CN115244728A

CN115244728A - Use of sulfone compounds in organic electronic devices

Info

Publication number: CN115244728A
Application number: CN202180018027.1A
Authority: CN
Inventors: 菲利普·斯托塞尔
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2020-03-02
Filing date: 2021-02-26
Publication date: 2022-10-25
Also published as: EP4115457A1; WO2021175706A1

Abstract

The present invention relates to the use of compounds in electronic devices. The invention also relates to novel compounds, in particular for use in electronic devices, and to electronic devices comprising these compounds.

Description

Use of sulfone compounds in organic electronic devices

The invention describes the use of sulfone compounds in organic electronic devices. The invention also relates to novel sulfone compounds and methods of making the compounds of the invention as well as electronic devices comprising these compounds.

The structure of organic electroluminescent devices in which organic semiconductors are used as functional materials is described, for example, in US 4539507, US 5151629, EP 0676461, WO 98/27136 and WO 2010/151006 A1. The light-emitting materials used are generally organometallic complexes which exhibit phosphorescence. For quantum mechanical reasons, up to four times the energy and power efficiency can be achieved using organometallic compounds as phosphorescent emitters. In general, there is still a need for improvement in electroluminescent devices, especially in electroluminescent devices exhibiting phosphorescence, for example in terms of efficiency, operating voltage and lifetime. Furthermore, organic electroluminescent devices are known which comprise fluorescent emitters or emitters which exhibit TADF (thermally activated delayed fluorescence).

The performance of an organic electroluminescent device depends not only on the luminophor used. Of particular importance here are also the other materials used, for example host/matrix materials, hole-blocking materials, electron-transport materials, hole-transport materials and electron-or exciton-blocking materials. Improvements to these materials can lead to significant improvements in electroluminescent devices.

In general, there is still a need for improvements, in particular in terms of lifetime, and in terms of efficiency and operating voltage of the devices, in the case of these materials, for example for use as emitters, preferably as fluorescent emitters, or as matrix materials, hole-transporting materials or electron-transporting materials. Furthermore, the compounds should have a high color purity.

It is a further object of the present invention to provide compounds which are suitable for use in organic electronic devices, in particular in organic electroluminescent devices, as fluorescent emitters or emitters exhibiting TADF (thermally activated delayed fluorescence) and which when used in such devices result in good device performance, and to provide corresponding electronic devices.

It is therefore an object of the present invention to provide compounds which are suitable for use in organic electronic devices, in particular in organic electroluminescent devices, and which lead to good device properties when used in such devices, and to provide corresponding electronic devices.

It is a particular object of the present invention to provide compounds which lead to a high lifetime, good efficiency and low operating voltage. In particular, the properties of the host material, the hole transport material or the electron transport material also have a crucial influence on the lifetime and efficiency of the organic electroluminescent device.

Another problem solved by the present invention may be considered to be to provide compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, in particular as matrix materials. More particularly, the problem addressed by the present invention is to provide a matrix material suitable for use in red, yellow and blue phosphorescent electroluminescent devices.

In addition, the compounds, especially when they are used as matrix materials, hole transport materials or electron transport materials in organic electroluminescent devices, will lead to devices with excellent color purity.

Furthermore, the compounds should be processable in a very simple manner and, in particular, exhibit good solubility and film-forming properties. For example, the compounds should exhibit increased oxidative stability and improved glass transition temperatures.

Another object may be considered to be to provide electronic devices with excellent performance as cheaply and at constant quality as possible.

Furthermore, it should be possible to use or adapt the electronic device for many purposes. More particularly, the performance of the electronic device should be maintained over a wide temperature range.

Surprisingly, it has been found that specific compounds, described in detail below, solve these problems and eliminate the disadvantages of the prior art. The use of said compounds leads to very good properties of the organic electronic devices, in particular of the organic electroluminescent devices, in particular with respect to lifetime, efficiency and operating voltage. The invention therefore provides electronic devices, in particular organic electroluminescent devices, comprising such compounds, and corresponding preferred embodiments.

The present invention therefore provides the use of a compound comprising at least one structure of formula (I), preferably a compound of formula (I), in an organic electronic device,

wherein:

w is C = O, C = N-Ar or SO ₂ ；

Ar is identical or different on each occurrence and is an aromatic or heteroaromatic ring system which has from 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups; the Ar group may here form a ring system with at least one second Ar group, R group, X group or another group;

x is N or CR, with the proviso that no more than two X groups in a ring are N;

r is identical or different on each occurrence and is H, D, OH, F, cl, br, I, CN, NO ₂ ，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) ₂ Ar'，S(＝O) ₂ R ¹ ，OSO ₂ Ar'，OSO ₂ R ¹ A linear alkyl, alkoxy or thioalkoxy group having from 1 to 40 carbon atoms, or an alkenyl or alkynyl group having from 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group can be substituted in each case by one or more R ¹ Substituted by radicals in which one or more non-adjacent CH ₂ The group can be represented 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 SO ₂ Instead of, or with 5 to 60 aromatic ring atoms and may in each case be substituted by one or more R ¹ Aromatic or heteroaromatic ring systems substituted by radicals, or having 5 to 60 aromatic ring atoms and which may be substituted by one or more R ¹ A group-substituted aryloxy or heteroaryloxy group; at the same time, two R groups may also form a ring system together or with further groups;

ar' is identical or different on each occurrence and is an aromatic ring having 5 to 60 aromatic ring atoms and may be substituted by one or more R ¹ Radical-substituted aromatic or heteroAn aromatic ring system; also, the two Ar' groups bound to the same carbon, silicon, nitrogen, phosphorus or boron atom may be via a bridging group by a single bond or 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、SO ₂ 、N(R ¹ )、P(R ¹ ) And P (= O) R ¹ Are linked together;

R ¹ in each case identical or different and are H, D, F, cl, br, I, CN, NO ₂ ，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 linear alkyl, alkoxy or thioalkoxy group having from 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 40 carbon atoms, or an alkenyl group having from 2 to 40 carbon atoms, each of which may be substituted by one or more R ² Substituted by radicals in which one or more non-adjacent CH ₂ The group may be represented 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 SO ₂ And in which one or more hydrogen atoms may be replaced by D, F, cl, br, I, CN or NO ₂ Instead of, or with 5 to 60 aromatic ring atoms and may in each case be substituted by one or more R ² Aromatic or heteroaromatic ring systems substituted by radicals, or having 5 to 60 aromatic ring atoms and which may be substituted by one or more R ² Aryloxy or heteroaryloxy radical substituted by radicals, or having 5 to 60 aromatic ring atoms and which may be substituted by one or more R ² A group-substituted aralkyl or heteroaralkyl group, or a combination of these systems; at the same time, two or more preferably adjacent R ¹ The groups may together form a ring system;at the same time, one or more R ¹ A group may form a ring system with another part of the compound;

ar "is identical or different on each occurrence and is a substituted or unsubstituted aromatic ring having from 5 to 30 aromatic ring atoms and may be substituted by one or more R ² A group-substituted aromatic or heteroaromatic ring system; also, the two Ar' groups bonded to the same carbon, silicon, nitrogen, phosphorus or boron atom may be via a bridging group by a single bond or 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、SO ₂ 、N(R ² )、P(R ² ) And P (= O) R ² Are linked together;

R ² identical or different on each occurrence and selected from H, D, F, CN, an aliphatic hydrocarbon radical having from 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, in which one or more hydrogen atoms may be replaced by D, F, cl, br, I or CN and which may be substituted by one or more alkyl radicals, each having from 1 to 4 carbon atoms; at the same time, two or more preferably adjacent substituents R ² May together form a ring system.

The compounds of the invention can preferably be used as active compounds in electronic devices. The active compounds are generally organic or inorganic materials, such as charge injection, charge transport or charge blocking materials, but especially light-emitting materials and matrix materials, which are introduced, for example, between the anode and the cathode in organic electronic devices, especially in organic electroluminescent devices. Organic materials are preferred here.

The compounds used according to the invention are preferably purely organic compounds. A purely organic compound is a compound that is not associated with a metal atom, i.e., a compound that does not form a coordination compound or a covalent bond with a metal atom. The pure organic compound here preferably does not contain any metal atoms used in phosphorescent emitters. These metals, such as copper, molybdenum, etc., and in particular rhenium, ruthenium, osmium, rhodium, iridium, palladium, will be discussed in detail later.

The compounds which can be used as active compounds in the organic electronic device can preferably be selected from fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, exciton blocking materials, electron injection materials, hole transport materials, hole injection materials, n-type dopants, p-type dopants, wide band gap materials, electron blocking materials and/or hole blocking materials. Preferred here are fluorescent emitters, emitters which exhibit TADF (thermally activated delayed fluorescence), host materials, electron transport materials, exciton blocking materials, electron injection materials, hole transport materials, hole injection materials, n-type dopants, p-type dopants, wide band gap materials, electron blocking materials and/or hole blocking materials. Especially preferably, the compounds comprising the structure of formula (I), preferably the compounds of formula (I), as detailed above are used as host materials, electron transport materials, hole blocking materials and/or emitters showing TADF (thermally activated delayed fluorescence), more preferably as host materials for phosphorescent emitters, and especially preferably if W is C = O or SO ₂ And then used as a host material for a blue phosphorescent emitter.

In the context of the present invention, adjacent carbon atoms are carbon atoms directly bonded to each other. In addition, "adjacent groups" in the group definitions means that these groups are bonded to the same carbon atom or adjacent carbon atoms. These definitions apply in particular correspondingly to the terms "adjacent group" and "adjacent substituent".

In the context of the present specification, the wording that two or more groups may together form a ring is to be understood as meaning in particular that the two groups are connected to each other by a chemical bond and formally eliminate two hydrogen atoms. This is illustrated by the following scheme:

however, in addition, the above wording is also understood to mean that if one of the two groups is hydrogen, the second group is bonded to the bonding position of the hydrogen atom, thereby forming a ring. This will be illustrated by the following scheme:

a fused aryl group, a fused aromatic ring system or a fused heteroaromatic ring system in the context of the present invention is a group in which two or more aromatic groups are fused (i.e. condensed) to each other along a common edge, so that for example two carbon atoms belong to at least two aromatic or heteroaromatic rings, as is the case for example in naphthalene. In contrast, for example, fluorene is not a fused aryl group in the context of the present invention because the two aromatic groups in fluorene do not have a common edge. The corresponding definitions apply to heteroaryl groups and to fused ring systems which may contain, but not necessarily also, heteroatoms.

If two or more preferably adjacent R, R ¹ And/or R ² The radicals together form a ring system, the result may then be a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system.

An aryl group in the context of the present invention contains from 6 to 60 carbon atoms, preferably from 6 to 40 carbon atoms, more preferably from 6 to 30 carbon atoms; heteroaryl groups in the context of the present invention contain from 2 to 60 carbon atoms, preferably from 2 to 40 carbon atoms, more preferably from 2 to 30 carbon atoms, and at least one heteroatom, with the proviso that the sum of carbon 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 here to mean a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.

An aromatic ring system in the context of the present invention contains from 6 to 60 carbon atoms, preferably from 6 to 40 carbon atoms, more preferably from 6 to 30 carbon atoms in the ring system. A heteroaromatic ring system in the context of the present invention contains from 1 to 60 carbon atoms, preferably from 1 to 40 carbon atoms, more preferably from 1 to 30 carbon atoms, and at least one heteroatom in the ring system, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the context of the present invention is understood to mean the following systems: it need not contain only aryl or heteroaryl groups, but wherein a plurality of aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of atoms other than H), for example carbon, nitrogen or oxygen atoms or carbonyl groups. For example, also aromatic ring systems such as 9,9' -spirobifluorene, 9-diarylfluorene, triarylamines, diaryl ethers, stilbene etc. should therefore be regarded in the context of the present invention, as well as systems in which two or more aryl groups are interrupted by, for example, a linear or cyclic alkyl group or by a silyl group. In addition, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, such as biphenyl, terphenyl, quaterphenyl or bipyridyl, are likewise to be regarded as aromatic or heteroaromatic ring systems.

Cyclic alkyl, alkoxy or thioalkoxy groups in the context of the present invention are understood to mean monocyclic, bicyclic or polycyclic groups.

In the context of the present invention, wherein the individual hydrogen atoms or CH ₂ C whose radicals may also be substituted by the radicals mentioned ₁ To C ₂₀ Alkyl radicals are understood as meaning, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo [ 2.2.2.2 ] cyclo]Octyl, 2-bicyclo [2.2.2 ]]Octyl, 2- (2, 6-dimethyl) octyl, 3- (3, 7-dimethyl) octyl, adamantyl, trifluoromethyl, pentafluoroethyl 2, 2-trifluoroethyl, 1-dimethyl-n-hex-1-yl, 1-dimethyl-n-hept-1-yl, 1-dimethyl-n-oct-1-yl 1, 1-dimethyl-n-decan-1-yl, 1-dimethyl-n-dodecane-1-yl, 1-dimethyl-n-tetradecan-1-yl 1, 1-dimethyl-n-hexadecan-1-yl, 1-dimethyl-n-octadecan-1-yl, 1-diethyl-n-hexyl-1-yl, 11-diethyl-n-hept-1-yl, 1-diethyl-n-oct-1-yl, 1-diethyl-n-decan-1-yl, 1-diethyl-n-dodecane-1-yl, 1-diethyl-n-tetradec-1-yl, 1-diethyl-n-hexadecan-1-yl 1, 1-diethyl-n-octadecan-1-yl, 1- (n-propyl) cyclohex-1-yl, 1- (n-butyl) cyclohex-1-yl, 1- (n-hexyl) cyclohex-1-yl, 1- (n-octyl) cyclohex-1-yl and 1- (n-decyl) cyclohex-1-yl radicals. Alkenyl groups are understood as meaning, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. Alkynyl radicals are understood as meaning, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. C ₁ To C ₄₀ Alkoxy groups are understood as meaning, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy.

Aromatic or heteroaromatic ring systems which have from 5 to 60, preferably from 5 to 40, more preferably from 5 to 30, aromatic ring atoms and may in each case also be substituted by the abovementioned radicals and may be connected to the aromatic or heteroaromatic system via any desired position are understood as meaning, for example, radicals derived from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, triphenylene, pyrene, chicory, perylene, fluoranthene, benzofluoranthene, tetracene, pentacene, benzopyrene, biphenyl, dibenzylidene, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, cis-or trans-monobenzindenofluorene, cis-or trans-dibenzoindenofluorene, triindene, isotridecylindene, spiroterphthalene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, phenothiazine, thiophene, pyridine

Oxazines, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthoimidazoles, phenanthroimidazoles, pyridoimidazoles, pyrazinoimidazoles, quinoxaloimidazoles,

Azole, benzo

Azoles, naphtho

Azole, anthracenes

Azole, phenanthro

Oxazole and iso

Oxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diaza anthracene, 2, 7-diaza pyrene, 2, 3-diaza pyrene, 1, 6-diaza pyrene, 1, 8-diaza pyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, thiophene

Oxazines, phenothiazines, fluorarenes, naphthyridines, azacarbazoles, benzocarbazoles, phenanthrolines, 1,2, 3-triazoles, 1,2, 4-triazoles, benzotriazoles, 1,2,3-

Oxadiazole, 1,2,4-

Oxadiazole, 1,2,5-

Diazole, 1,3,4-

Oxadiazole, 1,2, 3-thiadiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole, 1,3, 5-triazine, 1,2, 4-triazine, 1,2, 3-triazine, tetrazole, 1,2,4, 5-tetrazine, 1,2,3, 4-tetrazine, 1,2,3, 5-tetrazine, purine, pteridine, indolizine, and benzothiadiazole.

In a preferred configuration, the compounds used according to the invention may comprise at least one structure of the formulae (IIa), (IIb) and/or (IIc), preferably selected from the group consisting of compounds of the formulae (IIa), (IIb) and (IIc),

wherein the Ar and R groups have the definitions given above, especially for formula (I), the indices m are identical or different and are 0, 1,2,3 or 4, preferably 0, 1,2 or 3, more preferably 0, 1 or 2, especially preferably 0 or 1.

It is also possible that two Ar groups, preferably two Ar groups bound to the nitrogen atom in formula (IIb), together form an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups, wherein the R groups have the definitions detailed above, in particular for formula (I).

In a preferred configuration, the compounds used according to the invention may comprise at least one structure of the formulae (IIb-1), (IIb-2), (IIb-3) and/or (IIb-4), preferably selected from compounds of the formulae (IIb-1), (IIb-2), (IIb-3) and/or (IIb-4),

wherein the X and R groups have the definitions given above, especially for formula (I), the indices m are identical or different and are 0, 1,2,3 or 4, preferably 0, 1,2 or 3, more preferably 0, 1 or 2, especially preferably 0 or 1.

Preferably, at least one of the Ar and/or R groups is selected from: phenyl, fluorene, indenofluorene, spirobifluorene, carbazole, indenocarbazole, indolocarbazole, spirocarbazole, pyrimidine, triazine, quinazoline, quinoxaline, pyridine, quinoline, isoquinoline, lactam, triarylamine, dibenzofuran, dibenzothiophene, imidazole, benzimidazole, benzophenon, benz

Oxazole, benzothiazole, 5-arylphenanthridin-6-one, 9, 10-dehydrophenanthrene, fluoranthene, naphthalene, phenanthrene, anthracene, benzanthracene, indeno [1,2,3-jk]Fluorene, pyrene, perylene, chicory, borazine, boroxine, borazazole, ketone, phosphine oxide, aryl silane, siloxane, and combinations thereof.

It is also possible that preferably, any R group bonded directly to the nitrogen atom is not selected from the group consisting of: OH, F, cl, br, I, CN, NO ₂ 、N(Ar) ₂ 、N(R ¹ ) ₂ Wherein R is ¹ Having the definitions given above, in particular for formula (I). In a further preferred embodiment, the structures of formula (I) and preferred configurations of these structures shown above and below do not have any N-N bonds.

It is also possible that at least one of the Ar and/or R groups is selected from phenyl, o-biphenyl, m-biphenyl or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl or 4-fluorenyl, 9' -diarylfluorenyl, 1-spirobifluorenyl, 2-spirobifluorenyl, 3-spirobifluorenyl or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl or 4-dibenzofuranyl, 1-dibenzothienyl, 2-dibenzothienyl, 3-dibenzothienyl or 4-dibenzothienyl, pyrenyl, triazinyl, imidazolyl, benzimidazolyl, benzofuranyl, or 4-dibenzothienyl, pyrenyl

Oxazolyl, benzothiazolyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl or 9-carbazolyl, 1-naphthyl or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, trans-and cis-indenofluorenyl, indenocarbazolyl, indonocarbazolyl, spirocarbazolyl, 5-aryl-phenanthridin-6-one, 9, 10-dehydrophenanthrenyl, fluoranthenyl, tolyl, mesityl, phenoxytolyl, anisoyl, triarylamino, bis (triarylamino), tris (triarylamino), hexamethylindanyl, tetrahydronaphthyl, monocycloalkyl, bicycloalkyl, tricycloalkyl, alkyl (e.g. tert-butyl, methyl, propyl), alkoxy, alkylthio, alkylaryl, triarylsilyl, trialkylsilyl, xanthenyl, 10-arylthiophenyl

Oxazinyl, phenanthryl and/or terphenylidene, each of which may be substituted by one or more groups, but is preferably unsubstituted, particularly preferably phenyl, spirobifluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene, terphenylidene.

When the structures detailed above and below are substituted with substituents R, these substituents R are preferably selected from H, D, F, CN, N (Ar') ₂ ，C(＝O)Ar'，P(＝O)(Ar') ₂ A linear alkyl or alkoxy group having from 1 to 10 carbon atoms, or a branched or cyclic alkyl or alkoxy group having from 3 to 10 carbon atoms, or an alkenyl group having from 2 to 10 carbon atoms, each of which may be substituted by one or more R ¹ Radical substitution, in which one or more non-adjacent CH ₂ A radical which may be replaced by O and in which one or more hydrogen atoms may be replaced by D or F, has 5 to 24 aromatic ring atoms and may in each case be replaced by one or more R ¹ Substituted but preferably unsubstituted aromatic or heteroaromatic ring systems, or having 5 to 25 aromatic ring atoms and which may be substituted by one or more R ¹ A group-substituted aralkyl or heteroaralkyl group; also, two substituents R, preferably bonded to adjacent carbon atoms, may optionally be formed and may be substituted by one or more R ¹ Radical-substituted mono-or polycyclic aliphatic, aromaticOr a heteroaromatic ring system; wherein the Ar group has the definitions given above, especially for formula (I).

More preferably, these substituents R are selected from H, D, F, CN, N (Ar') ₂ A linear alkyl group having from 1 to 8 carbon atoms, preferably having 1,2,3 or 4 carbon atoms, or a branched or cyclic alkyl group having from 3 to 8 carbon atoms, preferably having 3 or 4 carbon atoms, or an alkenyl group having from 2 to 8 carbon atoms, preferably having 2,3 or 4 carbon atoms, each of which groups may be substituted by one or more R ¹ Substituted, but preferably unsubstituted, or having from 5 to 24 aromatic ring atoms, preferably from 6 to 18 aromatic ring atoms, more preferably from 6 to 13 aromatic ring atoms and in each case possibly being substituted by one or more nonaromatic R ¹ An aromatic or heteroaromatic ring system which is substituted but preferably unsubstituted; at the same time, optionally, two substituents R bonded to adjacent carbon atoms are preferred ¹ May optionally be formed and may be substituted by one or more R ² The radicals substituted but preferably unsubstituted mono-or polycyclic aliphatic ring systems, where Ar may have the definitions detailed above.

More preferably, the substituents R are selected from H or an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more non-aromatic R ¹ The radicals are substituted, but preferably unsubstituted. Examples of suitable substituents R are selected from phenyl, o-biphenyl, m-biphenyl or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl or 4-fluorenyl, 1-spirobifluorenyl, 2-spirobifluorenyl, 3-spirobifluorenyl or 4-spirobifluorenyl, pyridyl, pyrimidyl, triazinyl, quinazolinyl, quinoxalinyl, quinolyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl or 4-dibenzofuranyl, 1-dibenzothienyl, 2-dibenzothienyl, 3-dibenzothienyl or 4-dibenzothienyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl or 4-carbazolyl and indenocarbazolyl, each of which may be substituted by one or more R ¹ Radicals substituted, but preferablyIs unsubstituted.

It is furthermore possible that the substituents R of the structures shown above and below, preferably of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4), do not form any fused aromatic or heteroaromatic ring system, preferably any fused ring system, with one another. This includes the reaction with R or R ¹ Possible substituents R of the radical bond ¹ And R ² Forming a fused ring system.

In another embodiment, it is possible that the compounds used according to the invention comprise hole transporting groups, wherein at least one of the Ar and/or R groups detailed above which may be present in the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) preferably comprises, and preferably represents, a hole transporting group, inter alia. Hole transporting groups are known in the art and they preferably comprise triarylamine or carbazole groups.

It is preferably possible that the hole-transporting group comprises a group selected from the formulae (H-1) to (H-3) and preferably from the formulae (H-1) to (H-3),

wherein the dashed bonds mark the connection positions and the symbols define the following:

Ar ² 、Ar ³ 、Ar ⁴ independently at each occurrence, is an aromatic ring system having from 6 to 40 carbon atoms or a heteroaromatic ring system having from 3 to 40 carbon atoms, each of which may be substituted by one or more R ¹ Substituted by groups;

p is 0 or 1;

z is a bond or C (R) ¹ ) ₂ 、Si(R ¹ ) ₂ 、C＝O、NR ¹ 、NAr ¹ 、BR ¹ 、PR ¹ 、PO(R ¹ )、SO、SO ₂ Se, O or S, preferably a bond or C (R) ¹ ) ₂ 、N-Ar ¹ O or S;

wherein Ar is ¹ Is an aromatic ring system having from 6 to 40 carbon atoms or has from 3 to 40A heteroaromatic ring system of carbon atoms which may be substituted by one or more R ¹ Is substituted with radicals, and the R ¹ The radicals have the definitions detailed above, in particular for formula (I). Also, the presence of N-N bonds is preferably excluded.

It is also possible that the hole-transporting group comprises a group selected from the formulae (H-4) to (H-26) and preferably from the formulae (H-4) to (H-26),

wherein Y is ¹ Is O, S, C (R) ¹ ) ₂ Or NAr ¹ The dotted bond marks the position of the linkage, e is 0, 1 or 2, j is 0, 1,2 or 3, h is 0, 1,2,3 or 4, p is 0 or 1, R ¹ Having the definitions given above, especially for formula (I), and Ar ¹ And Ar ² Have the definitions given above, especially for formula (H-1) and/or (H-2). Also, the presence of N-N bonds is preferably excluded.

From the above wording it is clear that if the label is p =0, then the corresponding Ar ² The groups are absent and form bonds.

Preferably, ar is ² The group may be substituted with Ar of the formulae (H-1) to (H-26) ² The aromatic or heteroaromatic groups to which the groups may be bonded or the nitrogen atoms form complete conjugation.

In another preferred embodiment of the present invention, ar ² Is an aromatic or heteroaromatic ring system having from 5 to 14 aromatic or heteroaromatic ring atoms, preferably having from 6 to 12 carbon atoms and which may be substituted by one or more R ¹ Aryl substituted but preferably unsubstitutedGroup of ring systems, wherein R ¹ May have the definitions given above, especially for formula (I). More preferably, ar ² Is 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 may be substituted by one or more R ¹ Substituted, but preferably unsubstituted, with R ¹ May have the definitions given above, especially for formula (I).

More preferably, symbol Ar shown in formulae (H-1) to (H-26) ² In particular aryl or heteroaryl groups having from 5 to 24 ring atoms, preferably from 6 to 13 ring atoms, more preferably from 6 to 10 ring atoms, such that the aromatic or heteroaromatic groups of an aromatic or heteroaromatic ring system are bonded directly (i.e. via an atom of the aromatic or heteroaromatic group) to a corresponding atom of a further group.

It is also possible that Ar shown in the formulae (H-1) to (H-26) ² The groups comprise aromatic ring systems having no more than two fused aromatic and/or heteroaromatic 6-membered rings; preferably, it does not comprise any fused aromatic or heteroaromatic ring system with fused 6-membered rings. Thus, the naphthyl structure is preferred over the anthracene structure. In addition, fluorenyl, spirobifluorenyl, dibenzofuranyl, and/or dibenzothiophenyl structures are preferred over naphthyl structures. Particularly preferred are structures which do not have a fused-on structure, such as phenyl, biphenyl, terphenyl and/or quaterphenyl structures.

Alternatively, ar shown in the formulae (H-1) to (H-26) ² The radicals have in particular not more than 1 nitrogen atom, preferably not more than 2 heteroatoms, particularly preferably not more than 1 heteroatom and particularly preferably no heteroatoms.

In another preferred embodiment of the present invention, ar ³ And/or Ar ⁴ Are identical or different on each occurrence and are aromatic or heteroaromatic ring systems having from 6 to 24 aromatic ring atoms, preferably from 6 to 18 aromatic ring atoms, and more preferably are aromatic ring systems having from 6 to 12 aromatic ring atoms or heteroaromatic ring systems having from 6 to 13 aromatic ring atoms, each of which may be substituted by one or more R ¹ Radical (I)Substituted, but preferably unsubstituted, wherein R is ¹ May have the definitions given above, especially in formula (I).

In another embodiment, it is possible that the compounds used according to the invention comprise groups comprising electron transporting groups, wherein preferably at least one of the Ar and/or R groups detailed above, which may be present in the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4), comprises and preferably represents in particular a group comprising an electron transporting group. Electron transport groups are well known in the art and facilitate the ability of a compound to transport and/or conduct electrons.

In addition, the compounds used according to the invention show surprising advantages, comprising at least one structure selected from the group consisting of: pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and/or benzimidazole, with pyrimidine, triazine and quinazoline being particularly preferred. These structures generally facilitate the ability of the compound to transport and/or conduct electrons.

In a preferred configuration of the present invention, it is possible that the group containing an electron-transporting group is a group which can be represented by formula (QL),

wherein L is ¹ Represents a bond or has 5 to 40, preferably 5 to 30, aromatic ring atoms and may be substituted by one or more R ¹ A group-substituted aromatic or heteroaromatic ring system, and Q is an electron-transporting group, wherein R is ¹ Have the definitions given above, especially for formula (I), and the dashed bonds mark the connection positions.

Preferably, said L ¹ The group may be substituted with a Q group and L of formula (QL) ¹ The atoms (preferably carbon or nitrogen atoms) to which the groups are bonded form a complete conjugate. Once a direct bond is formed between adjacent aromatic or heteroaromatic rings, complete conjugation of the aromatic or heteroaromatic system is formed. Another bond between the aforementioned conjugated groups, e.g. via sulfur, nitrogenOr an oxygen atom or a carbonyl group, is not detrimental to conjugation. In the case of fluorene systems, the two aromatic rings are directly bonded, with sp in the 9 position ³ The hybridized carbon atom does prevent the fusion of these rings, but conjugation is possible because of the sp in position 9 ³ The hybridized carbon atom is not necessarily located between the electron transporting Q group and the atom through which the group of formula (QL) is bonded to other structural elements of the compound. In contrast, in the case of the second spirobifluorene structure, if the Q group is bonded to L of formula (QL) ¹ Complete conjugation can be formed if the bonds between the aromatic or heteroaromatic groups to which the groups are bonded are via the same phenyl group in the spirobifluorene structure or via phenyl groups bonded directly to one another in one plane in the spirobifluorene structure. If the Q group is bonded to L of the formula (QL) ¹ The bond between the aromatic or heteroaromatic groups to which the groups are bonded being via sp via position 9 ³ Different phenyl groups in the second spirobifluorene structure bonded by the hybridized carbon atom are bonded, so that conjugation is interrupted.

In another preferred embodiment of the present invention, L ¹ Is a bond or an aromatic or heteroaromatic ring system having from 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having from 6 to 12 carbon atoms, and which may be substituted by one or more R ¹ Substituted, but preferably unsubstituted, radicals in which R is ¹ May have the definitions given above, especially for formula (I). More preferably, L ¹ Is an aromatic ring system having from 6 to 10 aromatic ring atoms or a heteroaromatic ring system having from 6 to 13 heteroaromatic ring atoms, each of which may be interrupted by one or more R ² Substituted, but preferably unsubstituted, with R ² May have the definitions given above, especially for formula (I).

More preferably, symbol L shown in formula (QL) ¹ In particular identical or different on each occurrence, and is a bond or an aryl or heteroaryl radical having from 5 to 24 ring atoms, preferably from 6 to 13 ring atoms, more preferably from 6 to 10 ring atoms, such that the aromatic or heteroaromatic groups of the aromatic or heteroaromatic ring systems are bonded directly to the corresponding atoms of the other groups, i.e. via atoms of the aromatic or heteroaromatic groups.

It is also possible that L is shown in formula (QL) ¹ The group comprises aromatic ring systems having no more than two fused aromatic and/or heteroaromatic 6-membered rings, preferably without any fused aromatic or heteroaromatic ring systems. Thus, the naphthyl structure is preferred over the anthracene structure. In addition, fluorenyl, spirobifluorenyl, dibenzofuranyl, and/or dibenzothienyl structures are preferred over naphthyl structures.

Particularly preferably, no fused structures, such as phenyl, biphenyl, terphenyl and/or quaterphenyl structures, are present.

Suitable aromatic or heteroaromatic ring systems L ¹ Examples of (a) are selected from o-, m-or p-phenylene, o-, m-or p-biphenylene, terphenylene, especially branched terphenylene, quaterphenylene, especially branched quaterphenylene, fluorenylene, spirobifluorenylene, dibenzofuranene, dibenzothiophenylene and carbazolium, each of which may be substituted by one or more R ¹ The radicals are substituted, but preferably unsubstituted.

It is also possible that L is shown in formula (QL) ¹ The radicals have in particular not more than 1 nitrogen atom, preferably not more than 2 heteroatoms, particularly preferably not more than 1 heteroatom and more preferably no heteroatoms.

Preferably, the Q group or electron-transporting group shown in formula (QL) in particular may be selected from structures of formula (Q-1), (Q-2), (Q-3), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9) and/or (Q-10),

wherein the dashed key marks the location of the connection,

q' is identical or different in each case and is CR ¹ Or N, and

q' is NR ¹ O or S;

wherein at least one Q' is N, and

R ¹ as defined above, especially in formula (I).

In addition, the Q group or the electron-transporting group shown in formula (QL) in particular may preferably be selected from the structures of formula (Q-11), (Q-12), (Q-13), (Q-14) and/or (Q-15),

wherein the symbol R ¹ Having the definition given above, in particular for formula (I), X' is N or CR ¹ And the dashed bond marks the attachment position, wherein X' is preferably a nitrogen atom.

In another embodiment, especially the Q group or electron transport group shown in formula (QL) may be selected from structures of formula (Q-16), (Q-17), (Q-18), (Q-19), (Q-20), (Q-21) and/or (Q-22),

wherein the symbol R ¹ Having the definitions detailed above, especially for formula (I), the dotted bond marks the position of the attachment and m is 0, 1,2,3 or 4, preferably 0, 1 or 2, n is 0, 1,2 or 3, preferably 0, 1 or 2, and o is 0, 1 or 2, preferably 1 or 2. Preferred herein are structures of the formulae (Q-16), (Q-17), (Q-18) and (Q-19).

In another embodiment, the Q group or electron transport group, particularly shown in formula (QL), can be selected from structures of formula (Q-23), (Q-24), and/or (Q-25),

wherein the symbol R ¹ Have the definitions detailed above, particularly for formula (I), and the dashed bonds mark the attachment positions.

In another embodiment, in particular, the Q group or electron-transporting group shown in formula (QL) may be selected from structures of formula (Q-26), (Q-27), (Q-28), (Q-29), and/or (Q-30),

wherein the symbol Ar ¹ And R ¹ Having the definitions given above, especially for formula (I) and/or (H-2), (H-3), X' is N or CR ¹ And the dashed bonds mark the connection locations. Preferably, in the structures of formulae (Q-26), (Q-27) and (Q-28), exactly one X' is a nitrogen atom.

Preferably, the Q group or electron-transporting group shown in formula (QL) in particular may be selected from structures of formula (Q-31), (Q-32), (Q-33), (Q-34), (Q-35), (Q-36), (Q-37), (Q-38), (Q-39), (Q-40), (Q-41), (Q-42), (Q-43) and/or (Q-44),

wherein symbol Ar ¹ And R ¹ Having the definitions detailed above, in particular for formula (I) and/or (H-2) or (H-3), the dotted bond marks the attachment position and m is 0, 1,2,3 or 4, preferably 0, 1 or 2, n is 0, 1,2 or 3, preferably 0 or 1, n is 0, 1,2 or 3, preferably 0, 1 or 2, and l is 1,2,3,4 or 5, preferably 0, 1 or 2.

In another preferred aspect of the present inventionIn the embodiment, ar ¹ Are identical or different on each occurrence and are aromatic or heteroaromatic ring systems, preferably aryl or heteroaryl groups having from 5 to 24 aromatic ring atoms, preferably having from 6 to 18 aromatic ring atoms, and more preferably are aromatic ring systems, preferably aryl groups having from 6 to 12 aromatic ring atoms, or heteroaromatic ring systems, preferably heteroaryl groups having from 5 to 13 aromatic ring atoms, each of which may be substituted by one or more R ² Substituted, but preferably unsubstituted, with R ² May have the definitions detailed above, especially in formula (I).

Preferably, the symbol Ar ¹ Is an aryl or heteroaryl group such that the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is bonded directly (i.e., via an atom of the aromatic or heteroaromatic group) to a corresponding atom of another group, such as a carbon or nitrogen atom of the (H-1) to (H-26) or (Q-26) to (Q-44) groups shown above.

Advantageously, ar in the formulae (H-1) to (H-26) or (Q-26) to (Q-44) ¹ Is a compound having 6 to 12 aromatic ring atoms and may be substituted by one or more R ² Substituted but preferably unsubstituted aromatic ring systems, in which R is ² May have the definitions detailed above, especially for formula (I).

Preferably, R in the formulae (H-1) to (H-26) or (Q-1) to (Q-44) ¹ Or R ² The radicals not being identical to R ¹ Or R ² Aryl or heteroaryl groups Ar to which the groups are bonded ¹ 、Ar ² 、Ar ³ And/or Ar ⁴ Form a fused ring system. This includes and may be with R ¹ Possible substituents R of the radical bond ² Forming a fused ring system.

In addition, ar' and Ar may be ¹ 、Ar ² 、Ar ³ And/or Ar ⁴ The radicals being selected from phenyl, o-, m-or p-biphenylyl, terphenyl, in particular branched terphenyl, quaterphenyl, in particular branched quaterphenyl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl or 4-fluorenyl, 1-spirobifluorenyl, 2-spirobifluorenyl, 3-spirobifluorenyl or 4-spirobifluorenyl, pyridyl, pyrimidyl, 1-dibenzofuranyl2-dibenzofuranyl, 3-dibenzofuranyl or 4-dibenzofuranyl, 1-dibenzothienyl, 2-dibenzothienyl, 3-dibenzothienyl or 4-dibenzothienyl, pyrenyl, triazinyl, imidazolyl, benzimidazolyl, benzofuranyl

Oxazolyl, benzothiazolyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl or 4-carbazolyl, 1-naphthyl or 2-naphthyl, anthracyl, preferably 9-anthracyl, phenanthryl and/or triphenylidene, each of which may be substituted by one or more R ¹ Substituted, but preferably unsubstituted, particularly preferably phenyl, spirobifluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene, terphenylene radicals, where R is the radical ¹ The radicals have the definitions given above, especially in formula (I).

In a preferred embodiment, it is possible that at least two Ar and/or R groups in the structures of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) comprise a hole-transporting group and preferably represent a hole-transporting group.

It is also possible that at least one of the Ar and/or R groups in the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) comprises two hole-transporting groups. Hole transport groups may be considered herein as R ¹ A group, in this case, a substituent R in the structures of the formulae (H-1) to (H-26) ¹ Should be replaced by R ² And (4) substituting the group.

In a preferred embodiment, it is possible that at least two Ar and/or R groups in the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) comprise and preferably represent electron transport group-containing groups.

It is also possible that at least one of the Ar and/or R groups in the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) comprises two electron transport group-containing groups. The group containing an electron transport group may be considered herein as R ¹ A group, in this case, a substituent R in the structure of the formula (QL) and/or (Q-1) to (Q-44) ¹ Should be replaced by R ² The groups are replaced.

In a preferred configuration, it is possible that at least one of the Ar and/or R groups in the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) comprises and preferably represents a hole transporting group and at least one of the R and/or Ar groups comprises and preferably represents an electron transporting group containing group.

It is also possible that at least one of the Ar and/or R groups in the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) comprises an electron-transporting group-containing group and a hole-transporting group. An electron transport group-containing group or hole transport group may be considered herein as R ¹ A group, in this case, a substituent R in the structure of the formula (QL), (Q-1) to (Q-44) or (H-1) to (H-26) ¹ Should be replaced by R ² The groups are replaced.

In another configuration, it may be the case that at least one of the Ar and/or R groups comprises at least one group that results in a wide bandgap material. The expression "group leading to a wide bandgap material" indicates that the compound can be used as a wide bandgap material, and that the compound thus has a corresponding group. The wide bandgap material will be discussed in detail later.

It is also possible that at least one of the Ar and/or R groups comprises at least one group that results in a material that is used as the host material. The expression "a group leading to a material used as a host material" indicates that the compound can be used as a host material, and thus the compound has a corresponding group. The host material will be discussed in detail later.

In another configuration, it is possible that the compound comprises a fused aromatic or heteroaromatic ring system having at least 2, preferably three, fused rings which may optionally be substituted.

Preferably, at least one of the Ar and/or R groups in the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) comprises at least one aromatic or heteroaromatic ring system having two, preferably three, fused aromatic or heteroaromatic rings.

It is preferably possible for the aromatic or heteroaromatic ring systems having two, preferably three, fused aromatic or heteroaromatic rings to be selected from the group of the formulae (Ar-1) to (Ar-17),

wherein X' is N or CR ¹ Preferably CR ¹ ，L ¹ Represents a bond or has 5 to 40, preferably 5 to 30, aromatic ring atoms and may be substituted by one or more R ¹ An aromatic or heteroaromatic ring system substituted by a group, in which R ¹ Have the definitions detailed above, especially for formula (I), and the dashed bonds mark the attachment positions.

It is most preferably possible that the aromatic or heteroaromatic ring system having two, preferably three, fused aromatic or heteroaromatic rings is selected from the group of the formulae (Ar '-1) to (Ar' -17),

wherein L is ¹ Represents a bond or has 5 to 40, preferably 5 to 30, aromatic ring atoms and may be substituted by one or more R ¹ A radical-substituted aromatic or heteroaromatic ring system, in which R ¹ Having the definitions detailed above, especially for formula (I), the dashed bonds mark the attachment positions and are labeled as follows:

p is 0 or 1;

e is 0, 1 or 2, preferably 0 or 1;

j is independently in each occurrence 0, 1,2 or 3, preferably 0, 1 or 2, more preferably 0 or 1;

h is independently at each occurrence 0, 1,2,3 or 4, preferably 0, 1 or 2, more preferably 0 or 1;

s is an integer in the range from 0 to 7, preferably 0, 1,2,3,4, 5 or 6, particularly preferably 0, 1,2,3 or 4, particularly preferably 0, 1 or 2.

It is preferred that the sum of the indices p, e, j, h and s in the structures of the formulae (Ar '-1) to (Ar' -17) is in each case not more than 3, preferably not more than 2 and more preferably not more than 1.

The structures of formulae (Ar-1) to (Ar-17) and/or (Ar '-1) to (Ar' -17) shown above are particularly preferred groups for compounds suitable for use as fluorescent emitters or blue OLED materials.

In another preferred embodiment of the present invention, L in the structures of the formulae (Ar-1) to (Ar-17) and/or (Ar '-1) to (Ar' -17) shown above ¹ The radicals are those having from 5 to 40, preferably from 5 to 30, aromatic ring atoms and preferably substituted by one or more R ¹ A radical-substituted aromatic or heteroaromatic ring system, in which R ¹ Having the definitions given above, in particular for formula (I).

When the aromatic and/or heteroaromatic radical is substituted by a substituent R ¹ When substituted, these substituents R ¹ Preferably selected from H, D, F, CN, N (Ar') ₂ ，C(＝O)Ar”，P(＝O)(Ar”) ₂ A linear alkyl or alkoxy group having from 1 to 10 carbon atoms, or a branched or cyclic alkyl or alkoxy group having from 3 to 10 carbon atoms, or an alkenyl group having from 2 to 10 carbon atoms, each of which may be substituted by one or more R ² Substituted by radicals in which one or more non-adjacent CH ₂ The radicals being substitutable for O and in which one or more hydrogen atoms are substitutable for D or F, having 5 to 24 aromatic ring atoms and being substitutable in each case by one or more R ² Substituted but preferably unsubstituted aromatic or heteroaromatic ring systems, or having 5 to 25 aromatic ring atoms and which may be substituted by one or more R ² A group-substituted aralkyl or heteroaralkyl group; at the same time, two substituents R bonded to adjacent carbon atoms are preferred ¹ May optionally be formed and may be substituted by one or more R ¹ A group-substituted mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system;wherein the Ar' group has the definitions given above, especially for formula (I).

More preferably, these substituents R ¹ Selected from H, D, F, CN, N (Ar') ₂ A linear alkyl group having from 1 to 8 carbon atoms, preferably having 1,2,3 or 4 carbon atoms, or a branched or cyclic alkyl group having from 3 to 8 carbon atoms, preferably having 3 or 4 carbon atoms, or an alkenyl group having from 2 to 8 carbon atoms, preferably having 2,3 or 4 carbon atoms, each of which groups may be substituted by one or more R ² A group, but preferably unsubstituted, or have 5 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms and can in each case be substituted by one or more non-aromatic R ¹ The radicals substituted but preferably unsubstituted aromatic or heteroaromatic ring systems; at the same time, two substituents R bonded to adjacent carbon atoms are preferred ¹ May optionally be formed and may be substituted by one or more R ² The radicals substituted, but preferably unsubstituted, mono-or polycyclic aliphatic ring systems, in which Ar ¹ May have the definitions detailed above.

Most preferably, the substituent R ¹ Selected from H or an aromatic or heteroaromatic ring system having from 6 to 18 aromatic ring atoms, preferably from 6 to 13 aromatic ring atoms, which may in each case be substituted by one or more non-aromatic R ² The radicals are substituted, but preferably unsubstituted. Suitable substituents R ¹ Examples of (A) are selected from phenyl, o-, m-or p-biphenylyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-fluorenyl, 2-fluorenyl, 3-fluorenyl or 4-fluorenyl, 1-spirobifluorenyl, 2-spirobifluorenyl, 3-spirobifluorenyl or 4-spirobifluorenyl, pyridyl, pyrimidyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl or 4-dibenzofuranyl, 1-dibenzothienyl, 2-dibenzothienyl, 3-dibenzothienyl or 4-dibenzothienyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl or 4-carbazolyl and indenocarbazolyl, each of which may be substituted by one or more R, R ² The radicals are substituted, but preferably unsubstituted.

It is also possible for the substituents R to be aromatic or heteroaromatic ring systems ¹ Do not form a fused aromatic or heteroaromatic ring system, preferably any fused ring system, with further ring atoms of the aromatic or heteroaromatic ring system. This includes and may be with R ¹ Possible substituents R of the radical bond ² Forming a fused ring system.

It is also possible for at least one R in the structures of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) ¹ Or Ar' group is selected from the formula (R) ¹ -1) to (R) ¹ -43), or at least one R of the structures of formulae (H-1) to (H-26), (QL), (Q-1) to (Q-44), (Ar-1) to (Ar-17) and/or (Ar '-1) to (Ar' -17) ¹ Is selected from the formula (R) ¹ -1) to (R) ¹ -43) group:

the symbols used therein are as follows:

Y ³ is O, S or NR ² Preferably O or S;

k is independently in each occurrence 0 or 1;

i is independently in each occurrence 0, 1 or 2;

j is independently in each occurrence 0, 1,2 or 3;

h is independently at each occurrence 0, 1,2,3 or 4;

g is independently in each occurrence 0, 1,2,3,4 or 5;

R ² may have the definitions given above, especially for formula (I), and the dashed bonds mark the connection positions.

Preference is given here to the formula R ¹ -1 to R ¹ The radical of-28, particularly preferably R ¹ -1、R ¹ -3、R ¹ -4、R ¹ -10、R ¹ -11、R ¹ -12、R ¹ -13、R ¹ -14、R ¹ -16、R ¹ -17、R ¹ -18、R ¹ -19、R ¹ -20、R ¹ -21 and/or R ¹ -22 groups.

Preferably, the formula (R) ¹ -1) to (R) ¹ The sum of the indices k, i, j, h and g in the structure of-43) is in each case not more than 3, preferably not more than 2 and more preferably not more than 1.

Preferably, formula (R) ¹ -1) to (R) ¹ R in-43) ² The radicals not being identical to R ² The ring atoms of the aryl or heteroaryl group to which the groups are bonded form a fused aromatic or heteroaromatic ring system and preferably do not form any fused ring system.

Formula (R) as detailed above ¹ -1) to (R) ¹ The radical of-43) is preferably an Ar radical of the formula (I) or Ar of the formulae (H-1) to (H-3) ³ 、Ar ⁴ Preferred embodiments of the radicals or of these formulae, where, in this case, the formula (R) ¹ -1) to (R) ¹ R shown in-43) ² Radical R ¹ And (4) substituting the group. Hereinbefore with respect to formula (R) ¹ -1) to (R) ¹ -43) the preferences detailed are correspondingly applicable.

Preferably, it is possible that the compound comprises at least one compound selected from the formula (L) ¹ -1) to (L) ¹ A linking group of-76); preferably, in the structures of formulae (H-1) to (H-26), ar ² The group is selected from the formula (L) ¹ -1) to (L) ¹ -76), or the electron transport group is via a group selected from formula (L) ¹ -1) to (L) ¹ -76) to other structural units, or L in formulae (QL), (Ar-1) to (Ar-17) and/or (Ar '-1) to (Ar' -17) ¹ The radicals are selected from the formulae (L) ¹ -1) to (L) ¹ Group of-76)The shape of the ball is changed into a ball,

wherein the dashed bonds denote the joining position in each case, the mark k is 0 or 1, the mark l is 0, 1 or 2, the mark j is independently in each case 0, 1,2 or 3; the index h is in each case independently 0, 1,2,3 or 4 and the index g is 0, 1,2,3,4 or 5; symbol Y ² Is O, S or NR ¹ Preferably O or S; and the symbol R ¹ Having the definitions given above, in particular for formula (I).

Preferably, the case is that ¹ -1) to (L) ¹ The sum of the indices k, l, g, h and j in the structure of-76) is in each case at most 3, preferably at most 2 and more preferably at most 1.

Preferred compounds having a group of the formulae (H-1) to (H-26) comprise Ar ² Group of Ar ² The group is selected from the formula (L) ¹ -1) to (L) ¹ -46) and/or (L) ¹ -57) to (L) ¹ -76), preferably of formula (L) ¹ -1) to (L) ¹ -32) and/or (L) ¹ -57) to (L) ¹ One of the formulae (E) to (E) 76), particularly preferably of the formula (L) ¹ -1) to (L) ¹ -10) and/or (L) ¹ -57) to (L) ¹ -68).Advantageously, of the formula (L) ¹ -1) to (L) ¹ -46) and/or (L) ¹ -57) to (L) ¹ -76), preferably of formula (L) ¹ -1) to (L) ¹ -32) and/or (L) ¹ -57) to (L) ¹ -76), particularly preferably of formula (L) ¹ -1) to (L) ¹ -10) and/or (L) ¹ -57) to (L) ¹ The sum of the indices k, l, g, h and j in the structure of-68) may in each case be not more than 3, preferably not more than 2 and more preferably not more than 1.

Preferred compounds having a group of formula (QL) comprise L ¹ Group of the L ¹ The group represents a bond or is selected from the formula (L) ¹ -1) to (L) ¹ -46) and/or (L) ¹ -57) to (L) ¹ -76), preferably of formula (L) ¹ -1) to (L) ¹ -32) and/or (L) ¹ -57) to (L) ¹ One of the formulae (L) to (76), particularly preferably of the formula (L) ¹ -1) to (L) ¹ -10) and/or (L) ¹ -57) to (L) ¹ -68). Advantageously, formula (L) ¹ -1) to (L) ¹ -46) and/or (L) ¹ -57) to (L) ¹ -76), preferably of formula (L) ¹ -1) to (L) ¹ -32) and/or (L) ¹ -57) to (L) ¹ -76), particularly preferably of formula (L) ¹ -1) to (L) ¹ -10) and/or (L) ¹ -57) to (L) ¹ The sum of the indices k, l, g, h and j in the structure of-68) may in each case be not more than 3, preferably not more than 2 and more preferably not more than 1.

Preferred compounds having groups of the formulae (Ar-1) to (Ar-17) and/or (Ar '-1) to (Ar' -17) comprise L ¹ Group, said L ¹ The group is a bond or is selected from the formula (L) ¹ -1) to (L) ¹ -46) and/or (L) ¹ -57) to (L) ¹ -76), preferably of formula (L) ¹ -1) to (L) ¹ -32) and/or (L) ¹ -57) to (L) ¹ One of the formulae (E) to (E) 76), particularly preferably of the formula (L) ¹ -1) to (L) ¹ -10) and/or (L) ¹ -57) to (L) ¹ -68). Advantageously, formula (L) ¹ -1) to (L) ¹ -46) and/or (L) ¹ -57) to (L) ¹ -76), preferably of formula (L) ¹ -1) to (L) ¹ -32) and/or (L) ¹ -57) to (L) ¹ -76), particularly preferably of formula (L) ¹ -1) to (L) ¹ -10) and/or (L) ¹ -57) to (L) ¹ The sum of the indices k, l, g, h and j in the structure of-68) may in each case be not more than 3, preferably not more than 2 and more preferably not more than 1.

Preferably, formula (L) ¹ -1) to (L) ¹ R in-76) ¹ The radicals being different from R ¹ The ring atoms of the aryl or heteroaryl group to which the group is bonded form a fused aromatic or heteroaromatic ring system and preferably do not form any fused ring systems.

In a preferred configuration, the compounds useful according to the invention can be represented by at least one of the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4). Preferably, the compounds comprising the structures of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) have a molecular weight of not more than 5000g/mol, preferably not more than 4000g/mol, particularly preferably not more than 3000g/mol, particularly preferably not more than 2000g/mol and most preferably not more than 1200 g/mol.

In addition, preferred compounds which can be used according to the invention are characterized in that they are sublimable. These compounds generally have a molar mass of less than about 1200 g/mol.

When the compounds of the invention are substituted with aromatic or heteroaromatic R ¹ Or R ² When substituted, it is preferred that these are absent any aryl or heteroaryl groups having more than two aromatic six-membered rings directly fused to each other. More preferably, the substituents are completely free of any aryl or heteroaryl groups having six-membered rings directly fused to each other. The reason for this preference is the low triplet energy of such structures. Fused aryl radicals which have more than two aromatic six-membered rings directly fused to one another but which are still suitable according to the invention are phenanthrene and terphenylene since these also have high triplet energy levels.

In the case of configuring the compounds of the invention for use as fluorescent emitters or as blue OLED material, preferred compounds may contain corresponding groups, for example fluorene, anthracene and/or pyrene groups, which groups may be substituted by R ¹ Or R ² Substituted by radicals, or by radicals R ¹ Or R ² To (L) ¹ -1) to (L) ¹ -76) or (R) ¹ -1) to (R) ¹ -43) by corresponding substitution of the group.

In a further preferred embodiment of the invention, R is, for example, in the structures of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) and preferred embodiments of the structures or of the structures referring to the formulae ² Identical or different on each occurrence and selected from the group consisting of H, D, F, CN, aliphatic hydrocarbon radicals having from 1 to 10 carbon atoms, preferably having from 1,2,3 or 4 carbon atoms, or aromatic or heteroaromatic ring systems having from 5 to 30 aromatic ring atoms, preferably from 5 to 24 aromatic ring atoms, more preferably from 5 to 13 aromatic ring atoms, which may be substituted by one or more alkyl radicals each having from 1 to 4 carbon atoms, but are preferably unsubstituted.

Preferably, R ² The radicals being different from R ² The ring atoms of the aryl or heteroaryl group to which the groups are bonded form a fused aromatic or heteroaromatic ring system and preferably do not form any fused ring system.

It is also possible that the compounds of the invention are not in direct contact with the metal atom and are preferably not ligands of the metal complex.

The invention furthermore provides compounds comprising at least one structure of the formula (III), preferably compounds of the formula (III),

wherein the symbols X and W have the definitions given above, especially for formula (I), and HetAr is a compound having 5 to 60 aromatic ring atoms and which may be substituted by one or more R ¹ A group-substituted heteroaromatic ring system wherein the HetAr group may form a ring system together with at least one Ar group, R group or another group, wherein HetAr is preferably a group selected from formulae (H-1) to (H-26) as defined above or from formulae (QL) and (Q-1) to (Q-44) as defined above.

In another preferred embodiment, it is possible that the compounds of the invention comprise a structure of formula (IVa), (IVb) and/or (IVc), wherein the compounds of the invention may more preferably be selected from compounds of formula (IVa), (IVb) and/or (IVc):

wherein the symbols R and Ar have the definitions given above, especially for formula (I), the index m is 0, 1,2,3 or 4, preferably 0, 1 or 2, and HetAr has the definitions given above, especially for formula (III), and is preferably a radical selected from the groups of formulae (H-1) to (H-26) as defined above or from the groups of formulae (QL) and (Q-1) to (Q-44) as defined above.

Particular preference is given in addition to the compounds of the invention having the structure of formula (IVa), which have the following properties:

in the present context, the group of formulae Q-11 to Q-25 in the compounds having the structure of formula (IVa) detailed in the table shown above comprises R ¹ Group R ¹ The radical preferably represents an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more non-aromatic R ² Substitution of radicals; preferably, the groups of formulae Q-11 to Q-25 in the compounds having the structure of formula (IVa) detailed in the tables shown above have at least one R ¹ Radical, preferably at least two R ¹ Group R ¹ The radicals are selected from the formula (R) ¹ -1) to (R) ¹ -43), preferably of formula R ¹ -1 to R ¹ -28 and R ¹ -34 to R ¹ A radical of the formula-38, particularly preferably of the formula R ¹ -1、R ¹ -3、R ¹ -4、R ¹ -10、R ¹ -11、R ¹ -12、R ¹ -13、R ¹ -14、R ¹ -16、R ¹ -17、R ¹ -18、R ¹ -19、R ¹ -20、R ¹ -21、R ¹ -22、R ¹ -24 and/or R ¹ -37.

Particular preference is furthermore given to compounds of the invention having the formula (IVa) in which the HetAr group has and preferably represents at least one QL group, where Q is selected from Q-16 to Q-19 and Q-23 to Q-25, preferably Q-23 to Q-25, more preferably Q-23, having the following properties:

particular preference is furthermore given to compounds of the invention having the formula (IVa) in which the HetAr group has and preferably represents at least one hole-transporting group, where the hole-transporting group is selected from H-1 to H-3, which have the following properties:

particular preference is furthermore given to compounds of the invention having the structure of the formula (IVa) in which the HetAr group has and preferably represents at least one hole-transporting group, where the hole-transporting group is selected from H-4 to H-26, which compounds have the following properties:

particular preference is furthermore given to compounds of the invention having the structure of the formula (IVb), which have the following properties:

in the context of this text, the radicals of the formulae Q-11 to Q-25 in the compounds having the structure of the formula (IVb) detailed in the tables indicated above comprise R ¹ Group R ¹ The radical preferably represents an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more non-aromatic R ² Substitution of radicals; preferably, the groups of formulae Q-11 to Q-25 in the compounds having the structure of formula (IVa) detailed in the tables shown above have at least one R ¹ Radical, preferably at least two R ¹ Group R ¹ The radicals are selected from the formula (R) ¹ -1) to (R) ¹ -43), preferably of formula R ¹ -1 to R ¹ -28 and R ¹ -34 to R ¹ A radical of the formula-38, particularly preferably of the formula R ¹ -1、R ¹ -3、R ¹ -4、R ¹ -10、R ¹ -11、R ¹ -12、R ¹ -13、R ¹ -14、R ¹ -16、R ¹ -17、R ¹ -18、R ¹ -19、R ¹ -20、R ¹ -21、R ¹ -22、R ¹ -24 and/or R ¹ -37.

In a preferred embodiment, it is possible that at least one of the HetAr groups and Ar and/or R groups in the structures of formulae (III), (IVa), (IVb) and/or (IVc) each comprise and preferably represent a hole transporting group.

It is also possible that the HetAr group in the structures of formulae (III), (IVa), (IVb) and/or (IVc) comprises two hole transporting groups. The hole transport group may be considered herein as R ¹ A group, in this case, a substituent R in the structures of the formulae (H-1) to (H-26) ¹ Should be replaced by R ² The groups are replaced.

In a preferred embodiment, it is possible that at least one of the HetAr groups and Ar and/or R groups in the structures of formulae (III), (IVa), (IVb) and/or (IVc) each comprise and preferably represent an electron transport group-containing group.

It is also possible that the HetAr group in the structures of formulae (III), (IVa), (IVb) and/or (IVc) comprises two electron transport group containing groups. Groups containing electron transport groups may be considered herein as R ¹ A group, in this case a junction of the formulae (QL) and/or (Q-1) to (Q-44)Substituent R in the structure ¹ Should be replaced by R ² The groups are replaced.

In a preferred configuration, it is possible that at least one of the HetAr, ar and/or R groups in the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) comprises and preferably represents a hole transporting group and at least one of the HetAr, ar and/or R groups comprises and preferably represents an electron transporting group-containing group.

It is also possible that the HetAr group in the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) comprises an electron-transporting group-containing group and a hole-transporting group. An electron transport group-containing group or a hole transport group may be considered herein as R ¹ A group, in this case, a substituent R in the structure of the formula (QL), (Q-1) to (Q-44) or (H-1) to (H-26) ¹ Should be substituted by R ² The groups are replaced.

The invention furthermore provides compounds comprising at least one structure of the formula (V), preferably compounds of the formula (V),

wherein the symbols X and W have the definitions given above, especially for formula (I), and KonAr denotes an aromatic or heteroaromatic ring system having two, preferably three, fused aromatic or heteroaromatic rings and having from 10 to 60 aromatic ring atoms, preferably from 12 to 40 aromatic ring atoms, wherein the aromatic or heteroaromatic ring system may be interrupted by one or more R ¹ Group substitution, wherein the KonAr group may form a ring system with at least one Ar group, R group, X group or another group, wherein KonAr is preferably a group selected from the group consisting of the formulae (Ar-1) to (Ar-17) and (Ar '-1) to (Ar' -17) defined above, more preferably from the groups of the formulae (Ar-3) to (Ar-17) and (Ar '-3) to (Ar' -17) defined above.

In another preferred embodiment, it is possible that the compounds of the invention comprise a structure of formula (VIa), (VIb) and/or (VIc), wherein the compounds of the invention may more preferably be selected from compounds of formula (VIa), (VIb) and/or (VIc):

wherein the symbols R and Ar have the definitions given above, especially for formula (I), the index m is 0, 1,2,3 or 4, preferably 0, 1 or 2, and KonAr has the definitions given above, especially for formula (V), and is preferably a group selected from the formulae (Ar-1) to (Ar-17) and (Ar '-1) to (Ar' -17) as defined above, more preferably a group selected from the formulae (Ar-3) to (Ar-17) and (Ar '-3) to (Ar' -17) as defined above.

Particular preference is furthermore given to compounds of the invention having the structure of the formulae (V), (VIa), (VIb) and/or (VIc), which have the following properties:

in this context, the group of formula Ar-5 or Ar' -5 in a compound having a structure of formula (V), (VIa), (VIb) and/or (VIc) detailed in the tables shown above comprises R ¹ Group R ¹ The radical preferably denotes an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more nonaromatic R ² Substituted by groups; preferably, the group of formula Ar-5 or Ar' -5 in a compound having a structure of formula (V), (VIa), (VIb) and/or (VIc) detailed in the tables shown above has at least one R ¹ Group R ¹ The radicals are selected from the formula (R) ¹ -1) to (R) ¹ -43), preferably of formula R ¹ -1 to R ¹ -28 and R ¹ -34 to R ¹ Radicals of the formula-38, particularly preferably of the formula R ¹ -1、R ¹ -3、R ¹ -4、R ¹ -10、R ¹ -11、R ¹ -12、R ¹ -13、R ¹ -14、R ¹ -16、R ¹ -17、R ¹ -18、R ¹ -19、R ¹ -20、R ¹ -21、R ¹ -22、R ¹ -24 and/or R ¹ -37. These R preferably represent aromatic or heteroaromatic ring systems having from 6 to 18 aromatic ring atoms ¹ The group is preferably L in the formula (Ar-5) or the formula (Ar' -5) ¹ Para to the attachment site of the group, label p =1, and R ¹ The radicals preferably denote aromatic or heteroaromatic ring systems having from 6 to 18 aromatic ring atoms.

In a preferred configuration, the compound of the invention may comprise at least one structure of formula (VIb-1) and/or (VIb-2), preferably selected from compounds of formula (VIb-1) and/or (VIb-2),

wherein the X and R groups have the definitions given above, in particular for formula (I), the indices m are identical or different and are 0, 1,2,3 or 4, preferably 0, 1,2 or 3, more preferably 0, 1 or 2, particularly preferably 0 or 1, and the ring KON denotes an aromatic or heteroaromatic ring system having two, preferably three, fused aromatic or heteroaromatic rings and having from 10 to 60 aromatic ring atoms, preferably from 12 to 40 aromatic ring atoms, wherein the aromatic or heteroaromatic ring system may be substituted by one or more R ¹ Is substituted by radicals in which R ¹ May have the definitions given above, especially for formula (I).

It is also possible that the ring KON shown in the formula (VIb-1) and/or (VIb-2) is bonded to the ring having two nitrogen atoms via adjacent carbon atoms so that the ring fused with the ring KON is a 5-membered ring. The ring KON in the formula (VIb-1) and/or (VIb-2) is fused to the ring via two nitrogen atoms.

It is also possible that the ring KON in the structure of the formulae (VIb-1) and/or (VIb-2) forms a substructure of the formulae (KON-1) to (KON-10),

wherein X' is N or CR ¹ Preferably CR ¹ Wherein R is ¹ May have the definitions given above, especially for formula (I), and the nitrogen atoms each combine at the position indicated by o with an aromatic or heteroaromatic ring system having from 5 to 60 carbon atoms to form a ring.

It is also possible that the ring KON in the structure of the formulae (VIb-1) and/or (VIb-2) forms a substructure of the formulae (KON '-1) to (KON' -10),

wherein R is ¹ Having the definitions given above, especially for formula (I), the index o is 0, 1 or 2, preferably 0 or 1, the index n is 0, 1,2 or 3, preferably 0, 1 or 2, and the index m is 0, 1,2,3 or 4, preferably 0, 1 or 2, and the nitrogen atoms are each combined at the position identified by o with an aromatic or heteroaromatic ring having from 5 to 60 carbon atoms to form a ring.

In another preferred embodiment, it is possible that the compounds of the present invention comprise a structure of formulae (VIb-3) to (VIb-10), wherein the compounds of the present invention are more preferably selected from the compounds of formulae (VIb-3) to (VIb-10):

wherein the symbols R and R ¹ Having the definitions given above, especially for formula (I), the label s is 0, 1,2,3,4, 5 or 6, preferably 0, 1,2,3 or 4, more preferably 0, 1 or 2, the label m is 0, 1,2,3 or 4, preferably 0, 1 or 2, the label n is 0, 1,2 or 3, preferably 0, 1 or 2, and the label l is 0, 1 or 2.

With regard to the structures of formulae (VIb-1) to (VIb-8), the preferred features detailed above for the structures/compounds of formula (I) are applicable. This is especially true of the R group. The structures of formulae (VIb-1) to (VIb-8) may more preferably have hole transporting and/or hole conductor groups as defined above.

Particular preference is furthermore given to compounds of the invention having the structure of the formulae (VIb-1) to (VIb-8), which have the following properties:

in this context, the groups of formulae Q-11 to Q-25 in the compounds having the structures of formulae (VIb-1) to (VIb-8) detailed in the tables shown above comprise R ¹ Group R ¹ The radical preferably represents an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more non-aromatic R ² Substituted by groups; preferably, the groups of formulae Q-11 to Q-25 in compounds having a structure of formula (IVa) detailed in the tables shown above have at least one R ¹ Radical, preferably at least two R ¹ Group R ¹ The group is selected from the formula (R) ¹ -1) to (R) ¹ -43), preferably of formula R ¹ -1 to R ¹ -28 and R ¹ -34 to R ¹ A radical of formula R-38, particularly preferably of formula R ¹ -1、R ¹ -3、R ¹ -4、R ¹ -10、R ¹ -11、R ¹ -12、R ¹ -13、R ¹ -14、R ¹ -16、R ¹ -17、R ¹ -18、R ¹ -19、R ¹ -20、R ¹ -21、R ¹ -22、R ¹ -24 and/or R ¹ -37.

The present invention further provides compounds comprising at least one structure of formula (VII), preferably a compound of formula (VII):

wherein the symbols Ar and W have the aboveIn particular for the definition given for formula (I), and ring KON denotes an aromatic or heteroaromatic ring system having two, preferably three, fused aromatic or heteroaromatic rings and having from 10 to 60 aromatic ring atoms, preferably from 12 to 40 aromatic ring atoms, wherein the aromatic or heteroaromatic ring system may be substituted by one or more R ¹ Is substituted by radicals in which R ¹ May have the definitions given above, especially for formula (I).

It is also possible for the ring KON shown in formula (VII) to have W and SO via adjacent carbon atoms ₂ The five-membered rings of the groups are joined such that the ring fused to ring KON is a 5-membered ring. The ring KON in the formula (VII) has W and SO ₂ The rings of the group are fused.

It is also possible that the ring KON in the structure of formula (VII) forms a substructure of formulae (KON-1) to (KON-10) and/or (KON '-1) to (KON' -10) as detailed above, wherein the W or SO ₂ The radicals are in each case bound at the position indicated by o to an aromatic or heteroaromatic ring system having from 5 to 60 carbon atoms to form a ring.

In another preferred embodiment, it is possible that the compounds of the present invention comprise structures of formulae (VII-1) to (VII-10), wherein the compounds of the present invention may be more preferably selected from compounds of formulae (VII-1) to (VII-10):

wherein the symbol R ¹ And Ar has the definitions given above, especially for formula (I), the index s is 0, 1,2,3,4, 5 or 6, preferably 0, 1,2,3 or 4, more preferably 0, 1 or 2, the index m is 0, 1,2,3 or 4, preferably 0, 1 or 2, the index n is 0, 1,2 or 3, preferably 0, 1 or 2, and the index l is 0, 1 or 2.

With regard to the structures of the formulae (VII) and (VII-1) to (VII-10), the preferred features detailed above for the structures/compounds of the formula (I) are applicable. This is especially true for the W and Ar groups. The structures of formulae (VII) and (VII-1) to (VII-10) may more preferably have hole transporting and/or hole conductor groups as defined above.

Particular preference is furthermore given to compounds of the invention having the structures of the formulae (VII) and (VII-1) to (VII-10), which have the following properties:

in this context, the groups of formulae Q-11 to Q-25 in the compounds having the structures of formulae (VII) and (VII-1) to (VII-10) detailed in the tables shown above comprise R ¹ A radical, which preferably represents an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably having 6 to 13 aromatic ring atoms, each of which may be substituted by one or more non-aromatic R ² Substituted by groups; preferably, the group of formulae Q-11 to Q-25 in a compound having a structure of formula (IVa) detailed in the tables shown above has at least one R ¹ Radical, preferably at least two R ¹ Group R ¹ The radicals are selected from the formula (R) ¹ -1) to (R) ¹ -43), preferably of formula R ¹ -1 to R ¹ -28 and R ¹ -34 to R ¹ Radicals of the formula-38, particularly preferably of the formula R ¹ -1、R ¹ -3、R ¹ -4、R ¹ -10、R ¹ -11、R ¹ -12、R ¹ -13、R ¹ -14、R ¹ -16、R ¹ -17、R ¹ -18、R ¹ -19、R ¹ -20、R ¹ -21、R ¹ -22、R ¹ -24 and/or R ¹ -37.

The present invention also provides compounds comprising at least one structure of formula (VIII), preferably a compound of formula (VIII):

wherein the symbols X, ar and W have the definitions given above, especially for formula (I), wherein the structure/compound has at least one aromatic or heteroaromatic ring system having 5 to 60 carbon atoms and which is fused to a non-aromatic or non-heteroaromatic ring system.

It is preferably possible for the non-aromatic or non-heteroaromatic ring system fused to the aromatic or heteroaromatic ring system having from 5 to 60 carbon atoms to be a non-aromatic or non-heteroaromatic polycyclic ring system having at least 2 rings, preferably at least 3 rings.

It is preferably possible that the non-aromatic or non-heteroaromatic ring system fused to the aromatic or heteroaromatic ring system having from 5 to 60 carbon atoms is bound to two adjacent ring atoms, preferably carbon atoms, of the aromatic or heteroaromatic ring system having from 5 to 60 carbon atoms. Thus, the binding sites of the non-aromatic or non-heteroaromatic ring systems are preferably arranged ortho to the aromatic or heteroaromatic ring systems having 5 to 60 carbon atoms.

It is also possible that the nonaromatic or nonhomoaromatic ring system fused to the aromatic or heteroaromatic ring system having from 5 to 60 carbon atoms is formed by preferably adjacent at least two R groups. The at least two groups may be provided by X groups and/or substituents R bound to Ar groups, wherein Ar may be bound to the nitrogen atom shown in formula (VIII) and bound via a W group (C = N-Ar).

In the present context, in the structures/compounds of formula (VIII), it is possible that at least two, preferably adjacent, R groups form a fused ring together with the further group to which the two R groups are bound, wherein the two R groups form at least one structure of formulae (RA-1) to (RA-12):

wherein R is ¹ Having the meaning indicated above, especially for formula (I), the dotted bond represents a bond with two R groupsThe attachment site of the atom of the group to which the group is bound, and the further symbols have the following definitions:

Y ⁴ in each case identical or different and is C (R) ¹ ) ₂ 、(R ¹ ) ₂ C-C(R ¹ ) ₂ 、(R ¹ )C＝C(R ¹ )、NR ¹ NAr', O or S, preferably C (R) ¹ ) ₂ 、(R ¹ ) ₂ C-C(R ¹ ) ₂ 、(R ¹ )C＝C(R ¹ ) O or S;

R ^a identical or different on each occurrence and is F, a straight-chain alkyl, alkoxy or thioalkoxy group having from 1 to 40 carbon atoms, or an alkyl or alkenyl group having from 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group can in each case be substituted by one or more R ² Radical substitution of one or more non-adjacent CH ₂ The radical may be represented 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 ¹ ) -O-, -S-, SO or SO ₂ Instead of, or with 5 to 60 aromatic ring atoms and may in each case be substituted by one or more R ² Aromatic or heteroaromatic ring systems substituted by radicals, or having 5 to 60 aromatic ring atoms and which may be substituted by one or more R ² A group-substituted aryloxy or heteroaryloxy group; at the same time, two R ^a The radicals may also together form a ring system;

s is 0, 1,2,3,4, 5 or 6, preferably 0, 1,2,3 or 4, more preferably 0, 1 or 2;

t is 0, 1,2,3,4, 5,6, 7 or 8, preferably 0, 1,2,3 or 4, more preferably 0, 1 or 2;

v is 0, 1,2,3,4, 5,6, 7,8 or 9, preferably 0, 1,2,3 or 4, more preferably 0, 1 or 2.

It is also possible that at least two R groups forming the structures of formulae (RA-1) to (RA-12) and forming fused rings are R groups from adjacent X groups.

In a preferred embodiment of the invention, at least two R groups form a fused ring together with the further group to which the two R groups are bonded, wherein the two R groups preferably form at least one of the structures of formulae (RA-1 a) to (RA-4 f):

wherein the symbol R ^a And R ¹ And the indices s and t have the definitions given above, in particular for the formulae (RA-1) to (RA-12), the dashed bonds denote the attachment sites, and the index m is 0, 1,2,3 or 4, preferably 0, 1 or 2.

In one further preferred arrangement, at least two R groups form a fused ring together with the further group to which the two R groups are bonded, wherein the two R groups form a structure of formula (RB):

wherein R is ¹ Having the definitions described above, especially for formula (I), the dotted bond represents the attachment site, the index m is 0, 1,2,3 or 4, preferably 0, 1 or 2, and Y ⁵ Is C (R) ¹ ) ₂ 、NR ¹ NAr, O or S, preferably C (R) ¹ ) ₂ NAr or O.

It is possible here that at least two R groups forming the structure of formula (RB) and forming a fused ring are R groups from adjacent X groups.

It is also possible that at least two R groups forming the structure of formula (RB) and forming fused ring R groups are adjacent, especially in an ortho arrangement, such that the ring is adjacent to Y ⁵ The groups together are a 5-membered ring.

In another preferred embodiment, it is possible that the compounds of the present invention comprise structures of formulae (VIII-1) to (VIII-13), wherein the compounds of the present invention may more preferably be selected from compounds of formulae (VIII-1) to (VIII-13), wherein the compounds have at least one fused ring:

wherein the symbols R and Ar have the definitions given above, especially for formula (I), the index m is 0, 1,2,3 or 4, preferably 0, 1 or 2, the index n is 0, 1,2 or 3, preferably 0, 1 or 2, the index l is 0, 1 or 2, and the symbol o represents the attachment site of a fused ring.

Fused rings, especially in formulae (VIII) and (VIII-1) to (VIII-13), are preferably formed by at least one of the structures of formulae (RA-1) to (RA-12), formulae (RA-1 a) to (RA-4 f), and/or formula (RB) together with the ring atom marked by the symbol o, with the structures of formulae (RA-1) to (RA-12), formulae (RA-1 a) to (RA-4 f) being particularly preferred.

With respect to the structures of formulae (VIII) and (VIII-1) to (VIII-13), the preferred features detailed above for the structures/compounds of formula (I) are applicable. This is especially true for the W and Ar groups. The structures of formulae (VIII) and (VIII-1) to (VIII-13) may more preferably have hole transporting and/or hole conductor groups as defined above.

Particular preference is furthermore given to the compounds of the invention having the structures of the formulae (VIII) and (VIII-1) to (VIII-13), which have the following properties:

in this context, compounds having the structures of formulae (VIII) and (VIII-1) to (VIII-13) detailed in the tables shown above are of formulae Q-11 to QThe group of-25 contains R ¹ Group R ¹ The radical preferably represents an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more non-aromatic R ² Substituted by groups; preferably, the group of formulae Q-11 to Q-25 in a compound having a structure of formula (IVa) detailed in the tables shown above has at least one R ¹ Radical, preferably at least two R ¹ Group R ¹ The group is selected from the formula (R) ¹ -1) to (R) ¹ -43), preferably of formula R ¹ -1 to R ¹ -28 and R ¹ -34 to R ¹ A radical of formula R-38, particularly preferably of formula R ¹ -1、R ¹ -3、R ¹ -4、R ¹ -10、R ¹ -11、R ¹ -12、R ¹ -13、R ¹ -14、R ¹ -16、R ¹ -17、R ¹ -18、R ¹ -19、R ¹ -20、R ¹ -21、R ¹ -22、R ¹ -24 and/or R ¹ -37.

The present invention furthermore provides compounds which comprise exactly two, exactly three or exactly four structures of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) and/or preferred embodiments thereof, in particular structures of the formulae (III), (IVa) to (IVc), (V), (VIa) to (VIc), (VII-1) to (VII-10), (VIII-1) to (VIII-10).

More preferably, the compound is selected from compounds of formulae (IXa) to (IXc):

wherein the symbols Ar and W have the meanings given above, especially for formula (I), X is N, CR, if L ¹ A group is bonded to X, then X is C, provided that no more than two X groups in a ring are N; and L is ¹ RepresentA bond or have 5 to 40, preferably 5 to 30, aromatic ring atoms and may be substituted by one or more R ¹ A group-substituted aromatic or heteroaromatic ring system in which L ¹ Preferably a bond or selected from the formula (L) as defined above ¹ -1) to (L) ¹ -76), wherein, in formula (VIIa), said L ¹ More preferably, the group is not a bond.

More preferably, the compound is selected from compounds of formulae (Xa) to (Xc):

wherein the symbols R and Ar have the definitions given above, especially for formula (I), the index m is 0, 1,2,3 or 4, preferably 0, 1 or 2, and L ¹ Having the definitions given above, in particular for formulae (IXa) to (IXc), and preferably being selected from the formulae (L) defined above ¹ -1) to (L) ¹ -76), wherein, in formulae (IXa) to (IXc), said L ¹ More preferably, the group is not a bond.

More preferably, the compound is selected from compounds of formulae (XIa) to (XIc):

wherein the symbols R and Ar have the definitions given above, in particular for formula (I), the index n is 0, 1,2 or 3, preferably 0, 1 or 2, the index m is 0, 1,2,3 or 4, preferably 0, 1 or 2, and L ¹ Having the definitions given above, especially for formulae (IXa) to (IXc), and preferably being selected from the formulae (L) defined above ¹ -1) to (L) ¹ -76).

More preferably, the compound is selected from compounds of formulae (XIIa) to (XIIc):

wherein the symbols R and Ar have the definitions given above, especially for formula (I), the index n is 0, 1,2 or 3, preferably 0, 1 or 2, the index m is 0, 1,2,3 or 4, preferably 0, 1 or 2, and L ¹ Having the definitions given above, in particular for formulae (IXa) to (IXc), and preferably being selected from the formulae (L) defined above ¹ -1) to (L) ¹ -76).

In a preferred configuration, the compounds of the invention may comprise at least one structure of formula (XIII-1) and/or (XIII-2), preferably selected from compounds of formula (XIII-1) and/or (XIII-2):

wherein the X and R groups have the definitions given above, especially for formula (I), the indices m are identical or different and are 0, 1,2,3 or 4, preferably 0, 1,2 or 3, more preferably 0, 1 or 2, especially preferably 0 or 1, the index z is 2,3 or 4, and the ring AR is ⁿ Is a compound having 5 to 60 aromatic ring atoms and may be substituted by one or more R ¹ A radical-substituted aromatic or heteroaromatic ring system, in which R ¹ May have the definitions given above, especially for formula (I).

Preferably, the ring AR ⁿ Is an aromatic or heteroaromatic ring system having two, preferably three, fused aromatic or heteroaromatic rings and having from 10 to 60 aromatic ring atoms, preferably from 12 to 40 aromatic ring atoms.

It is also possible that the ring AR shown in the formulae (XIII-1) and/or (XIII-2) ⁿ The ring having two nitrogen atoms is bonded via adjacent carbon atoms so that the ring fused with the ring KON is a 5-membered ring. Ring AR in the formulae (XIII-1) and/or (XIII-2) ⁿ Fused to the ring through two nitrogen atoms.

It is also possible for the ring AR in the structure of the formula (XIII) ⁿ Form (AR) ⁿ -1) to (AR) ⁿ -29) substructure:

wherein X' is N or CR ¹ Preferably CR ¹ Wherein R is ¹ May have the definitions given above, especially for formula (I), U is selected from O, S, C (R) ¹ ) ₂ 、N(R ¹ )、B(R ¹ )、Si(R ¹ ) ₂ 、C＝O、S＝O、SO ₂ 、P(R ¹ ) And P (= O) R ¹ And W or SO ₂ Each of the groups is combined at the position identified by o with an aromatic or heteroaromatic ring having from 5 to 60 carbon atoms to form a ring.

It is also possible for the ring AR in the structure of the formula (XIII) ⁿ Form (AR) ^nl -1) to (AR) ^nl -30) of the sub-structure of,

wherein X' is N or CR ¹ Preferably CR ¹ Wherein R is ¹ May have the definitions given above, especially for formula (I), U is selected from O, S, C (R) ¹ ) ₂ 、N(R ¹ )、B(R ¹ )、Si(R ¹ ) ₂ 、C＝O、S＝O、SO ₂ 、P(R ¹ ) And P (= O) R ¹ The index o is 0, 1 or 2, preferably 0 or 1, the index n is 0, 1,2 or 3, preferably 0, 1 or 2, the index m is 0, 1,2,3 or 4, preferably 0, 1 or 2, and the index l is 0, 1,2,3,4, 5 or 6, preferably 0, 1 or 2, and W or SO ₂ Each of the groups is combined at the position identified by o with an aromatic or heteroaromatic ring having from 5 to 60 carbon atoms to form a ring.

It is also possible that in the formula (AR) ^nl -1) to (AR) ^nl -30), the sum of the indices o, n, m and l is not more than 6, preferably not more than 4 and more preferably not more than 2.

With respect to the structures of formula (XIII-1) and (XIII-2), the preferred features detailed above for the structures/compounds of formula (I) are applicable. This is especially true of the R group. The structures of formulae (XIII-1) and (XIII-2) may more preferably have hole transporting and/or hole conductor groups as defined above.

Particular preference is furthermore given to compounds of the invention having the structures of the formulae (XIII-1) and (XIII-2), which have the following properties:

in the present context, the groups of formulae Q-11 to Q-25 in the compounds having the structures of formulae (XIII-1) and (XIII-2) detailed in the tables shown above comprise R ¹ A radical, which preferably represents an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably having 6 to 13 aromatic ring atoms, each of which may be substituted by one or more non-aromatic R ² Substitution of radicals; preferably, the group of formulae Q-11 to Q-25 in a compound having a structure of formula (IVa) detailed in the tables shown above has at least one R ¹ Radical, preferably at least two R ¹ Group R ¹ The radicals are selected from the formula (R) ¹ -1) to (R) ¹ -43), preferably of formula R ¹ -1 to R ¹ -28 and R ¹ -34 to R ¹ A group of-38, particularly preferablyFormula R ¹ -1、R ¹ -3、R ¹ -4、R ¹ -10、R ¹ -11、R ¹ -12、R ¹ -13、R ¹ -14、R ¹ -16、R ¹ -17、R ¹ -18、R ¹ -19、R ¹ -20、R ¹ -21、R ¹ -22、R ¹ -24 and/or R ¹ -37.

The present invention furthermore provides a compound of formula (XIV):

wherein the symbols Ar and W have the definitions given above, in particular for formula (I), the index z is 2,3 or 4, and the ring AR ⁿ Is a compound having 5 to 60 aromatic ring atoms and may be substituted by one or more R ¹ An aromatic or heteroaromatic ring system substituted by a group, in which R ¹ May have the definitions given above, especially for formula (I).

It is also possible that the ring AR in the structure of the formula (XIV) ⁿ Form the formula (AR) as detailed above ⁿ -1) to (AR) ⁿ -29) and/or formula (AR) ^nl -1) to (AR) ^nl Substructure of-30), wherein W or SO ₂ The radicals are in each case bonded in the position identified by o to an aromatic or heteroaromatic ring having from 5 to 60 carbon atoms to form a ring.

It is also possible that the ring AR in the structure of the formula (XIV) ⁿ Via adjacent carbon atoms with W and SO ₂ The five-membered ring of the group being bound so as to be bound to the ring AR in the structure of the formula (XIV) ⁿ The fused ring is a 5-membered ring. The ring KON in the formula (XIV) has W and SO ₂ The rings of the groups are fused.

With regard to the structure of formula (XIV), the preferred features detailed above for the structures/compounds of formula (I) are applicable. This is especially true for the W and Ar groups. The structure of formula (XIV) may more preferably have hole transporting and/or hole conductor groups as defined above.

Particular preference is furthermore given to compounds of the invention having the structure of the formula (XIV) which have the following properties:

in this context, the groups of formulae Q-11 to Q-25 in the compounds having the structure of formula (XIV) detailed in the tables shown above comprise R ¹ Group, R ¹ The radical preferably represents an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, each of which may be substituted by one or more non-aromatic R ² Substitution of radicals; preferably, the groups of formulae Q-11 to Q-25 in compounds having a structure of formula (IVa) detailed in the tables shown above have at least one R ¹ Radical, preferably at least two R ¹ Group R ¹ The group is selected from the formula (R) ¹ -1) to (R) ¹ -43), preferably of formula R ¹ -1 to R ¹ -28 and R ¹ -34 to R ¹ Radicals of the formula-38, particularly preferably of the formula R ¹ -1、R ¹ -3、R ¹ -4、R ¹ -10、R ¹ -11、R ¹ -12、R ¹ -13、R ¹ -14、R ¹ -16、R ¹ -17、R ¹ -18、R ¹ -19、R ¹ -20、R ¹ -21、R ¹ -22、R ¹ -24 and/or R ¹ -37.

Preferred embodiments of the compounds of the invention are detailed in the examples, which compounds can be used for all purposes of the invention, either alone or in combination with further compounds.

The above-described preferred embodiments may be combined with each other as needed as long as the conditions described in claim 1 are satisfied. In a particularly preferred embodiment of the invention, the above-described preferred embodiments apply at the same time.

The compounds of the invention can in principle be prepared by various methods. However, the process described below has been found to be particularly suitable.

The present invention therefore also provides a process for preparing the compounds of the invention, preferably compounds comprising the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4), in which a compound comprising at least one benzisothiazolyl group is linked to a compound comprising at least one aromatic or heteroaromatic group in a coupling reaction.

Suitable compounds comprising at least one heterocyclic structure are in many cases commercially available, and the starting compounds detailed in the examples can be obtained by known methods, so reference is made to known methods.

These compounds can be reacted with further compounds comprising at least one aromatic or heteroaromatic group by known coupling reactions, the requirements for this purpose being known to the person skilled in the art, and the detailed description in the examples assists the person skilled in the art in carrying out these reactions.

All particularly suitable and preferred coupling reactions leading to C-C bond formation and/or C-N bond formation are those according to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA and HIYAYAMA. These reactions are widely known and the examples will provide further guidance to those skilled in the art.

The principle of the preparation processes detailed above is in principle known from the literature on analogous compounds and can be readily adapted by the person skilled in the art for the preparation of the compounds of the invention. Other information may be found in the embodiments.

By these methods, purification, if necessary, such as recrystallization or sublimation, is carried out to obtain high purity, preferably greater than 99% (by ¹ H NMR and/or HPLC) of a compound of the invention comprising the structure of formula (I).

The compounds of the invention may also have suitable substituents, such as longer alkyl groups (about 4 to 20 carbon atoms), in particular branched alkyl groups, or optionally substituted aryl groups, such as xylyl, mesitylyl or branched terphenyl or quaterphenyl groups, which bring about solubility in standard organic solvents, for example such that the compounds are soluble in toluene or xylene at room temperature in sufficient concentrations to enable processing of the compounds from solution. These soluble compounds are particularly well suited for processing from solution, for example by printing methods. In addition, it should be emphasized that the compounds of the invention comprising at least one structure of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) and their preferred embodiments shown in the further structures already have an enhanced solubility in these solvents.

In addition, the compounds of the present invention may contain one or more crosslinkable groups. "crosslinkable group" means a functional group capable of undergoing an irreversible reaction. This forms an insoluble cross-linked material. Crosslinking can generally be promoted by heating or by UV radiation, microwave radiation, x-radiation or electron beams. In this case, virtually no by-products are formed in the crosslinking. In addition, the crosslinkable groups which may be present in the functional compounds are very readily crosslinkable, so that relatively small amounts of energy are required for crosslinking (for example <200 ℃ in the case of thermal crosslinking).

Examples of crosslinkable groups are units containing double bonds, triple bonds, precursors capable of forming double or triple bonds in situ, or heterocyclic addition polymerizable groups. The crosslinkable groups include vinyl, alkenyl, preferably vinyl and propenyl, C _4-20 Cycloalkenyl, azide, oxirane, oxetane, di (hydrocarbyl) amino, cyanate, hydroxy, glycidyl ether, acrylic acid C _1-10 Alkyl esters, methacrylic acid C _1-10 Alkyl ester, alkenyloxy, preferably vinyloxy, perfluoroalkenyloxy, preferably perfluorovinyloxy, alkynyl, preferably ethynyl, maleimide, cyclobutylphenyl, tris (C) _1-4 ) -alkylsiloxy and tri (C) _1-4 ) -alkylsilyl groups. Particularly preferred are cyclobutylphenyl, vinyl and alkenyl groups.

The compounds of the invention may also be mixed with polymers. These compounds can likewise be covalently incorporated into polymers. Compounds substituted with a reactive leaving group such as bromo, iodo, chloro, boronic acid or boronic ester, or with a reactive polymerizable group such as alkene or oxetane are particularly feasible. These can be used as monomers for preparing corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization is preferably effected via halogen functions or boronic acid functions or via polymerizable groups. The polymers can additionally be crosslinked via such groups. The compounds and polymers of the invention may be used in the form of crosslinked or uncrosslinked layers.

The present invention therefore also provides oligomers, polymers or dendrimers which contain one or more of the structures of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) detailed above or of the compounds of the invention, where one or more linkages to the polymer, oligomer or dendrimer are present in the compounds of the invention or in the structures of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4). These thus form side chains or linkages of the oligomers or polymers in the main chain, according to the structures of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) or the linkages of the compounds. The polymer, oligomer or dendrimer may be conjugated, partially conjugated or non-conjugated. The oligomer or polymer may be linear, branched or dendritic. The same preferred features as described above apply to the repeating units of the compounds of the invention in oligomers, dendrimers and polymers.

To prepare the oligomers or polymers, the monomers of the invention are homopolymerized or copolymerized with additional monomers. Preference is given to copolymers in which the units of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) or the preferred embodiments described above and below are present in the range from 0.01 to 99.9 mol%, preferably from 5 to 90 mol%, more preferably from 20 to 80 mol%. Suitable and preferred comonomers forming the basic skeleton of the polymer are selected from fluorenes (for example according to EP 842208 or WO 2000/022026), spirobifluorenes (for example according to EP 7070707020, EP 894107 or WO 2006/061181), p-phenylene radicals (for example according to WO 92/18552), carbazoles (for example according to WO 2004/070772 or WO 2004/113468), thiophenes (for example according to EP 1028136), dihydrophenanthrenes (for example according to WO 2005/014689), cis-and trans-indenofluorenes (for example according to WO 2004/041901 or WO 2004/113412), ketones (for example according to WO 2005/040302), phenanthrenes (for example according to WO 2005/104264 or WO 2007/017066) or a plurality of these units. The polymers, oligomers and dendrimers may also contain further units, such as hole transport units, especially those based on triarylamines, and/or electron transport units.

Of particular interest are also the compounds of the invention having a high glass transition temperature. In this respect, particular preference is given to compounds comprising the structures of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) or the preferred embodiments described above and below, which have a glass transition temperature, measured according to DIN 51005 (version 2005-08), of at least 70 ℃, more preferably at least 110 ℃, even more preferably at least 125 ℃ and particularly preferably at least 150 ℃.

For processing the compounds of the invention from the liquid phase, for example by spin coating or by printing methods, formulations of the compounds of the invention are required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents may preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, bis-xylene

Alkanes, phenoxytoluenes, especially 3-phenoxytoluene, (-) -fenchone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylanisole, 3, 5-dimethylanisole, acetophenone, α -terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylene, octylbenzene, 1-bis (3, 4-dimethylphenyl) ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylene, menthyl isovalerate, hexanoateHexyl esters or mixtures of these solvents.

Accordingly, the present invention also provides a formulation or composition comprising at least one compound of the invention and at least one additional compound. The further compound may for example be a solvent, especially one of the above solvents or a mixture of these solvents. If the additional compound comprises a solvent, the mixture is referred to herein as a formulation. Alternatively, the further compound may be at least one further organic or inorganic compound, such as a luminescent compound and/or a further host material, also used in the electronic device. Suitable light-emitting compounds and further host materials in connection with the organic electroluminescent device are listed below. The additional compounds may also be polymeric.

Thus, the present invention further provides a composition comprising a combination comprising:

a) One or more compounds comprising at least one structure of formula (I), preferably one or more compounds of formula (I),

wherein the symbols X, W and Ar have the definitions given above, in particular for formula (I);

b) A further compound selected from: fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, exciton blocking materials, electron injecting materials, electron transporting materials, electron blocking materials, hole injecting materials, hole conducting materials, hole blocking materials, n-type dopants, p-type dopants, wide band gap materials, and/or charge generating materials.

The present invention also provides a composition comprising at least one compound comprising at least one structure of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) or the preferred embodiments described above and below, and at least one wide bandgap material, which is understood to mean a material in the sense of the disclosure of US 7,294,849. These systems exhibit particularly advantageous performance data in electroluminescent devices.

Preferably, the further compound may have a band gap of 2.5eV or more, preferably 3.0eV or more, very preferably 3.3eV or more. One way to calculate the bandgap is via the energy levels of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO).

The molecular orbitals of the material, in particular the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO), their energy levels and the lowest triplet state T, are determined via quantum chemical calculations ₁ Energy of and lowest excited singlet state S ₁ The energy of (a). To calculate the organic material without metal, first a geometric optimization was performed by the "ground state/semi-empirical/default spin/AM 1/charge 0/spin singlet" method. Subsequently, energy calculations are performed based on the optimized geometry. This was done with the "6-31G (d)" base set (charge 0, spin singlet) using the "TD-SCF/DFT/default spin/B3 PW91" method. For metal-containing compounds, the geometry was optimized via the "ground state/hartley-fox/default spin/LanL 2 MB/charge 0/spin singlet" method. Energy calculations were carried out analogously to the method described above for organic substances, with the difference that for the metal atoms a "LanL2DZ" group was used, whereas for the ligands a "6-31G (d)" group was used. The HOMO energy level HEh or LUMO energy level LEh measured in Hartree units is obtained from the energy calculation. This was used to determine the HOMO and LUMO energy levels in electron volts, calibrated by cyclic voltammetry measurements, as follows:

HOMO(eV)＝((HEh*27.212)-0.9899)/1.1206

LUMO(eV)＝((LEh*27.212)-2.0041)/1.385。

in the context of the present application, these values are considered as HOMO and LUMO energy levels of the material.

Lowest triplet state T ₁ Defined as the triplet energy with the lowest energy apparent from the quantum chemistry calculationsAmount of the compound (A).

Lowest excited singlet S ₁ Defined as the excited singlet energy with the lowest energy apparent from the quantum chemistry calculations.

The methods described herein are independent of the software package used and give the same results throughout. Examples of programs commonly used for this purpose are "Gaussian09W" (Gauss Corp.) and Q-Chem 4.1 (Q-Chem Corp.).

The invention also relates to a composition comprising at least one compound comprising a structure of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) or the preferred embodiments described above and below and at least one phosphorescent emitter, the term "phosphorescent emitter" also being understood to mean a phosphorescent dopant.

The dopant in the system comprising the matrix material and the dopant is understood to mean the component of the mixture having the smaller proportion. Accordingly, a host material in a system comprising a host material and a dopant is understood to mean a component in a mixture having a greater proportion.

Preferred phosphorescent dopants for use in the matrix system, preferably the mixed matrix system, are the preferred phosphorescent dopants specified below.

The term "phosphorescent dopant" generally encompasses compounds in which light emission is achieved by spin-forbidden transitions, e.g., transitions from an excited triplet state or a state with a higher spin quantum number, e.g., a quintet state.

Suitable phosphorescent compounds (= triplet emitters) are in particular the following compounds: which emits light when suitably excited, preferably in the visible region, and also contains at least one atom having an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially a compound of a metal having this atomic number. Preferred phosphorescent emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or platinum.

Examples of such emitters can be found in the following 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 377 WO 2014/094961, WO 2014/094960, WO 2015/036074, WO 2015/104045, WO 2015/117718, WO 2016/015815, WO 2016/124304, WO 2017/032439, WO 2018/011186, WO 2018/001990, WO 2018/019687, WO 2018/019688, WO 2018/041769, WO 2018/054798, WO 2018/069196, WO 2018/069197, WO 2018/920673, WO 2018/178001, WO 2018/177981, WO 2019/020538, WO 2019/115423, WO 2019/158453 and WO 2019/179909. In general, all phosphorescent complexes used in phosphorescent electroluminescent devices according to the prior art and known to the person skilled in the art of organic electroluminescence are suitable, and the person skilled in the art will be able to use further phosphorescent complexes without inventive step.

Examples of phosphorescent dopants are listed in the following table:

when the compound used according to the invention is used as a matrix material for phosphorescent compounds in the light-emitting layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). Phosphorescence in the context of the present invention is understood to mean emission from an excited state with a higher spin multiplicities, i.e. a spin state >1, in particular from an excited triplet state. In the context of the present application, all luminescent complexes containing transition metals or lanthanides, in particular all iridium, platinum and copper complexes, are to be regarded as phosphorescent compounds.

The mixture of compounds and luminescent compounds used according to the invention contains between 99 and 1% by volume, preferably between 98 and 10% by volume, more preferably between 97 and 60% by volume and in particular between 95 and 80% by volume of the compounds 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.%, more preferably between 3 and 40 vol.% and in particular between 5 and 20 vol.% of luminophores, based on the total mixture of luminophores and matrix material.

In one embodiment of the present invention, the compounds used according to the invention are used here as the sole matrix material ("single host") for phosphorescent emitters.

In a preferred embodiment of the present invention, the organic electroluminescent device contains the compounds used according to the invention, preferably comprising the structures of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) or the compounds of the preferred embodiments detailed above, as a matrix material in the light-emitting layer or layers, preferably as an electron-conducting matrix material, preferably in combination with a further matrix material, preferably a hole-conducting matrix material. In another preferred embodiment of the present invention, the further matrix material is an electron transport compound. In a further preferred embodiment, the further matrix material is a compound with a large band gap which, even if involved in hole and electron transport in the layer, does not participate to a significant extent in hole and electron transport. The light-emitting layer comprises at least one light-emitting compound.

In a further particularly preferred embodiment of the present invention, the organic electroluminescent device of the invention comprises the compounds used according to the invention, preferably compounds of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) or the preferred embodiments detailed above, in a hole-transporting layer or in an electron-transporting layer.

The present invention therefore also relates to a composition comprising at least one compound used according to the invention, preferably comprising the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) or the compounds of the preferred embodiments described above and below, and at least one further matrix material.

Suitable matrix materials which can be used in combination with the compounds of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) or according to a preferred embodiment are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680; triarylamines, carbazole derivatives, for example CBP (N, N-biscarbazolylbiphenyl) or carbazole derivatives disclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527, WO 2008/086851 or WO 2013/041176; indolocarbazole derivatives, for example according to WO 2007/063754 or WO 2008/056746; indenocarbazole derivatives, for example according to WO 2010/136109, WO 2011/000455, WO 2013/041176 or WO 2013/056776; azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160; bipolar matrix materials, for example according to WO 2007/137725; silanes, for example according to WO 2005/111172; boron-nitrogen heterocyclic-slow or boric acid esters, for example according to WO 2006/117052; triazine derivatives, for example according to WO 2007/063754, WO 2008/056746, WO 2010/015306, WO 2011/057706, WO 2011/060859 or WO 2011/060877; zinc complexes, for example according to EP 652273 or WO 2009/062578; silicon-diazacyclo-slow or silicon-tetraazazepine-slow derivatives, for example according to WO 2010/054729; phosphorus diazacyclo-slow derivatives, for example according to WO 2010/054730; bridged carbazole derivatives, for example according to WO 2011/042107, WO 2011/060867, WO 2011/088877 and WO 2012/143080; terphenyl derivatives, for example according to WO 2012/048781; dibenzofuran derivatives, for example according to WO 2015/16942, WO 2016/015810, WO 2016/023608, WO 2017/148564 or WO 2017/148565; or biscarbazoles, for example according to JP 3139321B 2; lactams, for example according to WO 2011/116865, WO 2011/137951 or WO 2013/064206; 4-spirocarbazole derivatives, for example according to WO 2014/094963 or WO 2015/192939. Additional phosphorescent emitters which emit at a shorter wavelength than the actual emitter may likewise be present as co-hosts in the mixture.

Preferred co-host materials are triazines, quinazolines, quinoxalines, triarylamine derivatives, especially monoamines, indenocarbazole derivatives, 4-spirocarbazole derivatives, lactams and carbazole derivatives.

It may also be preferred to use a plurality of different matrix materials, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material, in the form of a mixture. It is also preferred to use a mixture of a charge transport matrix material and an electrically inert matrix material which does not participate significantly even if it participates in charge transport, as described in, for example, WO 2010/108579. Particularly suitable as co-host materials in combination with the compounds according to the invention are compounds which have a large band gap and which themselves do not participate at least to a significant extent in the charge transport of the light-emitting layer. Such materials are preferably pure hydrocarbons. Examples of such materials may be found, for example, in WO 2009/124627 or WO 2010/006680.

It is furthermore preferred to use mixtures of two or more triplet emitters with a matrix. In this case, triplet emitters having a shorter-wave emission spectrum are used as co-hosts for triplet emitters having a longer-wave emission spectrum.

More preferably, in a preferred embodiment, the compounds used according to the invention comprising the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) can be used as matrix material in the light-emitting layer of an organic electronic device, in particular in an organic electroluminescent device, for example in an OLED or OLEC. In this case, a host material comprising a compound comprising a structure of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) or the preferred embodiments described above and below is present in the electronic device in combination with one or more dopants, preferably phosphorescent dopants.

The proportion of the matrix material in the light-emitting layer is in this case between 50.0% by volume and 99.9% by volume for fluorescent light-emitting layers, preferably between 80.0% by volume and 99.5% by volume, and more preferably between 92.0% by volume and 99.5% by volume, and between 85.0% by volume and 97.0% by volume for phosphorescent light-emitting layers.

Accordingly, the proportion of the dopant is between 0.1 and 50.0 vol%, preferably between 0.5 and 20.0 vol%, and more preferably between 0.5 and 8.0 vol% for the fluorescent light-emitting layer and between 3.0 and 15.0 vol% for the phosphorescent light-emitting layer.

The light-emitting layer of the organic electroluminescent device may also comprise systems containing a plurality of matrix materials (mixed matrix systems) and/or a plurality of dopants. Also in this case, the dopant is generally those materials having a smaller proportion in the system and the host material is those materials having a larger proportion in the system. However, in individual cases, the proportion of a single host material in the system may be less than the proportion of a single dopant.

In another preferred embodiment of the present invention, compounds comprising the structures of formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) or the preferred embodiments described above and below are used as components of the mixed matrix system. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials is a material having a hole transporting property, and the other material is a material having an electron transporting property. However, the desired electron transport and hole transport properties of the mixed matrix component may also be combined predominantly or completely in a single mixed matrix component, in which case the further mixed matrix component fulfils other functions. Two different matrix materials may be present in a ratio of 1. Preferably, mixed matrix systems are used in phosphorescent organic electroluminescent devices. One source of more detailed information on mixed matrix systems is application WO 2010/108579.

The invention also provides the use of the compounds according to the invention in electronic devices, in particular in organic electroluminescent devices.

The invention furthermore provides for the use of the compounds used according to the invention and/or of the oligomers, polymers or dendrimers of the invention as fluorescent emitters, emitters which exhibit TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole transport materials, hole injection materials, electron blocking materials, hole blocking materials and/or wide band gap materials in electronic devices, preferably as fluorescent emitters (singlet emitters), host materials, hole transport materials and/or electron transport materials.

The present invention furthermore provides an electronic device comprising at least one compound which can be used according to the invention and/or a compound of the invention. An electronic device in the context of the present invention is a device having an anode, a cathode and at least one intermediate layer comprising at least one organic compound. The component may also comprise an inorganic material or a layer formed entirely of an inorganic material.

The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), preferably Organic Light Emitting Diodes (OLED), small molecule based organic light emitting diodes (sOLED), polymer based organic light emitting diodes (PLED), light emitting electrochemical cells (LEC), organic laser diodes (O-laser), organic plasma light emitting devices (d.m.koller et al, nature Photonics 2008, 1-4), organic integrated circuits (O-IC), organic field effect transistors (O-FET), organic thin film transistors (O-TFT), organic light emitting transistors (O-LET), organic solar cells (O-SC), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQD) and organic electrical sensors, preferably organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), more preferably Organic Light Emitting Diodes (OLED), small molecule based organic light emitting diodes (sOLED), polymer based organic light emitting diodes (PLED), especially phosphorescent.

The organic electroluminescent device includes a cathode, an anode, and at least one light emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. An intermediate layer having an exciton blocking function may likewise be introduced, for example, between two light-emitting layers. However, it should be noted that each of these layers need not necessarily be present. In this case, the organic electroluminescent device may include one light emitting layer, or it may include a plurality of light emitting layers. If there are a plurality of light-emitting layers, these light-emitting layers preferably have a plurality of emission peaks between 380nm and 750nm in total, so that the overall result is white emission; in other words, a plurality of light-emitting compounds that can emit fluorescence or phosphorescence are used in the light-emitting layer. Particularly preferred are systems with three light-emitting layers, wherein the three layers exhibit blue, green and orange or red light emission. The organic electroluminescent device of the invention may also be a tandem electroluminescent device, in particular a white light-emitting OLED.

In another embodiment of the present invention, the organic electroluminescent device of the present invention does not contain any separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, which means that the light-emitting layer is directly adjacent to the hole injection layer or anode and/or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode, as described for example in WO 2005/053051. In addition, a metal complex which is the same as or similar to the metal complex in the light-emitting layer may be used as a hole transporting or hole injecting material of the directly adjacent light-emitting layer, as described in, for example, WO 2009/030981.

Depending on the exact structure, the compounds of the invention can be used in different layers. Organic electroluminescent devices comprising compounds of the formula (I) or the preferred embodiments detailed above as host materials for phosphorescent emitters, emitters which exhibit TADF (thermally activated delayed fluorescence), especially fluorescent emitters or phosphorescent emitters, in the light-emitting layer are preferred. In addition, the compounds according to the invention can also be used in electron-transport layers and/or in hole-transport layers and/or in exciton-blocking layers and/or in hole-blocking layers. The compounds according to the invention are particularly preferably used as matrix materials for red, orange or yellow phosphorescent emitters, in particular red phosphorescent emitters, in the light-emitting layer or as electron transport materials or hole blocking materials in an electron transport layer or hole blocking layer.

The invention also provides an electronic device, preferably an organic electroluminescent device, comprising one or more compounds according to the invention and/or at least one oligomer, polymer or dendrimer according to the invention as electron-conducting compound in one or more electron-conducting layers.

In the further layers, generally any material as used for said layers according to the prior art can be used, and the person skilled in the art is able to combine any of these materials with the inventive material in an electronic device without inventive effort.

The components are structured accordingly (depending on the application), contact connections are provided and finally sealed in a gas-tight manner, since the lifetime of these components is severely shortened in the presence of water and/or air.

Preference is furthermore given to electronic devices, in particular organic electroluminescent devices, which are characterized in that one or more layers are applied by a sublimation process. In this case, in vacuum sublimation systems, in general less than 10 ^-5 Mbar, preferably less than 10 ^-6 The material is applied by vapor deposition at an initial pressure of mbar. The initiationThe pressure may also be lower or higher, e.g. less than 10 ^-7 Millibar.

Preference is likewise given to electronic devices, in particular organic electroluminescent devices, which are characterized in that one or more layers are applied by the OVPD (organic vapor deposition) method or by sublimation with the aid of a carrier gas. In this case, 10 ^-5 The material is applied at a pressure of mbar to 1 bar. A particular example of such a method is the OVJP (organic vapour jet printing) method, in which the material is applied directly through a nozzle and is therefore structured (for example m.s. Arnold et al, appl.phys. Lett.2008,92, 053301).

Further preferred are electronic devices, especially organic electroluminescent devices, characterized in that one or more layers are produced from solution, for example by spin coating, or by any printing method, such as screen printing, flexographic printing, offset printing or nozzle printing, but more preferably LITI (photo induced thermal imaging, thermal transfer) or ink jet printing. For this purpose, soluble compounds are required, which are obtained, for example, by suitable substitution.

In addition, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.

These methods are generally known to the person skilled in the art and can be applied without inventive effort to organic electroluminescent devices comprising the compounds according to the invention.

The electronic device of the invention, in particular the organic electroluminescent device, is distinguished over the prior art by one or more of the following surprising advantages:

1. the electronic devices, in particular organic electroluminescent devices, which comprise the compounds, oligomers, polymers or dendrimers or preferred embodiments used according to the invention, in particular as emitters, preferably as fluorescent emitters, as electron-conducting and/or hole-transporting material or as matrix material, have very good lifetimes both above and below.

2. The electronic devices, in particular organic electroluminescent devices, comprising the compounds, oligomers, polymers or dendrimers or preferred embodiments used according to the invention, in particular as emitters, preferably as fluorescent emitters, as electron transport materials, hole transport materials and/or as host materials, described above and below, have excellent efficiency. More particularly, the efficiency is much higher than for similar compounds not containing the structure of the invention. In this context, the compounds, oligomers, polymers or dendrimers of the invention or the preferred embodiments described above and below result in low operating voltages when used in electronic devices. In this context, these compounds in particular lead to a low roll-off, i.e. a slight decrease in the power efficiency of the device at high luminous densities.

3. The electronic devices, in particular organic electroluminescent devices, comprising compounds, oligomers, polymers and dendrimers or preferred embodiments as emitters, preferably as fluorescent emitters, as electron transport materials, hole transport materials and/or as host materials, above and below, have very narrow emission bands with low Full Width at Half Maximum (FWHM) values and lead to particularly pure color emission that can be recognized by low CIE y values.

4. The compounds, oligomers, polymers or dendrimers or preferred embodiments used according to the invention, described above and below, exhibit very high thermal and photochemical stability and lead to compounds having a very long lifetime.

5. The use of compounds, oligomers, polymers or dendrimers or preferred embodiments as described above and below can avoid the formation of optical loss channels in electronic devices, especially organic electroluminescent devices. These devices are therefore characterized by a high PL efficiency and hence EL efficiency of the emitter, and excellent energy transport from the host to the dopant.

6. The compounds, oligomers, polymers or dendrimers or preferred embodiments described above and below have excellent glass film formation.

7. The compounds, oligomers, polymers or dendrimers or preferred embodiments described above and below form very good films from solutions.

These above-mentioned advantages are generally not accompanied by additional degradation of electronic properties.

In the further layers of the organic electroluminescent device according to the invention, any material conventionally used according to the prior art may be used. The person skilled in the art is therefore able, without inventive work, to use any materials known for use in organic electroluminescent devices in combination with the compounds of the invention, preferably comprising structures of the formulae (I), (IIa) to (IIc) and/or (IIb-1) to (IIb-4) or compounds according to preferred embodiments, which can be used as active compounds in organic electronic devices.

The compounds according to the invention generally have very good properties when used in organic electroluminescent devices. Especially in the case of the use of the compounds according to the invention in organic electroluminescent devices, the lifetime is significantly better than in comparable compounds according to the prior art. At the same time, other properties of the organic electroluminescent device, in particular efficiency and voltage, are equally better or at least comparable.

It should be noted that variations of the embodiments described in the present invention are covered by the scope of the invention. Any feature disclosed in this specification may be replaced by an alternative feature serving the same purpose, or an equivalent or similar purpose, unless expressly excluded. Thus, unless otherwise specified, any feature disclosed in this specification should be considered as a generic series of examples or as an equivalent or similar feature.

All of the features of the present invention may be combined with each other in any manner, unless the particular features and/or steps are mutually exclusive. This is particularly true of the preferred features of the present invention. Likewise, features that are not necessarily combined may be used separately (rather than in combination).

Furthermore, it should be noted that many of the features, especially those of the preferred embodiments of the present invention, should themselves be considered inventive, and should not be considered as merely some embodiments of the present invention. Independent protection may be sought for these features in addition to or in lieu of any presently claimed invention.

The teachings of the present disclosure may be extracted and combined with other embodiments.

The present invention is illustrated in detail by the following examples, which are not intended to be limiting thereby.

A person skilled in the art will be able to manufacture further electronic devices of the invention using the details given without inventive step and will thus implement the invention within the full scope of what is claimed.

Examples

Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in anhydrous solvents. In addition, the metal complexes are treated in the dark or under yellow light. Solvents and reagents may be purchased from, for example, sigma-ALDRICH or ABCR. The corresponding numbers in brackets or the reference numbers to individual compounds relate to the CAS numbering of the compounds known from the literature. In the case of compounds which may have a plurality of enantiomeric, diastereomeric or tautomeric forms, one form is shown in a representative manner.

Synthesis of Compounds of the invention

Example B1:

similar to the procedure of f.zhao et al Tetrahedron Letter,2017,58 (32), 3132. To a solution of 2.56g [ 2], [10mmol ] of 4-phenylbenzo [ h ] quinazoline [4786-81-6] and 2.02g [ 1mmol ] of saccharin [81-07-2] in 80ml of Ethyl Acetate (EA) was added 8.60g (20 mmol) of [ bis (trifluoroacetoxy) iodine ] benzene [2712-78-9], and the mixture was stirred at 60 ℃ for 12h. After cooling, 100ml of water are carefully added, the mixture is stirred for 10 minutes, and the organic phase is separated off, washed with saturated sodium chloride solution and concentrated to dryness. The soluble product was first purified by flash chromatography (silica gel, n-heptane/EA (ethyl acetate), torrents automated column system from a.semrau). Further purification was achieved by repeated chromatography or crystallization by thermal extraction from DCM (dichloromethane)/acetonitrile (1 to 1, vv) and fractional sublimation under high vacuum. Yield: 2.80g (6.3 mol) 63%; purity: about 99.9% according to HPLC.

The following compounds can be prepared analogously:

example B50:

similar to the program of Yu-Qing Ouyang et al, synth. The aryldiazonium tetrafluoroborate salt used was prepared from the corresponding arylamine (here 2-amino-9, 9' -spirobifluorene) as described therein and immediately converted further.

To a sufficiently stirred mixture of 1.83g [10mmol ] of saccharin [81-07-2], 1.38g [10mmol ] of potassium carbonate, 198mg [2mmol ] of cuprous chloride, 30g of glass beads (diameter 3 mm), and 50ml of DMSO was added dropwise a solution of 4.77g [ 111mmol ] of 2-spiro-9, 9' -bisfluorenyl diazonium tetrafluoroborate in 20ml of DMSO (note: gas evolution, bubbling!) at 25 ℃ over a period of 1 hour, followed by further stirring for 12 hours. The salts were filtered off as a DMSO slurry using a celite bed and rinsed with a small amount of DMSO, and the filtrate was poured into 500ml of water. The mixture was extracted three times with 100ml each of Dichloromethane (DCM) and the combined organic phases were washed three times with 200ml each of water and once with 200ml of saturated sodium chloride solution and concentrated to dryness. The soluble product was first purified by flash chromatography (silica gel, n-heptane/EA (ethyl acetate), torrents automated column system from a.semrau). Further purification was achieved by repeated chromatography or by crystallization from DCM/acetonitrile (1 to 1, vv) by thermal extraction and fractional sublimation under high vacuum. Yield: 2.85g (5.7 nmol), 57%; purity: according to HPLC, about 99.9%.

The following compounds can be prepared analogously:

example B100:

a mixture of 2.08g [10mmol ] of 9, 10-diaminophenanthrene [53348-04-2], 2.02g [10mmol ] of 2-cyanobenzenesulfonyl chloride [69360-26-5], 2.86ml [12mmol ] of tri-n-butylamine and 20ml of o-dichlorobenzene was stirred at 150 ℃ for 30 minutes. After cooling, 50ml of ethanol are carefully added, starting from about 100 ℃, and while the mixture is still warm the product is filtered off and washed three times with 15ml of ethanol each time and dried under reduced pressure. The soluble product was first purified by flash chromatography (silica gel, n-heptane/EA (ethyl acetate), torent automated column system from a.semrau). Further purification was achieved by repeated crystallization by thermal extraction from DCM (dichloromethane)/acetonitrile (1, vv) and fractional sublimation under high vacuum. Yield: 1.93g (5.4 mmol), 54%; purity: according to HPLC, about 99.9%.

The following compounds can be prepared analogously:

example (b): fabrication of OLEDs

1) And (3) processing the device in vacuum:

the OLED according to the invention and the OLED according to the prior art are manufactured by the general method according to WO2004/058911, which is adapted to the situation described here (variation of layer thickness, materials used).

In the following examples, the results of various OLEDs are presented. Clean glass plates coated with structured ITO (indium tin oxide) with a thickness of 50nm (cleaned in Miele laboratory glass washer, merck extra detergent) were pre-treated with UV ozone for 25 minutes (PR-100 UV ozone generator from UVP) and for improved processing 20nm pedot pss (poly (3, 4-ethylenedioxythiophene): poly (styrene sulfonate) was coated in 30 minutes ^TM P VP AI 4083 from Heraeus precius Metals GmbH Deutschland, spin coated from aqueous solution) and baked at 180 deg.C for 10 minutes. These coated glass plates form the substrate to which the OLED is applied.

The OLED has essentially the following layer structure: substrate/hole injection layer 1 (HIL 1) consisting of HTM1 doped with 5% ndp-9 (from Novaled), 20 nm/hole transport layer 1 (HTL 1) (consisting of HTM1 of 170nm for blue devices, 215nm for green/yellow devices, 110nm for red devices)/hole transport layer 2 (HTL 2)/emission layer (EML)/Hole Blocking Layer (HBL)/Electron Transport Layer (ETL)/optional electron injection layer (EIL, from ETM 2) and finally a cathode. The cathode is formed from a 100nm thick layer of aluminum.

First, vacuum processed OLEDs are described. For this purpose, all materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the light-emitting layer always consists of at least one host material (host material) and a light-emitting dopant (emitter) which is added to the host material or materials in a specific volume proportion by co-evaporation. The details given here in the form of, for example, M1: M2: ir (L1) (55%: 35%: 10%) indicate that the material M1 is present in the layer in a proportion by volume of 55%, that M2 is present in the layer in a proportion by volume of 35%, and that Ir (L1) is present in the layer in a proportion by volume of 10%. Similarly, the electron transport layer may also be composed of a mixture of two materials. The exact structure of the OLED can be seen in table 1. The materials used to make the OLED are shown in table 6.

The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra are determined, the current efficiency (measured in cd/a), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density, and the lifetime are calculated from current-voltage-luminous density characteristic lines (IUL characteristic lines) which exhibit lambert luminous characteristics. Electroluminescent spectrum is 1000cd/m ² And these are used to calculate the CIE 1931 x and y color coordinates.

Use of the compounds according to the invention as emitter materials in phosphorescent OLEDs

Among other uses, the compounds of the present invention can be used as electron-conducting host material eTMM in the emissive layer EML of phosphorescent OLEDs, and as electron-transporting material in HBLs and ETLs. The results of the OLEDs are collated in table 2.

Table 1: structure of OLED

Table 2: results of vacuum processed OLEDs

Use of the compounds according to the invention as emitter materials in fluorescent OLEDs

One use of the compounds according to the invention is as emitters (dopants) in fluorescent OLEDs. The results of the OLEDs are collated in table 3.

Table 3: structure of OLED

Table 4: results of vacuum processed OLEDs

2) Solution processed devices:

the compounds according to the invention can also be processed from solution and give, therein, OLEDs which are considerably simpler in terms of processing technology than vacuum-processed OLEDs, but nevertheless have good properties. The manufacture of these components is based on the manufacture of Polymer Light Emitting Diodes (PLEDs), the latter of which has been described many times in the literature (for example in WO 2004/037887). The structure comprises a substrate/ITO/hole injection layer (60 nm)/intermediate layer (20 nm)/light-emitting layer (60 nm)/hole blocking layer (10 nm)/electron transport layer (40 nm)/cathode. For this purpose, a substrate from Technoprint (soda lime glass) is used, to which an ITO structure (indium tin oxide, transparent conductive anode) is applied. The substrate was cleaned with deionized water and detergent (Deconex 15 PF) in a clean room and then activated by UV/ozone plasma treatment. Then, a 20nm hole injection layer (PEDOT: PSS from Clevios) was applied by spin coating also in the clean room ^TM ). The required spin rate depends on the degree of dilution and the particular spin coater geometry. In order to remove residues from the layerThe remaining water, the substrate was baked on a hot plate at 200 ℃ for 30 minutes. The interlayer used is for hole transport, in this case HL-X from Merck. Alternatively, the intermediate layer may also be replaced by one or more layers that need only satisfy conditions that are not re-leached by subsequent processing steps of EML deposition from solution. For the production of the light-emitting layer, the triplet emitters according to the invention are dissolved together with the matrix material in toluene or chlorobenzene. When a layer thickness of 60nm typical for the device is achieved as here by means of spin coating, the typical solids content of these solutions is 16 to 25g/l. The solution processed device contains a light emitting layer Ma: mb: ir (w%: x%: z%) or Ma: mc: ir (w%: x%: y%: z%); see table 3. The light-emitting layer was spin-coated in an inert gas atmosphere (argon in this example) and baked at 160 ℃ for 10 minutes. On top of the latter a hole blocking layer (10nm ETM1) and an electron transport layer (40nm ETM1 (50%)/ETM 2 (50%)) (vapor deposition system from Lesker et al, typical vapor deposition pressure was 5X 10 ^-6 Millibar). Finally, an aluminum cathode (100 nm) (high purity metal from Aldrich) was applied by vapor deposition. In order to protect the device from air and air humidity, the device is finally packaged and then characterized. The cited OLED embodiments have not been optimized. Table 5 summarizes the data obtained.

Table 5: results of materials processed from solution

Table 6: structural formula of the material

The inventive materials, when used in the light-emitting layer EML, the hole blocking layer HBL and the electron transport layer ETL, lead to an improved EQE (external quantum efficiency) together with a reduced voltage and thus an improved overall power efficiency.

Claims

1. Use of a compound comprising at least one structure of formula (I), preferably a compound of formula (I), in an organic electronic device,

wherein:

w is C = O, C = N-Ar or SO ₂ ；

Ar is identical or different on each occurrence and is an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups; the Ar group may here form a ring system with a second Ar group, an R group, an X group or another group;

x is N or CR, with the proviso that no more than two X groups in a ring are N;

r is identical or different on each occurrence and is H, D, OH, F, cl, br, I, CN, NO ₂ ，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) ₂ Ar'，S(＝O) ₂ R ¹ ，OSO ₂ Ar'，OSO ₂ R ¹ Straight-chain alkyl, alkoxy or thioalkoxy groups having from 1 to 40 carbon atoms, or alkenyl groups having from 2 to 40 carbon atoms orAn alkynyl group, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R ¹ Substituted by radicals in which one or more non-adjacent CH ₂ The group can be represented 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 SO ₂ Instead of, or with 5 to 60 aromatic ring atoms and can be substituted in each case by one or more R ¹ Aromatic or heteroaromatic ring systems substituted by radicals, or having 5 to 60 aromatic ring atoms and which may be substituted by one or more R ¹ A group-substituted aryloxy or heteroaryloxy group; also, two R groups may together form a ring system or form a ring system with another group;

ar' is identical or different on each occurrence and is an aromatic ring having 5 to 60 aromatic ring atoms and may be substituted by one or more R ¹ A group-substituted aromatic or heteroaromatic ring system; at the same time, the two Ar' groups bonded to the same carbon, silicon, nitrogen, phosphorus or boron atom may also be via a bridging group by a single bond or be 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、SO ₂ 、N(R ¹ )、P(R ¹ ) And P (= O) R ¹ Are linked together;

R ¹ in each case identical or different and are H, D, F, cl, br, I, CN, NO ₂ ，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 Straight-chain alkyl, alkoxy or thioalkoxy groups having from 1 to 40 carbon atoms, or branches having from 3 to 40 carbon atomsA chain or cyclic alkyl, alkoxy or thioalkoxy group, or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted with one or more R ² Substituted by radicals in which one or more non-adjacent CH ₂ The radical may be represented 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 SO ₂ And wherein one or more hydrogen atoms may be replaced by D, F, cl, br, I, CN or NO ₂ Instead of, or as aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R ² Substituted by radicals, or having 5 to 60 aromatic ring atoms and possibly being substituted by one or more R ² Aryloxy or heteroaryloxy radicals substituted by radicals, or having 5 to 60 aromatic ring atoms and which may be substituted by one or more R ² A group-substituted aralkyl or heteroaralkyl group, or a combination of these systems; simultaneously, two or more preferably adjacent R ¹ The groups may together form a ring system; at the same time, one or more R ¹ A group may form a ring system with another part of the compound;

R ² in each case identical or different and selected from H, D, F, CN, aliphatic hydrocarbon radicals having from 1 to 20 carbon atoms, or aromatic or heteroaromatic ring systems having from 5 to 30 aromatic ring atoms, one or moreA plurality of hydrogen atoms may be replaced by D, F, cl, br, I or CN and the aromatic or heteroaromatic ring systems may be substituted by one or more alkyl groups each having from 1 to 4 carbon atoms; simultaneously, two or more preferably adjacent substituents R ² May together form a ring system.

2. Use according to claim 1, the compound comprising the structure of formula (I), preferably the compound of formula (I), as a fluorescent emitter, phosphorescent emitter, emitter exhibiting TADF (thermally activated delayed fluorescence), host material, exciton blocking material, electron injecting material, electron transporting material, electron blocking material, hole injecting material, hole conducting material, hole blocking material, n-type dopant, p-type dopant, wide band gap material and/or charge generating material in an organic electronic device, preferably as a host material, electron transporting material, hole blocking material and/or emitter exhibiting TADF (thermally activated delayed fluorescence), more preferably as a host material for phosphorescent emitters, and especially preferably if W is C = O or SO ₂ It is used as a host material for blue phosphorescent emitters.

3. Use according to claim 1 or 2, characterized in that the compound comprises at least one structure of the formulae (IIa), (IIb) and (IIc) and is preferably selected from the compounds of the formulae (IIa), (IIb) and (IIc),

wherein the Ar and R groups have the definitions given in claim 1 and the index m is 0, 1,2,3 or 4, preferably 0, 1 or 2.

4. One or more of the preceding claimsSaid use being characterized in that two Ar groups, preferably two Ar groups bound to the nitrogen atom in formula (IIb), together form a ring having 5 to 60 aromatic ring atoms and which may be substituted by one or more R ¹ A group-substituted aromatic or heteroaromatic ring system, wherein R ¹ The radicals have the definitions specified in claim 1.

5. Use according to one or more of the preceding claims, characterized in that at least one of the Ar and/or R groups is selected from the following groups: phenyl, fluorene, indenofluorene, spirobifluorene, carbazole, indenocarbazole, indolocarbazole, spirocarbazole, pyrimidine, triazine, quinazoline, quinoxaline, pyridine, quinoline, isoquinoline, lactam, triarylamine, dibenzofuran, dibenzothiophene, imidazole, benzimidazole, benzophenon, benz

6. Use according to at least one of the preceding claims, characterized in that the compound comprises a hole transporting group, wherein preferably one of the Ar and/or R groups comprises a hole transporting group and is preferably a hole transporting group.

7. Use according to claim 6, characterized in that the hole transport group comprises a group selected from formulae (H-1) to (H-3) and preferably is a group selected from formulae (H-1) to (H-3),

wherein the dotted bond marks the connection position and the symbol defines:

Ar ² 、Ar ³ 、Ar ⁴ independently at each occurrence, is an aromatic ring system having 6 to 40 carbon atoms or a heteroaromatic ring system having 3 to 40 carbon atoms, each of which may be interrupted by one or more R ¹ Substituted by groups;

p is 0 or 1;

z is a bond or C (R) ¹ ) ₂ 、Si(R ¹ ) ₂ 、C＝O、NR ¹ 、N-Ar ¹ 、BR ¹ 、PR ¹ 、PO(R ¹ )、SO、SO ₂ Se, O or S, preferably a bond or C (R) ¹ ) ₂ 、N-Ar ¹ O or S;

wherein Ar ¹ Is an aromatic ring system having 6 to 40 carbon atoms or a heteroaromatic ring system having 3 to 40 carbon atoms which may be interrupted by one or more R ¹ Is substituted with radicals, and the R ¹ The radicals have the definitions detailed above, especially in claim 1.

8. Use according to claim 6 or 7, characterized in that the hole transport group comprises a group selected from the formulae (H-4) to (H-26) and preferably a group selected from the formulae (H-4) to (H-26),

wherein Y is ¹ Represents O, S, C (R) ¹ ) ₂ Or NAr ¹ The dotted bond marks the position of the linkage, e is 0, 1 or 2, j is 0, 1,2 or 3, h is 0, 1,2,3 or 4, p is 0 or 1, ar ¹ 、Ar ² And R ¹ Having the definitions given in claim 9.

9. Use according to at least one of the preceding claims, characterized in that the compound comprises a group comprising an electron transporting group, wherein preferably one of the Ar and/or R groups comprises and preferably represents a group comprising an electron transporting group.

10. Use according to claim 9, characterized in that the electron-transporting group is selected from structures of formula (Q-11), (Q-12), (Q-13), (Q-14) and/or (Q-15),

wherein the symbol R ¹ Having the definition given above in claim 1, X' is N or CR ¹ And the dashed bond marks the attachment position, wherein X' preferably represents a nitrogen atom.

11. Use according to claim 9 or 10, characterized in that the electron-transporting group is selected from structures of formula (Q-26), (Q-27), (Q-28), (Q-29) and/or (Q-30),

wherein symbol Ar ¹ And R ¹ Having the definition given above in claim 1 or 9, X' is N or CR ¹ And the dashed bonds mark the attachment position, wherein preferably exactly one X' represents a nitrogen atom.

12. Use according to at least one of the preceding claims, characterized in that at least one of the Ar and/or R groups comprises at least one aromatic or heteroaromatic ring system having two, preferably three, fused aromatic or heteroaromatic rings.

13. Use according to claim 12, characterized in that the aromatic or heteroaromatic ring system having two, preferably three, fused aromatic or heteroaromatic rings is selected from the group of formulae (Ar-1) to (Ar-17),

wherein X' is N or CR ¹ Preferably CR ¹ ，L ¹ Represents a bond or has 5 to 40, preferably 5 to 30, aromatic ring atoms and may be substituted by one or more R ¹ Radical-substituted aromatic or heteroaromatic ring systems, R ¹ Has the definitions detailed in claim 1 and the dashed bonds mark the connection positions.

14. A composition comprising a combination comprising:

wherein the symbols X, W and Ar have the definitions given in claim 1;

15. A compound comprising at least one structure of formula (III), preferably a compound of formula (III),

wherein the symbols X and W have the meanings given in claim 1 and HetAr is a substituted or unsubstituted heterocyclic ring having 5 to 60 aromatic ring atoms which may be substituted by one or more R ¹ A group-substituted heteroaromatic ring system; the HetAr group may here form a ring system together with the Ar group, the R group, the X group or a further group; wherein HetAr is preferably a group selected from formulae (H-1) to (H-26) as defined in claims 7 and 8 or from formulae (Q-11) to (Q-30) as defined in claims 10 and 11.

16. A compound comprising at least one structure of formula (V), preferably a compound of formula (V),

wherein the symbols X and W have the definitions given in claim 1 and KonAR represents an aromatic or heteroaromatic ring system having two, preferably three, fused aromatic or heteroaromatic rings and having from 10 to 60 aromatic ring atoms, preferably from 12 to 40 aromatic ring atoms, wherein the aromatic or heteroaromatic ring system may be substituted by one or more R ¹ Group substitution, wherein the KonAr group may form a ring system with the Ar group, the R group, the X group or another group, wherein KonAr is preferably a group selected from the group consisting of formulae (Ar-1) to (Ar-17) as defined in claim 13, more preferably a group selected from the group consisting of formulae (Ar-3) to (Ar-17) as defined in claim 13.

17. A compound comprising at least one structure of formula (VII), preferably a compound of formula (VIII),

wherein the symbols X, ar and W have the definitions given above, especially in claim 1, wherein the structure/compound has at least one aromatic or heteroaromatic ring system having 5 to 60 carbon atoms and onto which a non-aromatic or non-heteroaromatic ring system is fused.

18. A compound comprising exactly two, exactly three or exactly four structures of formula (I) as defined in claim 1 and/or formulae (IIa) to (IIc) as defined in claim 3.

19. A compound having at least one of formulas (IXa) through (IXc),

wherein the symbols Ar and W have the definitions given in claim 1, X is N, CR, if L ¹ A group is bonded to X, then X is C, provided that no more than two X groups in a ring are N; and L is ¹ Represents a bond or an aromatic or heteroaromatic ring system having from 5 to 40, preferably from 5 to 30, aromatic ring atoms which may be substituted by one or more R ¹ And (4) substituting the group.

20. Oligomer, polymer or dendrimer containing at least one of the compounds for use as defined in one or more of claims 1 to 14 or a compound according to any of claims 15 to 17, wherein, instead of hydrogen atoms or substituents, one or more bonds to the corresponding structural isomer in the mixture are present to form the polymer, oligomer or dendrimer.

21. A formulation comprising one or more compounds according to one or more of claims 15 to 19, an oligomer, polymer or dendrimer according to claim 20 or a composition according to claim 14 and at least one solvent.

22. An electronic device comprising at least one of the compounds in the use as defined in one or more of claims 1 to 14, a compound according to one or more of claims 15 to 19, an oligomer, polymer or dendrimer according to claim 22, or a composition according to claim 14, wherein the electronic device is preferably selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light emitting electrochemical cells and organic laser diodes.