Z, W and the C atoms connected to these groups, the residues R b This creates a symmetry with respect to the oxygen atom and the group Ar. Therefore, it is particularly preferred that the radicals Z and W are connected to the CR b-groups or the CR b -Group and the CR b 2-group and the C-atom to which the CR b -group, form a partial structure of the formulas (RC-1 ) to (RC-10), as previously explained and the groups Ra form an identical partial structure of the formulas (RC-1 ) to (RC-10).

[0102] In addition, it can be provided that the groups R bonded to different C atoms a are different.

[0103] Preferably, it can be provided that the groups R bonded to a C atom a are selected from straight-chain alkyl groups having 1 to 10 C atoms or branched or cyclic alkyl groups having 3 to 10 C atoms, each of which is substituted by one or more radicals R b may be substituted, or a phenyl group, each substituted with one or more radicals R 1 may be substituted, preferably deuterated, the groups R bonded to a C atom may be aform a ring system with each other, where in the case that R a each represents a phenyl group, the phenyl groups being connected via a single bond or a bridge selected from C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, O, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 , preferably C(R 1 )2, Si(R 1 )2or O. Furthermore, it can preferably be provided that the group R a represents methyl, ethyl, propyl or phenyl or two groups R a which bond to the same C-atom form a cycloalkyl radical with 5 or 6, preferably 5 carbon atoms, where the group R a preferably represents methyl, where these groups may be deuterated. Preferably, the group R a unsubstituted, except for D.

[0104] Preferably, it can be provided that at least one of the groups R arepresents a phenyl group or two groups R a which bond to the same C-atom each represent a phenyl group, wherein the phenyl groups are connected via a single bond or a bridge selected from C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, 0, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 , preferably C(R 1 )2, Si(R 1 )2 or O. Preferably, the group R a unsubstituted, except for D.

[0105] Preferably, it can be provided that the group R b represents H, D, methyl, ethyl, propyl, where these groups may be deuterated, where the group R b preferably represents H or D.

[0106] Preferably, it can be provided that the group R c represents H, D, methyl, ethyl, propyl, where these groups may be deuterated, where the group R cpreferably represents H or D.

[0107] In a preferred embodiment of the invention, R d identically or differently on each occurrence selected from the group consisting of a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl group is in each case substituted with one or more radicals R 1 may be substituted, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 2 can be substituted.

[0108] In a further preferred embodiment of the invention, R didentically or differently on each occurrence selected from the group consisting of a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl group is in each case substituted with one or more radicals R 2 may be substituted, an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, which is substituted with one or more radicals R 2 may be substituted. R is particularly preferably d identically or differently on each occurrence selected from the group consisting of a straight-chain alkyl group having 1 to 5 C atoms or a branched or cyclic alkyl group having 3 to 5 C atoms, where the alkyl group is in each case substituted with one or more radicals R 2may be substituted or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, particularly preferably having 6 to 13 aromatic ring atoms, each of which is substituted by one or more radicals R 2 can be substituted.

[0109] In a preferred embodiment of the invention, R d at each occurrence, identically or differently selected from the group consisting of a straight-chain alkyl group having 1 to 6 C atoms or a cyclic alkyl group having 3 to 6 C atoms, where the alkyl group is in each case substituted with one or more radicals R 2 may be substituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 2 can be substituted; two radicals R d also form a ring system with each other. R is particularly preferably dat each occurrence, identically or differently selected from the group consisting of a straight-chain alkyl group 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 is in each case substituted with one or more radicals R 2 may be substituted, but is preferably unsubstituted, or an aromatic ring system having 6 to 12 aromatic ring atoms, in particular having 6 aromatic ring atoms, each substituted by one or more, preferably non-aromatic radicals R 2 may be substituted, but is preferably unsubstituted; two radicals R d form a ring system with each other. R is particularly preferably d at each occurrence, identically or differently selected from the group consisting of a straight-chain alkyl group having 1, 2, 3 or 4 C atoms, or a branched alkyl group having 3 to 6 C atoms. R is most preferably dfor a methyl group or for a phenyl group, where two phenyl groups together can form a ring system, with a methyl group being preferred over a phenyl group.

[0110] Preferred aromatic or heteroaromatic ring systems for which the substituents R, R a , R d , R e , R dor Ar or Ar' 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 may be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which may be linked via the 1-, 2-, 3- or 4-position, naphthalene, in particular 1- or -linked naphthalene, indole, benzofuran, benzothiophene, carbazole, which may be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, which may be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, which may be linked via the 1-, 2-, 3- or 4-position, Indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, anthracene, pyrene, perylene, chrysene, phenanthrene or triphenylene,which are each substituted with one or more radicals R, R, 1 or R 2 may be substituted. The structures Ar-1 to Ar-76 listed above are particularly preferred, with structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), (Ar-76) being preferred and structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16) being particularly preferred. With regard to the structures Ar-1 to Ar-76, it should be noted that these can be substituted with a substituent R 1 In the case of the ring systems Ar, these substituents are R 1 by R and in case R d these substituents R 1 by R 2 to replace.

[0111] Other suitable groups R are groups of the formula -Ar 4 -N(Ar 2 )(Ar 3 ), where Ar 2 , Ar 3 and Ar 4identically or differently on each occurrence represent an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which is each substituted by one or more radicals R 1 The total number of aromatic ring atoms of Ar 2 , Ar 3 and Ar 4 maximum 60 and preferably maximum 40.

[0112] Ar 4 and Ar 2 with each other and / or Ar 2 and Ar 3 with each other also by a group selected from C(R 1 )2, NR 1 , O or S. Preferably, the linking of Ar 4 and Ar 2 with each other or from Ar 2 and Ar 3 are ortho to the position of the linkage to the nitrogen atom. In a further embodiment of the invention, none of the groups Ar 2 , Ar 3 or Ar 4 connected to each other.

[0113] Ar is preferred 4 an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted. Particularly preferred is Ar 4 selected from the group consisting of ortho-, meta- or para-phenylene or ortho-, meta- or para-biphenyl, each of which is substituted by one or more radicals R 1 may be substituted, but are preferably unsubstituted. Ar is particularly preferred 4 an unsubstituted phenylene group.

[0114] Preference is given to Ar 2 and Ar 3 identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 1 Particularly preferred groups Ar 2 or Ar 3are, identically or differently at each occurrence, selected from the group consisting of benzene, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spiro-bifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene, 1-, 2-

[0115] 3- or 4-carbazole, 1-, 2-, 3- or 4-dibenzofuran, 1-, 2-, 3- or 4-di-benzothiophene, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2-,

[0116] 4- or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene or triphenylene, each of which is substituted with one or more radicals R 1 may be substituted. Particularly preferred are Ar 2 and Ar 3identically or differently on each occurrence selected from the group consisting of benzene, 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, in particular 1-, 2-, 3- or 4-fluorene, or spirobifluorene, in particular 1-, 2-, 3- or 4-spirobifluorene.

[0117] In a further preferred embodiment of the invention, R 1 identically or differently on each occurrence selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl group is in each case substituted with one or more radicals R 2 may be substituted, or an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, each substituted by one or more radicals R2 may be substituted. In a particularly preferred embodiment of the invention, R 1 identically or differently on each occurrence selected from the group consisting of H, 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 is substituted with one or more radicals R 2 may be substituted, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms, each substituted by one or more radicals R 5 can be substituted, but is preferably unsubstituted.

[0118] In a further preferred embodiment of the invention, R 2identical or different on each occurrence H, 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.

[0119] In compounds according to the invention that are processed by vacuum evaporation, the alkyl groups preferably have no more than five carbon atoms, particularly preferably no more than 4 carbon atoms, and most preferably no more than 1 carbon atom. Also suitable for compounds that are processed from solution are compounds that are substituted by alkyl groups, particularly branched alkyl groups, with up to 10 carbon atoms, or that are substituted by oligoarylene groups, for example ortho-, meta-, para-, or branched terphenyl or quaterphenyl groups.

[0120] When the compounds of formulas (Ia) or (Ib) 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 fused aryl or heteroaryl groups in which more than two six-membered rings are directly fused to one another. Exceptions to this are phenanthrene and triphenylene, which may be preferred due to their high triplet energy despite the presence of fused aromatic six-membered rings.

[0121] Preferably, in one embodiment, the compound may not comprise an aromatic or heteroaromatic ring system having three aromatic 6 rings fused to one another.

[0122] In a further embodiment, the compound may comprise an aromatic or heteroaromatic ring system comprising three fused aromatic rings. This applies in particular to use in combination with or as a fluorescent emitter.

[0123] Furthermore, it may be provided that the connection is excluded from protection.

[0124] The present compounds preferably serve as components in electronic devices, particularly preferably as functional components, and can therefore preferably contain functional groups. These include, among others, the hole-transport groups, electron-transport groups, and emitting groups described above and below.

[0125] Preferably, it can be provided that the connection comprises at least one hole transport group.

[0126] Hole-transport groups are widely known in the scientific community. These include, in particular, di- and triarylamine groups, carbazole groups, and groups with similar properties. Preferred groups include, for example, residues Ar-76, as defined above.

[0127] Preferably, the compound may comprise at least one electron transport group.

[0128] Electron-transport groups are widely known in the art and enhance the ability of compounds to transport and / or conduct electrons. These include, in particular, nitrogen-containing heteroaryl groups with 5 to 12 ring atoms, particularly preferably with 6 to 12 ring atoms, which are generally electron-poor heteroaryl groups.

[0129] Preferably, it can be provided that the compound comprises at least one electron transport group selected from pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and / or benzimidazole groups, preferably pyrimidine, pyrazine, triazine, quinazoline, quinoxaline and / or benzimidazole groups, particularly preferably a pyrimidine, triazine, quinazoline and / or quinoxaline group, particularly preferably pyrimidine and / or triazine groups, very particularly preferably triazine groups, which are reacted with one or more radicals R, R 1 or R 2 may be substituted, depending on the position at which the group is formed or bonded. In one embodiment, the compound may not contain a carbazole group, preferably a carbazole group and / or substituents of the formula N(Ar')2, N(R 1 )2 and particularly preferably does not comprise a hole transport group.

[0130] Compounds having one or more electron transport groups that do not comprise a hole transport group are particularly suitable as electron injection material, electron transport material or hole blocking material that are used in a corresponding layer, wherein this layer generally does not contain an emitting compound.

[0131] In a further embodiment, it can be provided that the group L 1 a hole transport group, preferably a carbazole group and / or a substituent of the formula N(Ar')2, and particularly preferably a carbazole group.

[0132] Furthermore, it can be provided that the compound does not comprise a triazine group, preferably no pyrimidine and / or triazine group and particularly preferably no electron transport group.

[0133] Compounds with one or more hole transport groups that do not comprise an electron transport group are particularly suitable as hole injection material, hole transport material or electron blocking material that are used in a corresponding layer, whereby this layer generally does not contain an emitting compound.

[0134] In a further embodiment, it can be provided that the compound comprises at least one electron transport group and at least one hole transport group, preferably at least one carbazole group and / or at least one substituent of the formula N(Ar')2, and particularly preferably a carbazole group.

[0135] Compounds with one or more electron transport groups that include at least one hole transport group are particularly suitable as host materials that are used in combination with an emitting compound.

[0136] Compound according to at least one of the preceding claims, characterized in that the compound comprises at least one emitting group.

[0137] Emitting groups are also widely known and lead to, among others, fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF.

[0138] Groups that lead to fluorescent emitters are well known, and these groups often have condensed aromatic rings, such as fluorene, anthracene and / or pyrene groups, which are linked to groups R 1 or R 2may be substituted. Phosphorescent emitters are widely known in the art, with particular use being made of metal complexes, which are described later herein. Emitters exhibiting TADF are also well described. Preferred emitters include, among others, DABNA types and compounds with similar properties, including, for example, the compounds shown in formulas (III-1) to (III-4), which compounds preferably contain at least one B and at least one N atom.

[0139] Furthermore, it can be provided that the compound comprises exactly two, exactly three or exactly four structures according to formulas (Ia) or (Ib).

[0140] In a preferred embodiment, the compounds are selected from compounds of the formulas (D-1), (D-2) or (D-3), where group L 1represents a connecting group, preferably a bond or an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R, and the further symbols and indices used have the meanings given above, in particular for formulas (Ia) or (Ib), where the group L 1 forms a bond to the basic structure instead of a hydrogen atom or a substituent, preferably the group L 1 to the residues Ar or the residues Ar together with the group L 1 forms an aromatic or heteroaromatic ring system having 5 to 60, preferably 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.

[0141] In a further preferred embodiment of the invention, L 1represents a bond or an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having 6 to 12 carbon atoms, which may be substituted by one or more radicals R, but is preferably unsubstituted, where R may have the meaning given above, in particular for formulas (Ia) or (Ib). L is particularly preferably 1 represents an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, but is preferably unsubstituted, where R 1 which may have the meaning given above, in particular for formulas (Ia) or (Ib).

[0142] Furthermore, the symbol L shown inter alia in formula (D1 ) is preferably 1identical or different on each occurrence for a bond or an aryl or heteroaryl radical having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, particularly preferably 6 to 10 ring atoms, so that an aromatic or heteroaromatic group of an aromatic or heteroaromatic ring system is bonded directly, ie via an atom of the aromatic or heteroaromatic group, to the respective atom of the further group.

[0143] Furthermore, it can be provided that the group L shown in formula (D1 ) 1an aromatic ring system with at most four, preferably at most three, particularly preferably at most two fused aromatic and / or heteroaromatic 6-membered rings, preferably no fused aromatic or heteroaromatic ring system. Accordingly, naphthyl structures are preferred over anthracene structures. Furthermore, fluorenyl, spirobifluorenyl, dibenzofuranyl, and / or dibenzothienyl structures are preferred over naphthyl structures.

[0144] Particularly preferred are structures which do not exhibit condensation, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0145] Examples of suitable aromatic or heteroaromatic ring systems L 1are selected from the group consisting of ortho-, meta- or para-phenylene, ortho-, meta- or para-biphenylene, terphenylene, in particular branched terphenylene, quaterphenylene, in particular branched quaterphenylene, fluorenylene, spirobifluorenylene, dibenzofuranylene, dibenzothienylene and carbazolylene, each of which is substituted by one or more radicals R 1 may be substituted, but are preferably unsubstituted.

[0146] In a preferred embodiment, the compounds are selected from compounds of the formulas (D-1-1) to (D-3-2),

[0147] where the symbols R, R a , R b, W, and Z have the meanings given above, in particular for formulas (Ia) or (Ib), and the following applies to the further indices used: i is, independently at each occurrence, 0, 1 or 2, preferably 0 or 1; j is, independently at each occurrence, 0, 1, 2 or 3, preferably 0 or 1; h is, independently at each occurrence, 0, 1, 2, 3 or 4, preferably 0, 1 or 2; and g is, independently at each occurrence, 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2.

[0148] In a preferred embodiment, the compounds according to the invention have a high degree of deuteration. Preferably, the degree of deuteration is at least 50%, preferably at least 80%, especially preferably at least 90%, and most preferably at least 95%. The degree of deuteration is determined from the numerical ratio of deuterium to the sum of deuterium and 1 H-hydrogen (D / (D+H)*100). The compounds are particularly preferably fully deuterated.

[0149] According to a preferred embodiment, a compound according to the invention can be represented by at least one of the structures according to formulas (Ia), (Ib), (Ia-1) to (Ib-7), (IIa-1) to (IIb-7), (III-1) to (III-4), (IV-1) to (IV-16), (V-1) to (V-5) and / or (VI-1) to (VI-12). Preferably, compounds according to the invention, preferably comprising structures according to formulas (Ia), (Ib), (Ia-1) to (Ib-7), (IIa-1) to (IIb-7), (III-1) to (III-4), (IV-1) to (IV-16), (V-1) to (V-5) and / or (VI-1) to (VI-12) have a molecular weight of less than or equal to 5000 g / mol, preferably less than or equal to 4000 g / mol, particularly preferably less than or equal to 3000 g / mol, especially preferably less than or equal to 2000 g / mol, more especially preferably less than or equal to 1200 g / mol and very particularly preferably less than or equal to 900 g / mol.

[0150] Furthermore, preferred compounds according to the invention are characterized by their sublimability. These compounds generally have a molecular weight of less than approximately 1200 g / mol.

[0151] Preferably, the compound may not comprise any alkoxy, thioalkoxy or hydroxy groups.

[0152] Furthermore, it can be provided that the compound comprising structures according to formulas (Ia) or (Ib), preferably the compound according to formulas (Ia) or (Ib) or a preferred embodiment of these structures / compounds is not in direct contact with a metal atom, preferably does not represent a ligand for a metal complex.

[0153] In a further preferred embodiment, it can be provided that the compound comprising structures according to formulas (Ia) or (Ib), preferably the compound according to formulas (Ia) or (Ib) or a preferred embodiment of these structures / compounds is coordinated to a transition metal, preferably represents a ligand for a metal complex.

[0154] A further subject of the present invention is therefore a metal complex containing one or more compounds according to one of claims 1 to 36, wherein the metal complexes correspond to the general formula (1):

[0155] M(L) n (L')m Formula (1 ) where the symbols and indices used are:

[0156] M is a transition metal, preferably Cu, Mo, W, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au or Eu, particularly preferably Pt, Ir,

[0157] L is a bidental ligand;

[0158] L' is, identical or different on each occurrence, a ligand; n is 1, 2 or 3, preferably 2, particularly preferably 3; m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, particularly preferably 0; several ligands L can be linked to one another or L to L' via a single bond or a bivalent or trivalent bridge and thus form a tridentate, tetradentate, pentadentate or hexadentate ligand system; where at least one of the ligands L, L' represents a structure according to formula (Ia) or (Ib) or a preferred embodiment of these structures / compounds. Furthermore, it can be provided that the metal complexes of the general

[0159] Formula (1 ) a substructure M(L) n of formula (2) where M has the meaning given in claim 37 and the symbols and indices used are:

[0160] CyC is an aryl or heteroaryl group having 5 to 18 aromatic ring atoms or a fluorene or azafluorene group, each of which is coordinated to Ir via a carbon atom and which may be substituted by one or more radicals R and which is linked to CyD via a covalent bond, where R has the meaning given above, in particular for formulas (Ia) and (Ib);

[0161] CyD is a heteroaryl group having 5 to 18 aromatic ring atoms, which is coordinated to Ir via a neutral nitrogen atom or via a carbene carbon atom and which may be substituted by one or more radicals R and which is linked to CyC via a covalent bond, where R has the meaning given above, in particular for formulas (Ia) and (Ib); n is 1, 2 or 3, preferably 2, particularly preferably 3; several ligands L can also be linked to one another via a single bond or a bivalent or trivalent bridge and thus form a tridentate, tetradentate, pentadentate or hexadentate ligand system; a substituent can also additionally coordinate to M; where at least one of the group CyC or CyD represents a structure according to formula (Ia) or (Ib) or a preferred embodiment of these structures / compounds.The disclosure of patent application WO 2018 / 001990A1 (with application number PCT / EP2017 / 065763) relating to this application, in particular the disclosure relating to the metal complexes described by formulas (1) and (2), is incorporated by reference into the present application for disclosure purposes. This application is limited to Ir complexes, and the present application encompasses further complexes and is expanded accordingly. In particular, the CyC and CyD groups are exemplified in this application.

[0162] 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.

[0163] Examples of preferred compounds according to the embodiments listed above are the compounds listed in the following table. GO cn o

[0164]

[0165]

[0166] The basic structure of the compounds of the invention can be prepared according to the methods outlined in the following schemes. The individual synthesis steps, such as coupling reactions leading to C–C and / or C–N bond formations, are known in principle to those skilled in the art. These include, among others, reactions according to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA, and HIYAMA.

[0167] Further information on the synthesis of the compounds according to the invention can be found in the synthesis examples.

[0168] The compounds according to the invention can be prepared starting from unfunctionalized or functionalized, in particular chlorine-functionalized, 1,2-dibromobenzenes (1a), 1,8-dibromonaphthalenes (1b) and 2,2'-dibromobiphenyls and derivatives (1c) known from the literature, as shown by way of example in Scheme 1. The compounds according to the invention can also be obtained by processes other than those shown in Scheme 1. Furthermore, Scheme 1 sets out the use of a specific ketone K2, which is not absolutely necessary. Instead, an open-chain or monocyclic ketone can also be used. The same applies to the aromatic or heteroaromatic compounds Ar shown.

[0169] These compounds can first be monolithiated by reaction with n-butyllithium and then reacted with a bi-, tri-, or oligo-cyclic ketone K1 to give the alcohol (2), as described by way of example in step 1. The isolated bromine-functionalized alcohol (2) can in turn be lithiated using two equivalents of n-butyllithium, and the intermediate aryllithium species can then be reacted with the bi-, tri-, or oligo-cyclic ketone K2, as described by way of example in step 2. Alternatively to K2, an open-chain or monocyclic ketone can be used.

[0170] Steps 1 and 2 can also be carried out consecutively without intermediate isolation of the alcohol (2). The diol (3) can then be cyclized under acid catalysis to the ether (4), whereby the water formed can optionally be removed by physical methods (distillative water entrainment, e.g., in a water separator) or captured by chemical methods (water-binding agents, e.g., organic or inorganic anhydride, acetals, orthoesters, etc.), as exemplified in step 3. Finally, the ether (4) can be converted into the compounds (5) according to the invention.

[0171] The activation of unfunctionalized aromatics Ar can be carried out by deprotoborylation, see e.g. TE Hurst et al., Chem. Eur. J., 2010, 16(27), 8155 or DN Coventry et al., Chem. Commun., 2005, (16), 2172. The boronate esters thus obtained can be coupled to the materials according to the invention by means of functionalization reactions familiar to the person skilled in the art, such as Suzuki-type CC couplings, with suitable aryl / heteroaryl halides. The functionalized, in particular chlorine-functionalized, ethers (4) can be converted into the materials according to the invention by means of functionalization reactions familiar to the person skilled in the art, such as CC or CN couplings of the Suzuki, Negishi, Yamamoto-Grignard-Cross, Buchwald-Hartwig, Ullmann, etc. type, with suitable aryl / heteroaryl boronic acids or esters or amines.

[0172] X: CR, NY: single bond, BR, CR2, SiR2, NR, O, S The meaning of the symbols used in the scheme presented above essentially corresponds to those defined for formulas (Ia) and / or (Ib), whereby for reasons of clarity, numbering and a complete representation of all symbols have been omitted and preferred radicals for the group Ar are shown.

[0173] The present invention therefore further provides a process for preparing a compound according to the invention, wherein a compound having an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms is synthesized and reacted with a ketone having a bicyclic alkyl group in the alpha position. In addition to bicyclic ketones, tricyclic or oligocyclic ketones can also be used.

[0174] By these processes, optionally followed by purification, such as recrystallization or sublimation, the compounds according to the invention can be obtained in high purity, preferably more than 99% (determined by 1 H-NMR and / or HPLC).

[0175] The compounds of the invention can also be mixed with a polymer. It is also possible to covalently incorporate these compounds into a polymer. This is particularly possible with compounds substituted by reactive leaving groups, such as bromine, iodine, chlorine, boronic acid, or boronic acid esters, or by reactive, polymerizable groups, such as olefins or oxetanes. These can be used as monomers to produce corresponding oligomers, dendrimers, or polymers. The oligomerization or polymerization preferably takes place via the halogen functionality or the boronic acid functionality, or via the polymerizable group, respectively. It is also possible to crosslink the polymers via such groups. The compounds and polymers of the invention can be used as crosslinked or uncrosslinked layers.

[0176] The invention therefore further provides oligomers, polymers or dendrimers comprising one or more of the above-listed structures of the formulas (Ia) and / or (Ib) and preferred embodiments of this formula or compounds according to the invention, wherein one or more bonds of the compounds according to the invention or of the structures of the formulas (Ia) and / or (Ib) and preferred embodiments of this formula to the polymer, oligomer or dendrimer are present. Depending on the linkage of the structures of the formulas (Ia) and / or (Ib) and preferred embodiments of this formula or of the compounds, these therefore form a side chain of the oligomer or polymer or are linked in the main chain. The polymers, oligomers or dendrimers can be conjugated, partially conjugated or non-conjugated. The oligomers or polymers can be linear, branched or dendritic.The same preferences as described above apply to the repeating units of the compounds according to the invention in oligomers, dendrimers and polymers.

[0177] To prepare the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. Copolymers are preferred, wherein the units according to formulas (Ia) and / or (Ib) or the preferred embodiments described above and below are present in amounts of 0.01 to 99.9 mol%, preferably 5 to 90 mol%, particularly preferably 20 to 80 mol%. Suitable and preferred comonomers which form the polymer backbone are selected from fluorenes (e.g. according to EP 842208 or WO 2000 / 022026), spirobifluorenes (e.g. according to EP 707020, EP 894107 or WO 2006 / 061181), para-phenylenes (e.g. according to WO 92 / 18552), carbazoles (e.g. according to WO 2004 / 070772 or WO 2004 / 113468), thiophenes (e.g. according to EP 1028136), dihydrophenanthrenes (e.g. according to WO 2005 / 014689), cis- and trans-indenofluorenes (e.g. according to WO 2004 / 041901 or WO 2004 / 113412), ketones (e.g. according to WO 2005 / 040302), phenanthrenes (e.g.according to WO 2005 / 104264 or WO 2007 / 017066) or several of these units. The polymers, oligomers and dendrimers can contain further units, for example hole transport units, in particular those based on triarylamines, and / or electron transport units. Of particular interest are also compounds according to the invention which are characterized by a high glass transition temperature. In this context, particular preference is given to compounds according to the invention comprising structures according to the formulas (Ia) and / or (Ib) or the preferred embodiments set out above and below which have a glass transition temperature of at least 70 °C, more preferably of at least 110 °C, most preferably of at least 125 °C and especially preferably of at least 150 °C, determined according to DIN 51005 (version 2005-08).

[0178] 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, a-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, Cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP,p-Cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butylmethyl ether, triethylene glycol butylmethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyloctanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents. The present invention therefore further provides a formulation or composition comprising at least one compound according to the invention and at least one further compound. The further compound can be, for example, a solvent,in particular, one of the above-mentioned solvents or a mixture of these solvents. If the further compound comprises a solvent, this mixture is referred to herein as a formulation. 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 matrix material. Preferably, it can be provided that at least one further compound is selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF, host materials, electron-transport materials, electron-injection materials, hole-conductor materials, hole-injection materials, electron-blocking materials, and hole-blocking materials, preferably host materials.

[0179] The present invention further provides for the use of a compound according to the invention in an electronic device, in particular in an organic electroluminescent device. Preferably, the compounds according to the invention are used in an electronic device as an emitter, host material, hole-conductor material, hole-injection material, electron-blocking material, electron-transport material, electron-injection material, or hole-blocking material. The preferred use depends on the groups the compound contains; in this context, reference is made to the above and following description of the groups the compounds may contain.

[0180] The present invention further relates to an electronic device comprising at least one compound according to the invention. 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.

[0181] Particularly preferably, the electronic device is selected from the group consisting of organic electroluminescent devices (OLEDs, sOLEDs, PLEDs, LECs, etc.), preferably organic light-emitting diodes (OLEDs), organic light-emitting diodes based on small molecules (sOLEDs), organic light-emitting diodes based on polymers (PLEDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers), “organic plasmon emitting devices” (DM Koller et al., Nature Photonics 2008, 1- 4); 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), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs) and organic electrical sensors, preferably organic electroluminescent devices (OLEDs, sOLEDs, PLEDs, LECs, etc.), particularly preferably organic light-emitting diodes (OLEDs), organic light-emitting diodes based on small molecules (sOLEDs), organic light-emitting diodes based on polymers (PLEDs), in particular phosphorescent OLEDs.

[0182] 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 multiple 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 electroluminescent device, particularly for white-emitting OLEDs.

[0183] The compound according to the invention can be used in different layers, depending on the precise structure. An organic electroluminescent device comprising a compound according to formulas (Ia) and / or (Ib) or the preferred embodiments described above is preferred in an emitting layer as a matrix material for phosphorescent emitters or for emitters exhibiting 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-blocking layer.The compound according to the invention is particularly preferably used as a matrix material for phosphorescent emitters, in particular for red, orange, blue, green, or yellow, preferably for blue or green phosphorescent emitters, in an emitting layer, as a host material, electron-transport material, electron-injection material, or hole-blocking material. In a further preferred embodiment, the compound according to the invention can be used as a matrix material for phosphorescent emitters, in particular for red, orange, blue, green, or yellow, preferably for blue or green phosphorescent emitters, in an emitting layer, as a host material, hole-conductor material, hole-injection material, or electron-blocking material.Furthermore, the compound according to the invention can be used in an organic electroluminescent device as a fluorescent emitter, emitter exhibiting TADF, or as a phosphorescent emitter, wherein a previously described metal complex, which is also the subject of the present invention, is preferably used as the phosphorescent emitter.

[0184] Preferably, it can be provided that the organic electroluminescent device comprises at least one emission layer and at least one electron transport layer and the electron transport layer contains the compound according to the present invention.

[0185] If 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, is understood to mean 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.

[0186] 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.

[0187] In one embodiment of the invention, the compound according to the invention is used as the sole matrix material ("single host") for the phosphorescent emitter. A further embodiment of the present invention is the use of the compound according to the invention as a matrix material for fluorescent emitters. Fluorescent emitters are widely known in the art, with preferred examples of fluorescent emitters being listed in the following table. The fluorescent emitters presented above by way of example may preferably have structures according to formulas (Ia) and / or (Ib) or preferred embodiments of these structures, these compounds having the structures according to the invention representing particularly preferred fluorescent emitters of the present invention.

[0188] A further embodiment of the present invention is the use of the compound according to the invention as a matrix material for emitters exhibiting TADF. A further embodiment of the present invention is the use of the compound according to the invention as a matrix material for a fluorescent emitter. Emitters exhibiting TADF are widely known in the art, with preferred examples of fluorescent emitters being listed in the table below.

[0189]

[0190]

[0191] The emitters exhibiting TADF presented above by way of example can preferably have structures according to formulas (Ia) and / or (Ib) or preferred embodiments of these structures, wherein these compounds with the structures according to the invention represent particularly preferred emitters exhibiting TADF of the present invention. A further 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.CBP (N,N-biscarbazolylbiphenyl) or those described in 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. B. according to WO 2007 / 137725, silanes, e.g. B. according to WO 2005 / 111172, azaboroles or boronate esters, e.g. B. according to WO 2006 / 117052, triazine derivatives, e.g. B. 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. B. according to EP 652273 or WO 2009 / 062578, diazasilole or tetraazasilole derivatives, e.g. according to WO 2010 / 054729, diazaphosphole derivatives, e.g. 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 , dibenzofuran derivatives, e.g. according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565 or biscarbazoles, e.g. according to JP 3139321 B2.

[0192] Likewise, another phosphorescent emitter which emits at a shorter wavelength than the actual emitter can be present in the mixture as a co-host. Particularly good results are achieved when a red phosphorescent emitter is used as the emitter and a yellow phosphorescent emitter is used as the co-host in combination with the compound according to the invention. Furthermore, a compound which does not participate, or does not participate to a significant extent, in charge transport can be used as the co-host, as described, for example, in WO 2010 / 108579. In particular, compounds which have a large band gap and themselves do not participate, or at least not participate to a significant extent, in the charge transport of the emitting layer are suitable as co-matrix material in combination with the compound according to the invention. Such materials are preferably pure hydrocarbons.Examples of such materials can be found, for example, in WO 2009 / 124627 or WO 2010 / 006680. In this context, it should be noted that compounds according to the invention without specific functional groups, such as hole-transport groups and / or electron-transport groups, exhibit advantageous properties.

[0193] 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.

[0194] 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 and WO 2018 / 011186. In general, all phosphorescent complexes as used according to the prior art for phosphorescent electroluminescent devices 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.

[0195] Examples of phosphorescent dopants are listed in the following table.

[0196]

[0197] The phosphorescent dopants presented above by way of example may preferably have structures according to formulas (Ia) and / or (Ib) or preferred embodiments of these structures, these compounds having the structures according to the invention representing particularly preferred metal complexes of the present invention.

[0198] The compounds of the invention are also particularly suitable as matrix materials for phosphorescent emitters in organic electroluminescent devices, as described, for example, in WO 98 / 24271, US 2011 / 0248247, and US 2012 / 0223633. In these multi-color display components, an additional blue emission layer is vapor-deposited over the entire surface of all pixels, even those with a color other than blue.

[0199] In a further embodiment of the invention, the organic electroluminescent device according to the invention does not contain a separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, i.e. the emitting layer directly adjoins the hole injection layer or the anode, and / or the emitting layer directly adjoins the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051. Furthermore, it is possible to use a metal complex that is the same as or similar to the metal complex in the emitting layer as a hole transport or hole injection material directly adjacent to the emitting layer, as described, for example, in WO 2009 / 030981.

[0200] In the further layers of the organic electroluminescent device according to the invention, all materials commonly used in the prior art can be used. Therefore, without inventive effort, the skilled person can use all materials known for organic electroluminescent devices in combination with the compounds according to the invention according to formulas (Ia) and / or (Ib) or the preferred embodiments described above.

[0201] Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10' 5 mbar, preferably less than 10' 6 mbar. However, it is also possible that the initial pressure is even lower, for example less than 10' 7 mbar.

[0202] 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 sublimated at a pressure between 10' 5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured.

[0203] 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.

[0204] Formulations for applying a compound according to formula (Ia) and / or (Ib) or the preferred embodiments thereof set out above are novel. A further subject of the present invention is therefore a formulation comprising at least one solvent and a compound according to formula (Ia) and / or (Ib) or the preferred embodiments thereof set out above.

[0205] 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.

[0206] These processes are generally known to the person skilled in the art and can be applied by him without inventive step to organic electroluminescent devices containing the compounds according to the invention.

[0207] The compounds of the invention and the organic electroluminescent devices of the invention are distinguished from the prior art in particular by a low refractive index (RI). Furthermore, these compounds and the organic electroluminescent devices obtainable therefrom exhibit an improved lifetime. The other electronic properties of the electroluminescent devices, such as efficiency or operating voltage, remain at least equally good. In a further variant, the compounds of the invention and the organic electroluminescent devices of the invention are distinguished from the prior art in particular by improved efficiency and / or operating voltage and a longer lifetime.

[0208] 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:

[0209] 1. Electronic devices, in particular organic electroluminescent devices comprising compounds according to formulas (Ia) and / or (Ib) or the preferred embodiments described above and below, in particular as emitters, as matrix materials, as hole-conducting materials, or as electron-conducting materials, exhibit excellent efficiency. Compounds according to the invention according to formulas (Ia) and / or (Ib) or the preferred embodiments described above and below achieve a low operating voltage when used in electronic devices.

[0210] 2. Electronic devices, in particular organic electroluminescent devices comprising compounds according to formulas (Ia) and / or (Ib) or the preferred embodiments described above and below, in particular as emitters, as matrix materials, as hole-conducting materials, or as electron-conducting materials, exhibit a very good lifetime. These compounds, in particular, result in low roll-off, i.e., a low drop in the power efficiency of the device at high luminance levels.

[0211] 3. The compounds according to the invention according to formulas (Ia) and / or (Ib) or the preferred embodiments described above and below show a very high stability and lifetime.

[0212] 4. Electronic devices, in particular organic electroluminescent devices comprising compounds according to formulas (Ia) and / or (Ib) or the preferred embodiments described above and below, in particular as emitters, as matrix materials, as hole-conducting materials, or as electron-conducting materials, have very low refractive indices. 5. Electronic devices, in particular organic electroluminescent devices comprising compounds according to formulas (Ia) and / or (Ib) or the preferred embodiments described above and below, in particular as emitters or as matrix materials, have very high color purity.

[0213] 6. Using compounds according to formulas (Ia) and / or (Ib) 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.

[0214] 7. Compounds according to formulas (Ia) and / or (Ib) or the preferred embodiments described above and below have excellent glass film formation.

[0215] 8. Compounds according to formulas (Ia) and / or (Ib) or the preferred embodiments described above and below form very good films from solutions.

[0216] These advantages mentioned above are not accompanied by an excessive deterioration of the other electronic properties.

[0217] 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.

[0218] 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).

[0219] It should further be noted that many of the features, and in particular those of the preferred embodiments of the present invention, are inventive in their own right and should not be considered merely part of the embodiments of the present invention. Independent protection may be sought for these features in addition to or alternatively to any presently claimed invention.

[0220] The teaching of technical action disclosed in the present invention can be abstracted and combined with other examples.

[0221] The invention is further illustrated by the following examples, without intending to limit it. From these descriptions, one skilled in the art can practice the invention within the entire disclosed scope and, without inventive step, prepare further compounds according to the invention and use them in electronic devices or apply the method according to the invention.

[0222] Examples:

[0223] Unless otherwise stated, the following syntheses were carried out under a protective gas atmosphere in dried solvents. The 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 isomeric, enantiomeric, diastereomeric, or tautomeric forms, one form is shown as a representative example.

[0224] A: Literature-known synthons, bromides LB and ketones LK:

[0225] A well-stirred mixture of 24.1 g (100 mmol) LB1, 250 ml tetrahydrofuran (THF) and 250 ml diethyl ether is treated dropwise over a period of 10 minutes with 40.0 ml of n-butyllithium 2.5 M in n-hexane, cooled to -110 °C, while keeping the temperature below -100 °C. The mixture is stirred for 30 minutes at -110 °C, and then a solution of 15.0 g (100 mmol) LK7 in 50 ml THF is added dropwise over a period of 20 minutes, while keeping the temperature below -100 °C. The reaction mixture is stirred for 1 hour at -110 °C, the cooling bath is removed and the mixture is allowed to warm slowly to RT. The mixture is quenched by adding 200 ml saturated ammonium chloride solution, and the org. The organic phase was separated, the organic phase was evaporated to dryness, and the residue was chromatographed using a Torrent column chromatography system from A. Semrau. Yield: 24.2 g (78 mmol) 78%. Purity: 97% n. 1 H-NMR.

[0226] A well-stirred mixture of 24.1 g (100 mmol) of S1a, 250 ml of tetrahydrofuran (THF), and 250 ml of diethyl ether, cooled to -78 °C, is treated dropwise with 80.0 ml (200 mmol) of n-butyllithium 2.5 M in n-hexane over a period of 20 minutes, while keeping the temperature below -70 °C. The mixture is stirred for 30 minutes at -78 °C, and then a solution of 15.0 g (100 mmol) of LK7 in 50 ml of THF is added dropwise over a period of 15 minutes, while keeping the temperature below -70 °C. The reaction mixture is stirred for 1 hour at -78 °C, the cooling bath is removed, and the mixture is allowed to warm slowly to room temperature. The mixture is quenched by adding 200 ml of saturated ammonium chloride solution, and the organic phase is separated. The organic phase is separated, dried over magnesium sulfate, and the organic phase is evaporated to dryness at a maximum of 30 °C in vacuo. The residue is taken up in approximately 250 ml of warm n-heptane, triturated, and cooled overnight at -25 °C. The crystals are filtered off with suction, washed once with a small amount of n-heptane, and dried in vacuo.A second crystal fraction can be obtained from the mother liquor. Yield: 20.6 g (54 mmol) 54%. Purity: 97% n. 1 H-NMR. c) S1:

[0227] A well-stirred mixture of 37.9 g (100 mmol) of S1b, 3.0 g of Amberlyst R 15 (hydrogen form), and 500 ml of toluene was heated on a water separator until the reaction was complete (approx. 2 h). The mixture was allowed to cool to room temperature, filtered off the Amberlyst, and the filtrate was evaporated to dryness. The residue was chromatographed on a Torrent column system from A. Semrau. Yield: 16.6 g (82 mmol), 82%. Purity: 98% n. 1 H-NMR.

[0228] The following connections can be represented analogously.

[0229]

[0230] Procedure analogous to WO2012068589. Instead of PCy3, S-Phos can be used for chlorides. 36.0 g (100 mmol) of S2 was used. Yield: 45.3 g (93 mmol) 93%; purity approx. 97%. 1 H-NMR.

[0231]

[0232] Preparation analogous to Y. Hu et al., ACS Appl. Polymer Mater. 2019, 1 (2), 221, Compound 8. 1.05 eq of NBS was used, and the crude product was purified by chromatography (Torrent column system from A. Semrau). Batch: 52.8 g (100 mmol) of S15. Yield: 56.8 g (90 mmol), 90%. Purity: 97% (nn). 1 H-NMR.

[0233] C: Preparation of synthons S and the compounds according to the invention E: Example E1 : Preparation analogous to a) JF Hartwig et al., J. Org. Chem. 1999, 64(15), 5575, b) M. Watanabe et al., Tetrahedron Lett. 2000, 41 (4), 481 , c) Y. Zhang et al., Chem. Sci. 2023, 14(19), 5125. As an alternative to tri-tert-butylphosphine, other electron-rich phosphines such as SPhos, AmPhos, RuPhos, etc. can be used. Analogous to a): 39.5 g (100 mmol) S2 and 32.1 g (100 mmol) bis(4-biphenylyl)amine [102113-98-4]. Purification is carried out by repeated hot extraction crystallization (conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) or chromatography and fractional sublimation or annealing under high vacuum. Yield: 57.0 g (84 mmol) 84%; Purity: > 99.9% by HPLC.

[0234]

[0235] A well-stirred solution of 39.4 g (100 mmol) of S2, 44.1 g (110 mmol) of B-[4-[bis([1,1'-biphenyl]-4-yl)amino]phenyl]boronic acid [943836-24-6], 42.4 g (200 mmol) of tripotassium phosphate [7778-53-2], 1.64 g (4 mmol) of SPhos [657408-07-6], 449 mg (2 mmol) of palladium(II) acetate, 400 ml of toluene, 100 ml of dioxane, and 300 ml of water is heated under reflux for 24 h. After cooling, the organic phase is separated, washed three times with 300 ml of water each time, once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is removed by filtration, the filtrate is concentrated to dryness, and the residue is chromatographed (Torrent column from A. Semrau). Further purification of the crude product is carried out by chromatography and / or repeated hot extraction crystallization (conventional 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: 52.3 g (69 mmol) 69%; Purity: approximately 99.9% pure.HPLC.

[0236] Analogously, the following compounds can be prepared by adjusting the stoichiometry of the reactants

[0237]

[0238] A solution of 45.2 g (105 mmol) of S16 in 300 ml of DMF is treated portionwise with 2.4 g (100 mmol) of sodium hydride (caution: evolution of hydrogen!). Then, 37.8 g (110 mmol) of 2-[1,1'-biphenyl]-4-yl-4-chloro-6-phenyl-1,3,5-triazine [1472062-94-4] is added, and the mixture is stirred for 2 h at room temperature and for 3 h at 50 °C. While stirring, 2000 ml of water is added dropwise. The precipitated solid is filtered off, washed three times with 100 ml of water each time, twice with 100 ml of ethanol each time, and dried in vacuo. The solid is dissolved in dichloromethane and filtered through a silica gel bed pre-slurried with DCM. The filtrate is slowly concentrated in a rotary evaporator, continuously replacing the distilled DCM with ethanol. The crystallized product is collected, washed twice with 50 ml of ethanol each time, and dried under vacuum. Further purification of the crude product is carried out by chromatography and / or repeated hot extraction crystallization (standard organic solvents).Solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) and fractional sublimation or annealing under high vacuum. Yield: 53.0 g (70 mmol) 70%; Purity: approx. 99.9% by HPLC.

[0239]

[0240] Preparation analogous to S. Oda et al., Angew. Chem. Int. Ed. 2021, 60, 2882, compound "CzDABNA-NP-M / TB". Preparation: 9.8 g (10 mmol) S300, yield: 4.0 g (4.1 mmol), 41%; purity: > 99.5% by HPLC.

[0241]

[0242] Example: Production of OLEDs

[0243] 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).

[0244] The following examples present the results of various OLEDs. Cleaned glass plates (cleaned in a Miele laboratory dishwasher, cleaner Merck Extran) coated with structured ITO (indium tin oxide) with a thickness of 50 nm 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 fluorescence OLED components - BF: The compounds E according to the invention can be used in the hole transport layer (HTL), electron blocking layer (EBL), 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 (dopant, emitter) D, which is added to the matrix material oris added to the matrix materials by co-evaporation in a specific volume fraction. A specification such as SMB:D (95%:5%) means that the SMB material is present in the layer at a volume fraction of 95% and the dopant D at a volume fraction of 5%. 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 or refer to the previously presented synthesis examples.

[0245] 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 (IUL) curves assuming a Lambertian radiation pattern. The EQE (%) and voltage (V) are expressed at a luminance of 1000 cd / m². 2

[0246] The OLEDs have the following layer structure:

[0247] Substrat

[0248] Hole injection layer (HIL) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0249] Hole transport layer (HTL), made of HTM1, 180 nm

[0250] Electron blocking layer (EBL), see Table 1

[0251] Emission layer (EML), see Table 1

[0252] Hole blocking layer (HBL), see Table 1

[0253] Electron transport layer (ETL), see Table 1 Electron injection layer (EIL) made of ETM2, 1 nm

[0254] Cathode made of aluminum, 100 nm b) Phosphorescent OLED components:

[0255] The compounds E according to the invention can be used in the hole transport layer (HTL), electron blocking layer (EBL), hole blocking layer (HBL), electron transport layer (ETL), and in the emission layer (EML) as hole-conducting or electron-conducting matrix material (host material) (hTMM or 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 fabricate the OLEDs are shown in Table 5 or refer to the synthesis examples presented previously.

[0256] 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 (IUL) curves assuming a Lambertian radiation pattern. The EQE (%) and voltage (V) are expressed at a luminance of 1000 cd / m². 2

[0257] The OLEDs have the following layer structure:

[0258] Substrate hole injection layer (HIL) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0259] Hole transport layer (HTL) made of HTM1, 180 nm for blue, 50 nm for green, yellow and red

[0260] Electron blocking layer (EBL), see Table 3

[0261] Emission layer (EML), see Table 3

[0262] Hole blocking layer (HBL), see Table 3

[0263] Electron transport layer (ETL), see Table 3 Electron injection layer (EIL) made of ETM2, 1 nm

[0264] Cathode made of aluminum, 100 nm

Claims

Patent claims 1 . A compound comprising at least one structure of formula (Ia) or formula (Ib), where the symbols are: Z stands for a group -(CR b 2)n-, where n is an integer in the range from 1 to 6; W stands for a group -(CR b 2)m-, where m is an integer in the range from 1 to 6, where the group W can be bridged to the group Z via one or more groups V, where V on each occurrence, identically or differently, represents a single bond or an alkylene group having 1 to 40 C atoms which reacts with one or more radicals R 2 may be substituted and wherein one or more non-adjacent CH2 groups are substituted 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; Ar is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, the radical Ar may be coordinated to a transition metal; R a is at each occurrence, identically or differently, H, D, F, a straight-chain alkyl group having 1 to 40 C atoms, a branched or cyclic alkyl group having 3 to 40 C atoms, each of which is substituted by one or more radicals R b may be substituted, or an aromatic or heteroaromatic ring system with 5 to 60, each substituted with one or more radicals R 1 can be substituted, two radicals R a form a ring system with each other; R bis at each occurrence, identically or differently, H, D, F, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, each of which is substituted by one or more radicals R 2 can be substituted, two or more radicals R b form a ring system with each other; R c is at each occurrence, identically or differently, H, D, F, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 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; two or more radicals R c form a ring system with each other; R is, at each occurrence, the same or different, H, D, OH, F, CI, Br, I, CN, NO2, N(Ar')2, N(R 1 )2, C(=O)N(Ar')2, C(=O)N(R 1 )2, C(Ar')3, C(R 1 )3, Si(Ar')3, Si(R 1 )3, B(Ar')2, B(R 1 )2, C(=O)Ar', C(=O)R 1 , P(=O)(Ar')2, P(=O)(R 1 )2, P(Ar')2, P(R 1 )2, S(=O)Ar', S(=O)R 1 , S(=O)2Ar', S(=O)2R 1 , OSO2Ar', OSO2R 1 , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group is each substituted with one or more radicals R 1 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by R 1 C=CR 1 , C=C, Si(R 1 )2, C=O, C=S, C=Se, C=NR 1, -C(=O)O-, -C(=O)NR 1 -, NR 1 , P(=O)(R 1 ), -O-, -S-, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 1 can be substituted, two radicals R can also be substituted with each other or a radical R can be substituted with another group, in particular a radical R b form a ring system, whereby the radical R can be coordinated to a transition metal; Ar' is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is substituted with one or more radicals R 1may be substituted, whereby two radicals Ar' which bind to the same C-atom, Si-atom, N-atom, P-atom or B-atom may also be substituted by a single bond or a bridge selected from B(R 1 ), C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, O, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 , are bridged to each other, whereby the residue Ar' can be coordinated to a transition metal; R 1 is, at each occurrence, the same or different: H, D, F, CI, Br, I, 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 or more residues R 2 may be substituted, wherein one or more non-adjacent CH2 groups are substituted by - R 2 C=CR 2 -, -CEC-, 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 where one or more H atoms can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each substituted by one or more radicals R 2 may be substituted, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2 may be substituted, or an aralkyl or heteroaralkyl group having 5 to 60 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 radicals R 1form a ring system, whereby one or more residues R 1 form a ring system with another part of the compound, whereby the residue R 1 be coordinated to a transition metal; Ar” is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is substituted by one or more radicals R 2 may be substituted, whereby two radicals Ar” which bind to the same C-atom, Si-atom, N-atom, P-atom or B-atom can also be linked by a single bond or a bridge selected from B(R 2 ), C(R 2 )2, Si(R 2 )2, C=O, C=NR 2 , C=C(R 2 )2, O, S, S=O, SO2, N(R 2 ), P(R 2 ) and P(=O)R 2 , are bridged to each other, whereby the residue Ar" can be coordinated to a transition metal; R 2is selected, identically or differently at each occurrence, from the group consisting of 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, in which 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 substituents R 2 form a ring system with each other.

2. Compound according to claim 1, characterized in that the sum of the indices m and n is 3 to 6 3. A compound according to claim 1 or 2, comprising at least one structure of formulas (Ia-1) to (Ib-7), where the symbols R, R a , R b, W and Z have the meanings given in claim 1 and the following applies to the other symbols: Y is, identically or differently at each occurrence, O, S, NR, Si(R)2, C(R)2 or an ortho-linked phenylene group which may be substituted by one or more radicals R; Y 1 is, at each occurrence, the same or different, C(R)2, Si(R)2, C=O, P(O)R, P(R), O, S, NR or BR; and X is the same or different CR or N at each occurrence.

4. A compound according to one or more of claims 1 to 3, comprising at least one structure of the formulas (IIa-1) to (IIb-7), where the symbols R, R a , R b , W, and Z have the meanings given in claim 1, the symbols Y and Y 1have the meanings given in claim 3 and the following applies to the further symbols: j is, at each occurrence, independently 0, 1, 2 or 3; h is, at each occurrence, independently 0, 1, 2, 3 or 4; and g is, at each occurrence, independently 0, 1, 2, 3, 4 or 5.

5. A compound according to one or more of claims 1 to 4, comprising at least one structure of the formulas (III-1) to (III-4), where the symbols R, R a , R b , W, and Z have the meanings given in claim 1 and the following applies to the other symbols: Y 2 is the same or different at each occurrence B(R 1 ), C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, 0, S, S=0, S02, N(R 1 ), P(R 1 ) and P(=O)R 1 ; Y 3 is the same or different at each occurrence B(R 1 ), C(R 1 )2, Si(R 1)2, 0=0, C=NR 1 , C=C(R 1 )2, 0, S, S=0, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 ; and j is 0, 1, 2, or 3 independently at each occurrence.

6. Compound according to one or more of claims 1 to 5, characterized in that the radicals Z and W are substituted by the CR b - Groups or the CR b -Group and the CR b 2-group and the C-atom to which the CR b -group, form a partial structure of the formulas (RC-1 ) to (RC-10) where R b has the meaning set out in claim 1, the dashed bonds represent the attachment points to the oxygen atom and the group Ar, and the further symbols have the following meaning: r is 0, 1, 2, 3, 4, 5 or 6; s is 0, 1, 2, 3, 4, 5, 6, 7 or 8; t is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; v is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

7. A compound according to one or more of claims 1 to 6, comprising at least one structure of the formulas (IV-1) to (IV-16), where the symbols R, R a and R b have the meanings given in claim 1, the symbols Y and Y 1 have the meanings given in claim 3 and the following applies to the further symbols: j is independently 0, 1, 2 or 3 at each occurrence; h is independently 0, 1, 2, 3 or 4 at each occurrence; r is 0, 1, 2, 3, 4, 5 or 6; and v is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

8. A compound according to claim 6 or 7, characterized in that the two radicals R a form a partial structure of the formulas (RC-1) to (RC-10).

9. A compound according to at least one of the preceding claims 1 to 8, characterized in that the groups R bonded to a C atom aare selected from straight-chain alkyl groups having 1 to 10 C atoms or branched or cyclic alkyl groups having 3 to 10 C atoms, each of which is substituted by one or more radicals R b may be substituted, or a phenyl group, each substituted with one or more radicals R 1 may be substituted, preferably deuterated, the groups R bonded to a C atom may be a form a ring system with each other, where in the case that R a each represents a phenyl group, the phenyl groups being connected via a single bond or a bridge selected from C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, O, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 O can be bridged together.

10. A compound according to at least one of the preceding claims 1 to 9, characterized in that the group R bstands for H, D, methyl, ethyl, propyl, where these groups may be deuterated.

11. Oligomer, polymer or dendrimer containing one or more compounds according to any one of claims 1 to 10, wherein instead of a hydrogen atom or a substituent, one or more bonds of the compounds to the polymer, oligomer or dendrimer are present.

12. Formulation comprising at least one compound according to one or more of claims 1 to 10 or an oligomer, polymer or dendrimer according to claim 11 and at least one further compound, wherein the further compound is preferably selected from one or more solvents.

13. A composition comprising at least one compound according to one or more of claims 1 to 10 or an oligomer, polymer or dendrimer according to claim 11 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF, host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocking materials and hole blocking materials.

14. A process for preparing a compound according to one or more of claims 1 to 10, characterized in that a compound having an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms is synthesized and reacted with a ketone having a bicyclic alkyl group in the alpha position.

15. Use of a compound according to one or more of claims 1 to 10 or of an oligomer, polymer or dendrimer according to claim 11 in an electronic device, preferably as an emitter, host material, hole conductor material, hole injection material, electron blocking material, electron transport material, electron injection material or hole blocking material.

16. Electronic device comprising at least one compound according to one or more of claims 1 to 10 or an oligomer, polymer or dendrimer according to claim 11.

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