Compounds for electronic devices, in particular compounds for oleds

Abstract

The present invention relates to OLED materials, to methods for producing said materials, and to the use of said materials in OLEDs.

Description

[0001] Compounds for electronic devices, in particular compounds for OLEDs

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

[0003] Electronic devices containing organic, organometallic, and / or polymeric semiconductors are becoming increasingly important. Due to their cost and performance, these semiconductors are used in many commercial products. Examples include organic-based charge transport materials (e.g., triarylamine-based hole transporters) in copiers, organic light-emitting diodes (OLEDs) in display devices, and organic photoreceptors in copiers. Organic solar cells (O-SC), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic switching elements (O-ICs), organic optical amplifiers, and organic laser diodes (O-lasers) are at an advanced stage of development and have the potential to become very important in the future.

[0004] Electronic devices within the meaning of this invention are understood to be organic electronic devices that contain organic semiconductor materials as functional materials. In particular, the electronic devices represent electroluminescent devices such as OLEDs.

[0005] The structure of OLEDs, in which organic compounds are used as functional materials, is known to those skilled in the art. Generally, OLEDs are electronic devices that have one or more layers comprising organic compounds and emit light when a voltage is applied. In electronic devices, especially OLEDs, there is a great need to improve the performance characteristics, particularly lifetime, efficiency, and operating voltage. No satisfactory solution has yet been found for these aspects.

[0006] Electronic devices typically comprise a cathode, an anode, and at least one functional, preferably emissive, layer. In addition to these layers, they may contain further layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generation layers.

[0007] The object of the present invention is to provide compounds which are suitable for use in an electronic device, in particular an OLED, in particular as host material, as material for hole-transport layers, and / or as material for electron-transport layers, and which lead to good properties there. A further object of the present invention is to provide materials for electron-blocking layers or hole-blocking layers. An electron-blocking layer is understood to be a layer which is arranged between the emitting layer and the hole-transport layer and reduces the passage of electrons. A hole-blocking layer is understood to be a layer which is arranged between the emitting layer and the electron-transport layer and reduces the passage of holes.Due to their sufficiently high T1 value and matching HOMO / LUMO levels, compounds according to the present application are excellently suited for use as host material in an emitting layer, in particular a blue emitting layer, and for use in a hole blocking layer.

[0008] Furthermore, there is a need to provide compounds for use in OLEDs that contain a molecular moiety that contributes to good film-forming properties, but is electronically or photophysically inactive or only slightly active. Such a molecular moiety preferably has a certain spatial extent, i.e., is not merely a sterically small group like phenyl or methyl.

[0009] A further object of the present invention is to provide compounds whose ability to form exciplexes can be varied as needed. The variation in the propensity to form exciplexes is achieved by substitution with suitable chemical residues. At the same time, the HOMO / LUMO levels of the compounds serving as electron-transporting host materials should be tunable with those of a hole-transporting host material and potential emitter or sensitizer compounds, whereby the compounds should have a suitable T1 level for this purpose.

[0010] A further object of the present invention is to provide emitter or sensitizer compounds that prevent exciplex formation with other materials through steric shielding. Likewise, steric shielding can be used in fluorescent emitter compounds to prevent unwanted Dexter transfer. The group of formula (1) creates the steric shielding when bound to a corresponding compound, especially an emitter or sensitizer compound.

[0011] Compounds of the present application are particularly suitable as electron-transporting host materials in both phosphorescent and hyperphosphorescent components, as well as in hyperfluorescent components and components containing a TADF emitter (TADF = thermally activated delayed fluorescence). Due to the above-mentioned properties, they exhibit advantages in these components. Use as one of three or four different components in the emitting layer is preferred, especially in components with hyperphosphorescent, hyperfluorescent, or TADF-based emitting layers.

[0012] A further object of the present invention is to provide compounds that exhibit sufficient solubility, particularly due to steric bulk and twisting of the molecular structure, and that have a high glass transition temperature. Adequate solubility is an important property for enabling efficient synthesis and purification of the compounds. A high glass transition temperature is important for the vapor deposition process and film formation.

[0013] According to an embodiment which is preferred under certain circumstances, the compounds of the invention do not form undesirable exciplexes with emitter or sensitizer compounds in the emission layer.

[0014] Surprisingly, it has been found that certain nitrogen-containing compounds, described in more detail below, achieve the above-mentioned objectives and are well suited for use in electronic devices, particularly OLEDs. The OLEDs exhibit, in particular, a long lifetime, high efficiency, and low operating voltage, as well as the specific positive properties mentioned below. These compounds and electronic devices, particularly organic electroluminescent devices, containing these compounds are therefore the subject of the present invention.

[0015] The present invention relates to a compound containing one or more units according to formula (1),

[0016] where the symbols are:

[0017] W is C or Si and preferably C;

[0018] X a is the same or different at each occurrence N or CR a, where at most two of the groups X a per ring represent N, preferably at most one of the groups X a per ring represents N and particularly preferably all groups X a for CR a stand;

[0019] X b is the same or different at each occurrence N or CR b , where at most two of the groups X b per ring represent N, preferably at most one of the groups X b per ring represents N and particularly preferably all groups X b for CR b stand;

[0020] R a , R bis, identically or differently on each occurrence, H, D, F, CI, Br, I, OAr, SAr, N(R)2, N(Ar)2, B(OR)2, B(R)2, B(Ar)2, CHO, C(=O)R, CR=C(R)2, CN, C(=O)OR, C(=O)NR, C(R)3, Si(R)3, Si(Ar)3, Ge(R)3, NO2, P(=O)(R)2, P(Ar)2, P(R)2, OSO2R, OR, S(=O)R, S(=O)2R, SR, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group may each be substituted by one or more radicals R other than H, where one or more non-adjacent CH2 groups may be replaced by -RC=CR-, -CEC-, Si(R)2, CONR, NR, C=O, C=S, -C(=O)O-, P(=O)(R), -O-, -S-, SO or SO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may each be substituted by one or more radicals R other than H, or a transition metal complex,especially of platinum, where two radicals R, a , R b also form a ring with each other;

[0021] Ar is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R other than H, wherein two radicals Ar which bond to the same Si atom, N atom, P atom or B atom may also be bridged to one another by a single bond or a bridge selected from B(R), C(R)2, Si(R)2, C=O, C=NR, C=C(R)2, O, S, S=O, SO2, N(R), P(R) and P(=O)R;

[0022] R is the same or different at each occurrence: H, D, F, CI, Br, I, OAr', SAr', N(R 1 )2, N(Ar')2, B(OR 1 )2, B(R 1 )2, B(Ar')2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , C(R 1 ) 3I Si(R 1 )3, Si(Ar')3, Ge(R 1)3, NO2, P(=O)(R 1 )2, P(Ar')2, P(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1 , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted by other than H, where one or more non-adjacent CH2 groups are substituted by -R 1 C=CR 1 -, -C=C-, Si(R 1 )2, CONR 1 , NR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), -O-, -S-, SO or SO2, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ring atoms, each substituted by one or more radicals R 1may be substituted by other than H, or a transition metal complex, in particular of platinum, where two radicals R can also form a ring with each other; Ar' is, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is substituted by one or more radicals R 1 may be substituted by other than H, whereby two radicals Ar' which are bonded to the same Si atom, N atom, P atom or B atom may also be bonded by a single bond or a bridge selected from B(R 1 ), C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, 0, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 , be bridged together;

[0023] R 1 is the same or different at each occurrence H, D, F, CI, Br, I, N(R 2 )2, B(OR 2 ) 2I B(R 2 ) 2I CHO, C(=O)R 2 , CR 2 =C(R 2)2, CN, C(=O)OR 2 , C(R 2 )3, Si(R 2 )3, Ge(R 2 )3, NO2, P(=O)(R 2 )2, P(R 2 )2, OSO2R 2 , SR 2 , S(=O)R 2 , S(=O)2R 2 , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 2 may be substituted by other than H and wherein one or more CH2 groups in the above-mentioned groups are replaced by -R 2 C=CR 2 -, -C^C-, Si(R 2 )2, NR 2 , C=O, C=S, -C(=O)O-, CONR 2 , P(=O)(R 2), -S-, SO or SO2 and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, CI, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 2 may be substituted by other than H, or a transition metal complex, in particular of platinum, where two or more radicals R 1 can form a ring with each other;

[0024] R 2 is, identically or differently at each occurrence, H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by D or F; two or more substituents R 2 form a ring with each other.

[0025] A compound containing one or more units of the

[0026] Formula (1) refers to a compound which, in addition to formula (1), may contain further molecular moieties. These may, for example, be chemical groups that do not fall under formula (1), such as transition metal complexes. Compounds containing one or more units of formula (1) are exemplified by compounds 71 ​​and 72 in the table of preferred embodiments of compounds according to the application. The compound according to the application is preferably a single organic compound, whereby the term "organic compound" is not intended to exclude transition metal complexes.

[0027] The compound according to the present application preferably has a molecular weight of not more than 2000 Da, more preferably not more than 1500 Da, most preferably not more than 1000 Da.

[0028] Preferably, the compound according to the application is a compound according to formula (1).

[0029] An aryl group within the meaning of this invention contains 6 to 40 C atoms; a heteroaryl group within the meaning of this invention contains 5 to 40 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is understood to be either a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc., or a condensed (fused) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatics linked to one another by a single bond, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as an aromatic ring system.

[0030] An aromatic ring system within the meaning of this invention contains 6 to 60 C atoms, preferably 6 to 40 C atoms in the ring system. An aromatic ring system within the meaning of this invention does not contain any heteroaryl group. A heteroaromatic ring system within the meaning of this invention contains 1 to 60 C atoms, preferably 1 to 40 C atoms and at least one heteroaryl group, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system within the meaning of this invention is to be understood as a system which does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be replaced by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as, for example, B. a C, N or O atom or carbonyl group.Likewise, this includes systems in which two or more aryl or heteroaryl groups are directly linked to one another, such as biphenyl, terphenyl, bipyridine, or phenylpyridine. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are also to be understood as aromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are linked, for example, by a linear or cyclic alkyl group or by a silyl group. Preferred aromatic or heteroaromatic ring systems are simple aryl or heteroaryl groups, as well as groups in which two or more aryl or heteroaryl groups are directly linked to one another, for example biphenyl, terphenyl, quaterphenyl, or bipyridine, as well as fluorene or spirobifluorene.

[0031] An electron-deficient heteroaryl group within the meaning of the present invention is a six-membered-ring heteroaryl group having at least one nitrogen atom or a five-membered-ring heteroaryl group having at least two heteroatoms, one of which is a nitrogen atom and the other is oxygen, sulfur, or a substituted nitrogen atom, wherein further aryl or heteroaryl groups may be fused to each of these groups. Examples of electron-deficient heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, or quinoxaline.

[0032] In contrast, electron-rich heteroaryl groups are five-membered-ring heteroaryl groups with exactly one heteroatom selected from oxygen, sulfur, or substituted nitrogen, to which further aryl groups and / or further electron-rich five-membered-ring heteroaryl groups can be fused. Examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, or indenocarbazole.

[0033] In the context of the present invention, the term "alkyl group" is used as a generic term for both linear or branched alkyl groups and cyclic alkyl groups. Analogously, the terms "alkenyl group" and "alkynyl group" are used as generic terms for both linear or branched alkenyl or alkynyl groups, as well as for cyclic alkenyl or alkynyl groups.

[0034] A cyclic alkyl, alkoxy or thioalkoxy group within the meaning of this invention is understood to mean a monocyclic, a bicyclic or a polycyclic group.

[0035] In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which may contain 1 to 40 C atoms and in which individual H atoms or CH2 groups may be substituted by the above-mentioned groups, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclo-hexyl, n-octyl, cyclooctyl, 2-ethylhexyl, 1-bicyclo[2,2,2]octyl, 2-bicyclo[2,2,2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-Dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1 , 1 -dimethyl-n-hex-1 -yl, 1 , 1 -dimethyl-n-hept-1 -yl, 1 , 1 -dimethyl-n-oct-1 -yl, 1 , 1 -dimethyl-n-dec-1 -yl, 1 , 1-Dimethyl-n-dodec-1-yl,1 , 1 -Dimethyl-n-tetradec-1 -yl, 1 , 1 -Dimethyl-n- hexadec-1 -yl, 1 ,1 -Dimethyl-n-octadec-1 -yl, 1 , 1 -Diethyl-n-hex-1 -yl, 1 ,1 - Diethyl-n-hept-1 -yl, 1 , 1 -Diethyl-n-oct-1 -yl, 1 , 1 -Diethyl-n-dec-1 -yl, 1 ,1 - Diethyl-n-dodec-1 -yl, 1 , 1 -Diethyl-n-tetradec-1 -yl, 1 , 1 -Diethyl-n-hexadec-1 - yl, 1 ,1 -Diethyl-n-octadec-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 und 1- (n-Decyl)-cyclohex-l-yl, Ethenyl, Propenyl, Butenyl, Pentenyl, Cyclo- pentenyl, Hexenyl, Cyclohexenyl, Heptenyl, Cycloheptenyl, Octenyl, Cyclooctenyl, Cyclooctadienyl, Ethinyl, Propinyl, Butinyl, Pentinyl, Hexinyl, Heptinyl oder Octinyl verstanden. Unter einer Alkoxygruppe OR, 1mit 1 bis 40 C-Atomen werden bevorzugt Methoxy, Trifluormethoxy, Ethoxy, n-Propoxy, i-Propoxy, n-Butoxy, i-Butoxy, s-Butoxy, t-Butoxy, n-Pentoxy, s-Pentoxy, 2-Methylbutoxy, n-Hexoxy, Cyclohexyloxy, n-Heptoxy, Cyclo- heptyloxy, n-Octyloxy, Cyclooctyloxy, 2-Ethylhexyloxy, Pentafluorethoxy und 2,2,2-Trifluorethoxy verstanden. Unter einer Thioalkylgruppe SR 1mit 1 bis 40 C-Atomen werden insbesondere Methylthio, Ethylthio, n-Propyl- thio, i-Propylthio, n-Butylthio, i-Butylthio, s-Butylthio, t-Butylthio, n-Pentyl- thio, s-Pentylthio, n-Hexylthio, Cyclohexylthio, n-Heptylthio, Cycloheptyl- thio, n-Octylthio, Cyclooctylthio, 2-Ethylhexylthio, Trifluormethylthio, Pentafluorethylthio, 2,2,2-Trifluorethylthio, Ethenylthio, Propenylthio, Butenylthio, Pentenylthio, Cyclopentenylthio, Hexenylthio, Cyclohexenyl- thio, Heptenylthio, Cycloheptenylthio, Octenylthio, Cyclooctenylthio, Ethinylthio, Propinylthio, Butinylthio, Pentinylthio, Hexinylthio, Heptinylthio oder Octinylthio verstanden.In general, alkyl, alkoxy, or thioalkyl groups according to the present invention may be straight-chain, branched, or cyclic, wherein one or more non-adjacent CH2 groups may be replaced by the above-mentioned groups; furthermore, one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, preferably D, F, Cl, or CN, particularly preferably D, F, or CN.

[0036] An aromatic or heteroaromatic ring system with 5 - 60 aromatic ring atoms, preferably 5 - 40 aromatic ring atoms, which may also be substituted by the above-mentioned radicals or a hydrocarbon radical and which may be linked to the aromatic or heteroaromatic ring via any desired positions, is understood to mean, in particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, cis- or trans-monobenzoindenofluorene, cis- or trans- Dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,Indol, Isoindol, Carba- zol, Pyridin, Chinolin, Isochinolin, Acridin, Phenanthridin, Benzo-5,6-chino- lin, Benzo-6,7-chinolin, Benzo-7,8-chinolin, Phenothiazin, Phenoxazin, Pyrazol, Indazol, Imidazol, Benzimidazol, Benzimidazolobenzimidazol, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Oxazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, 1 ,2-Thiazol, 1 ,3-Thiazol, Benzothiazol, Pyridazin, Hexaazatriphenylen, Benzopyridazin, Pyrimidin, Benzpyrimidin, Chinoxalin, 1 ,5-Diazaanthracen, 2,7-Diazapyren, 2,3-Diazapyren, 1 ,6-Diazapyren, 1 ,8-Diazapyren, 4,5-Diazapyren, 4,5,9,10-Tetra- azaperylen, Pyrazin, Phenazin, Phenoxazin, Phenothiazin, Fluorubin, Naphthyridin, Azacarbazol, Benzocarbolin, Phenanthrolin, 1 ,2,3-Triazol, 1 ,2,4-Triazol, Benzotriazol, 1 ,2,3-Oxadiazol, 1 ,2,4-Oxadiazol, 1 ,2,5-Oxa- diazol, 1 ,3,4-Oxadiazol, 1 ,2,3-Thiadiazol, 1 ,2,4-Thiadiazol, 1 ,2,5-Thiadi- azol, 1 ,3,4-Thiadiazol, 1 ,3,5-Triazin, 1 ,2,4-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, or groups derived from combinations of these systems. These groups can also be deuterated.

[0037] For the purposes of this description, the phrase "two or more residues can form a ring" is understood to mean, among other things, that the two residues are linked by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme: Furthermore, the above formulation should also be understood to mean that if one of the two residues represents hydrogen, the second residue binds to the position to which the hydrogen atom was bonded, forming a ring. This is illustrated by the following scheme:

[0038] In a preferred embodiment, the compound according to the invention corresponds to the following formula (2):

[0039] Formula (2) where the symbols R a , R b and W, have the meanings set out above, in particular for formula (1 ) and at least one of the radicals R a and / or R b , preferably at least one of the radicals R a , represents a group selected from N(Ar)2 or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R other than H. Preferably, at least one of the radicals R a and / or R b , preferably at least one of the radicals R a, a heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may each be substituted by one or more radicals R other than H. Also for the above-mentioned formula (1 ) it is preferred that at least one of the radicals R a and / or R b , preferably at least one of the radicals R a , represents a group selected from N(Ar)2 or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R other than H. It is preferred that at least one of the radicals R a and / or R b , preferably at least one of the radicals R a, represents a heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R other than H.

[0040] Preference is given to all substituents of the basic structure of formula (1 ) which carry groups with a short conjugation length, ie a short length of the conjugated system. In particular, this refers to groups which have a shorter conjugation length than para-biphenyl. This preference particularly applies to the radicals R a and R b Also important are residues that, due to steric demands, lead to a twisting of the conjugated system and thus also to a limitation of the conjugation length. Such residues and their effects on the spatial structure of the basic structures to which they are bound are known to those skilled in the art.

[0041] Preferably, it can be provided that at least one of the groups R a and / or R b , preferably at least one of the radicals R a , represents a group selected from structures of the formula -(L) q -(Z) S , where L is, identically or differently at each occurrence, a bivalent, trivalent or tetravalent aromatic or heteroaromatic ring system having 6 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R c may be substituted by other than H; q is 0 or 1, where q = 0 means that the group L is not present and that the corresponding aromatic or heteroaromatic group is directly bonded to the associated atom, for example a carbon atom, where the group Z is selected from structures of the formulas (Z-1) to (Z-19),

[0042] where W has the meaning previously defined, in particular for formula (1 ), the dashed bond represents the bond to the group L or, in the case of q=0, to the spiro skeleton according to formula (1 ), s is 1, 2 or 3, preferably 1 or 2, where in the case of q=0 the index s is 1, and the following applies to the other symbols:

[0043] X c is the same or different at each occurrence N, CR C or, in the event that at this point this group binds to another group, C, preferably CR C or C, where at most two of the groups X c per ring represent N, preferably at most one of the groups X c per ring represents N and particularly preferably all groups X c for CR C or C;

[0044] X d is the same or different at each occurrence N or CR d , where at least one group X drepresents N, preferably at least two of the groups X d represent N; Y is chosen from C(R C )2, Si(R c )2, C=O, P(O)R C , PR C , NR C or BR C , 0 or S, preferably C(R C )2 or 0, particularly preferably C(R C )2;

[0045] Y 1 stands for 0, S, NR d or C(R d )2;

[0046] R c , R d is the same or different at each occurrence H, D, F, CI, Br, I, OAr', SAr', N(R 1 )2, N(Ar')2, B(OR 1 )2, B(R 1 )2, B(Ar')2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , C(R 1 ) 3I Si(R 1 )3, Si(Ar')3, Ge(R 1 )3, NO2, P(=O)(R 1 ) 2I P(Ar')2, P(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted by other than H, where one or more non-adjacent CH2 groups are substituted by -R 1 C=CR 1 -, -C=C-, Si(R 1 )2, CONR 1 , NR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), -O-, -S-, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted by other than H, two residues may be selected from residues R c and R d also form a ring with each other, where R 1 has the meaning given above, in particular for formula (1).

[0047] It is preferred that exactly one of the groups R a and / or R b , prefers exactly one of the groups R a , represents a group selected from structures of the formula -(L) q -(Z) S as defined above, and preferably defined according to the preferred embodiments set out above and below.

[0048] Preferably, it can be provided that the group Z in formula -(L) q -(Z)s is selected from structures of formulas (Z-20) to (Z-44),

[0049]

[0050] where the dashed bond represents the bond to the group L or, in case q= 0, to the spiro skeleton according to formula (1) and the symbols Y 1 , R c and R d have the meanings given above, in particular for formulas (Z-1) to (Z-19).

[0051] In a preferred embodiment, L is, identically or differently at each occurrence, a bivalent, trivalent or tetravalent aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, which is in each case substituted with one or more radicals R c may be substituted other than H, but is preferably unsubstituted or deuterated. In a particularly preferred embodiment, the compound according to the invention corresponds to one of the following formulas (3-1) to

[0052] (3-8):

[0053] Formula (3-5) Formula (3-6)

[0054] where the symbols R a and R b have the meanings set out above, in particular for formula (1 ), the symbols q, s, L and Z have the meanings set out above, in particular in connection with formula -(L) q -(Z) Sor formulas (Z-1) to (Z-44), preferably have the meanings set out above, particularly in connection with formulas (Z-20) to (Z-44). Compounds according to formulas (3-1) and (3-2) are preferred, and compounds of formula (3-2) are particularly preferred.

[0055] In a further particularly preferred embodiment, the compound according to the invention corresponds to at least one of the following formulas (4-1) to (4-16):

[0056] where the symbols R a and R b have the meanings set out above, in particular for formula (1 ), the symbols q, s, L and Z have the meanings set out above, in particular in connection with formula -(L) q -(Z) Sor formulas (Z-1) to (Z-44), preferably as defined above, particularly in connection with formulas (Z-20) to (Z-44). Compounds according to formulas (4-1) to (4-8) are preferred, especially compounds according to formula (4-1).

[0057] In a preferred embodiment, it can be provided that the group — (L) q - in formula-(L) q -(Z) s a structure of the formula -(L c )0- such that at least one of the groups R a and / or R b represents a group selected from structures of the formula -(L C ) O -(Z) S , where the index o is 0, 1 , 2, 3, 4 or 5, where o = 0 means that the group L cis not present and that the corresponding aromatic or heteroaromatic group is directly bonded to the associated atom, for example a carbon atom, where o is preferably 0, 1 or 2 and particularly preferably 0 or 1 and the radical L c is chosen from structures of the formulas (L c -1 ) to (L c -14)

[0058] Formula (L c -1 ) Formula (L c -2) Formula (L c -3)

[0059]

[0060] Formula (L c -14) where the dashed bonds represent the attachment points and the other symbols are:

[0061] X c is the same or different at each occurrence N, CR C or, in the event that at this point this group binds to another group, C, preferably CR C or C, preferably with a maximum of 3 groups X cper ring represent N, particularly preferably at most 2 and very particularly preferably all groups X c for CR C or C;

[0062] Y c is chosen from C(R C )2, NR C , 0 or S, preferably C(R C )2 or 0, particularly preferably 0; where R c has the meaning given above, in particular for formulas (Z-1) to (Z-19), wherein the structure of the formula -(L c )0- for the index s =1 in formula

[0063] -( L c )o-(Z)s is bivalent, for s=2 trivalent and for s=3 tetravalent. Here, structures of the formulas (L c -1 ) and (L c -2) is preferred.

[0064] Furthermore, it can preferably be provided that the group L c is chosen from structures of the formulas (L c -14) to (L c -29)

[0065] Formula (L c -22) Formula (L c -23) Formula (L c-24) Formula (L c -25)

[0066] Formula (L c -26) Formula (L c -27) Formula (L c -28) Formula (L c -29) where the dashed bonds represent the attachment points, the symbols R c and X c has the meaning given above, in particular for formulas (Z-1) to (Z-19), and the following applies to the other symbols: i is 1 or 2; and j is 0, 1 or 2.

[0067] Particularly preferably, it can be provided that the group L c is chosen from structures of the formulas (L c -30) to (L c -41 )

[0068] Formula (L c -35) Formula (L c -36) Formula (L c -37)

[0069] where the dashed bonds represent the attachment points, the R c has the meaning given above, in particular for formulas (Z-1) to (Z-19).

[0070] The compounds according to the invention according to formula (1 ) can be used as electron-transporting material or hole-transporting material, depending on the configuration of the radicals R a and / or R b . Possible residues to be selected R a and / or R b , in order to achieve the desired properties of the compounds, are generally known to the person skilled in the art, with particular electron-poor heteroaryl groups being used as radicals R a and / or R b lead to electron-transporting materials according to formula (1 ).

[0071] In particular, compounds according to the invention with electron-deficient heteroaryl groups can be used in hole-blocking layers, electron-transport layers, electron-injection layers and / or as host material in emitting layers.

[0072] Hole-transporting materials are characterized in particular by di- or triarylamine groups as residues R a and / or Rb obtained as represented by the groups of the formulas (Z-5), (Z-23), and (Z-24) presented above and below. Depending on the radical Y, groups of the formula (Z-4) also lead to hole-transporting materials. Compounds according to the invention with di- or triarylamine groups can be used in many ways in electron-blocking layers, hole-transport layers, hole-injection layers, and / or as host material in emitting layers.

[0073] Preferably, the group Z can be selected from groups of the formulas (Z-4-1) to (Z-4-3), (Z-23-1) and (Z-24-1 to Z-24-24) where the bond marked with * is the bond to the group L or L c or, in case q= 0, to the spiro skeleton according to formula (1 ), R cwhich has the meaning set out above, in particular for formulas (Z-1) to (Z-19) and the groups at all free positions are substituted by one or more radicals R c may be substituted. It is preferred that radicals R c are defined according to their preferred embodiments. The compounds are preferably unsubstituted or substituted by D in their free positions. The groups of the formulas (Z-4-1) to (Z-4-3), (Z-23-1) and (Z-24-1) to (Z-24-24) preferably lead to hole-transporting materials and represent preferred embodiments of the groups of the formulas (Z-4), (Z-5), (Z-23) and (Z-24).

[0074] In a preferred embodiment, at least one radical R a and / or at least one radical R b , preferably exactly one of the residues R a or R b , particularly preferably exactly one residue R a, on each occurrence, identically or differently selected from an aromatic or heteroaromatic, preferably heteroaromatic, ring system having 6 to 24 aromatic ring atoms, which may each be substituted by one or more radicals R other than H, but is preferably unsubstituted or substituted by D. Furthermore, at least one radical R a and / or at least one radical R b , particularly preferably exactly one residue R a , identically or differently on each occurrence selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, benzimidazolobenzimidazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, where these groups are each substituted by one or more radicals R 1may be substituted, but are preferably unsubstituted or substituted by D. With regard to the compounds of formulas (3-1) to (3-8) and formulas (4-1) to (4-16), it should be noted that in these structures at least one group of the formula -(L) q -(Z) S is contained, so that in these compounds of the formulas (3-1 ) to (3-8) and the formulas (4-1 ) to (4-16) preferably the radicals R shown in these structures of the formulas (3-1 ) to (3-8) and (4- 1 ) to (4-16) a and / or R b In a preferred embodiment, no group of the formula -(L) q -(Z) S particularly preferably not an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms.

[0075] In a preferred embodiment, it can be provided that at least one radical R a a structure of the formula -(L) q -(Z) S , prefers exactly one residue R aa structure of the formula -(L) q -(Z) S where the indices q and s and the symbol Z have the meanings set out in the following table:

[0076] Preferably, it can be provided that at least one radical R b a structure of the formula -(L) q -(Z) S , prefers exactly one residue R b a structure of the formula -(L) q -(Z) S where the indices q and s and the symbol Z have the meanings set out in the following table:

[0077] In a preferred embodiment, it can be provided that at least one radical R a a structure of the formula -(L C ) O -(Z) S , prefers exactly one residue R a a structure of the formula -(L C ) O -(Z) S where the indices o and s and symbols L cand Z preferably have the meanings set out in the following table:

[0078] In a preferred embodiment, it can be provided that at least one radical R b a group of structures of the formula -(L C ) O -(Z) S particularly preferably exactly one radical R a a group of structures of the formula -(L C ) O -(Z) S where the indices o and and symbols L c and Z preferably have the meanings set out in the following table:

[0079] According to a preferred embodiment, the compound corresponds to the above-mentioned formula (2), wherein exactly one radical selected from the radicals R a and R b represents a group selected from structures of the formula -(L) q -(Z) S , where q is 0 or 1, L is either absent or equal to carbazole, which reacts with residues Rc is substituted, in particular formula (L c -25), s is 1, and Z is formula (Z-22); and wherein the further radicals are selected from the radicals R a and R b are H or D, preferably H.

[0080] With regard to the compounds of formulas (3-1) to (3-8) and formulas (4-1) to (4-16), it should be noted that in these structures at least one group of the formula -(L) q -(Z) S is included, where the group -(L c )0- a preferred variant of the group -(L) q - so that in these compounds of formulas (3-1) to (3-8) and formulas (4-1) to (4-16) the radicals R shown in these structures of formulas (3-1) to (3-8) and (4-1) to (4-16) are preferably a and / or R b In a preferred embodiment, no group of the formula -(L C ) O -(Z) S represent.

[0081] In the context of the present invention, the term substituent means in particular that the radicals R, R a , R b , R c , R d , R 1 are not equal to H. Furthermore, the substituents R, R a , R b , R c , R d , R 1 etc. may be the same or different if two or more substituents are present. In a preferred embodiment of the invention, the groups R, R a , R b , R c , R d no substituted or unsubstituted amino groups. Preferably, the group R, R a , R b , R c , R d therefore no triarylamino groups, but can contain, for example, carbazole groups, i.e. heteroaryl groups that contain nitrogen.

[0082] If the compound according to the invention is reacted with aromatic or heteroaromatic groups R, R a , R b , R c , R d, R 1 or R 2 is substituted, it is preferred in one embodiment if these do not have any aryl or heteroaryl groups with more than two directly fused aromatic six-membered rings. Particularly preferably, the substituents do not have any aryl or heteroaryl groups with directly fused six-membered rings. This preference is due to the low T1 energy level of such structures. Condensed aryl groups with more than two directly fused aromatic six-membered rings that are nevertheless also suitable according to the invention are phenanthrene and triphenylene, since due to their specific structure they do not have a low T1 energy level, even though they have more than two directly fused aromatic six-membered rings. Ti is determined as stated in section 2) of the patent examples.

[0083] In a preferred embodiment, R, Ra , R b , R c , R d and the associated groups are not an aromatic or heteroaromatic ring system which has three linearly condensed aromatic 6 rings, wherein preferably none of the radicals R, R a , R b , R c , R d an aromatic or heteroaromatic ring system having three linearly condensed aromatic 6-membered rings. Particularly preferably, R, R a , R b , R c , R d and the corresponding groups do not contain condensed aryl groups.

[0084] If two residues, which can be selected in particular from R a , R b , R c , R d , R 1 and / or R 2, form a ring, this ring can be mono- or polycyclic, aliphatic, heteroaliphatic, aromatic, or heteroaromatic. The radicals forming a ring can be adjacent, meaning that these radicals are bonded to the same carbon atom or to carbon atoms that are directly bonded to one another, or they can be further apart.

[0085] Furthermore, the residues R a , R b , R c , R d , R 1 and / or R 2 the respective groups to which these residues are bonded may optionally represent a bond, so that the associated groups, preferably rings or ring systems, can be directly connected to one another, so that a ring closure can be effected.

[0086] Furthermore, it can be provided that the residues or substituents R a , R b , R c , R d and R 1according to the above formulas, with the ring atoms of the respective ring or ring system to which the radicals are bonded, do not form a fused aromatic or heteroaromatic ring system, preferably not a fused ring system. This embodiment, in which the radicals are substituents R a , R b , R c , R d and R 1 do not form a ring, the formation of a condensed ring system with possible substituents R 1 and R 2 also, which are attached to the residues R a , R b , R c , R d , R 1 may be bound.

[0087] In a further preferred embodiment of the invention, it can be provided that at most four of the groups R, R c , R d are not equal to H or D, preferably at most two of the groups R, R c , R d are not H or D. In a particularly preferred embodiment, none of the groups R, Rc , R d not equal to H or D.

[0088] Preferred are R a and R b at each occurrence, identically or differently selected from H and D, preferably H, provided they do not contain a group of the formula -(L) q -(Z) S are. Preference is given to all groups selected from the groups R a and R b , except for one group chosen from the groups R a and R b , equal to H or D, preferably H.

[0089] In a preferred embodiment of the invention, R a and R bat each occurrence, identically or differently selected from H, D, F, CN, Si(R)s, Si(Ar)s, straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, where the alkyl groups may each be substituted by one or more radicals R other than H, and aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which may each be substituted by one or more radicals R other than H. Preferably, all groups are selected from the groups R a and R b , with the exception of one group chosen from the groups R a and R b , equal to H or D, preferably H.

[0090] Preferred substituents R, R c and R d , Ar', R 1 and R 2 In a particularly preferred embodiment of the invention, the following preferences for Rc , R d , Ar', R 1 and R 2 simultaneously and apply to the structures of formula (1 ) as well as to all preferred embodiments listed above.

[0091] In a preferred embodiment of the invention, R, R c and R d at each occurrence, the same or different, selected from the group consisting of H, D, F, CN, OR 1 , a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherein the alkyl group is in each case substituted with one or more radicals R 1 may be substituted by other than H, but is preferably unsubstituted, and wherein one or more non-adjacent CFh groups may be replaced by O, and an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, each substituted by one or more radicals R 1may be substituted other than H. Particularly preferably, R is selected at each occurrence, identically or differently, from the group consisting of H, F, CN, a straight-chain alkyl group having 1 to 6 C atoms, in particular having 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group having 3 to 6 C atoms, where the alkyl group is substituted in each case with one or more radicals R 1 may be substituted, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 1 , preferably non-aromatic residues R 1 , may be substituted. Very particularly preferably, R is selected at each occurrence, identically or differently, from the group consisting of H, D, CN or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 1, preferably non-aromatic residues R 1 , may be substituted. Particularly preferably, all radicals R are the same or different on each occurrence and are selected from an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 18 aromatic ring atoms, which can each be substituted by one or more radicals R 1 , preferably non-aromatic residues R 1 can be substituted.

[0092] Suitable aromatic or heteroaromatic ring systems R, R a , R b , R c and R dare selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which may be linked via the 1-, 2-, 3- or 4-position, spirobifluorene, which may be linked via the 1-, 2-, 3- or 4-position, naphthalene, which may be linked via the 1- or 2-position, indole, benzofuran, benzothiophene, which may be linked via the 1-, 2-, 3- or 4-position, dibenzofuran, carbazole, which may be linked via the 1-, 2-, 3- or 4-position, dibenzothiophene, which may be linked via the 1-, 2-, 3- or 4-position, indenocarbazole, Indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, benzimidazole, phenanthrene, triphenylene or a combination of two or three of these groups,which each have one or more radicals R or R, 1 can be substituted. If R, R a R b , R c or R d represents a heteroaryl group, in particular triazine, pyrimidine or quinazoline, aromatic or heteroaromatic radicals R 1 at this heteroaryl group may be preferred.

[0093] The groups R, R c and / or R d , if they represent an aromatic or heteroaromatic ring system, preferably selected from the groups of the following formulas R-1 to R-186,

[0094]

[0095] R-16 R-17 R-18

[0096]

[0097] R-28 R-29 R-30

[0098] 35

[0099]

[0100]

[0101]

[0102] R-114 R-115 R-116 R-117

[0103]

[0104]

[0105]

[0106] R-186 where R 1 has the meanings given above, the dashed bond represents the bond to the corresponding group and furthermore:

[0107] Ar 3 is at each occurrence, identically or differently, a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, each of which is substituted by one or more radicals R 1 can be substituted;

[0108] A 1 is the same or different each time it occurs BR 1 , C(R 1 )2, Si(R 1 )2, C=O, NR 1 , 0 or S, where A 1 in the formulas R-150 and R-151 for BR 1 , C=O, NR 1 , 0 or S; A 2 is the same or different at each occurrence C(R 1)2, NR 1 , 0 or S; p is 0 or 1 , where p = 0 means that the group Ar 3 is not present and that the corresponding aromatic or heteroaromatic group is directly bonded to the associated atom, for example a carbon atom or to a heteroatom such as nitrogen, where, in the case of bonding to a heteroatom, for the formulas R-44, R-49, R-53, R-57, R-58, R-62, R-66, R-70, R-71, R-112, R-152 to R-160, R-167, R-172, R-177, R-182 p is 1; r is 0 or 1, where r = 0 means that no group A is present at this position. 1 and the corresponding carbon atoms are instead bound to residues R 1 are bound.

[0109] In a preferred embodiment, Ar comprises 3 bivalent aromatic or heteroaromatic ring systems based on the groups R-1 to R-186, where p is 0 and the dashed bond represents the bond to the corresponding group and an R 1represents the bond to the aromatic or heteroaromatic group according to R-1 to R-186.

[0110] If the above mentioned groups R-1 to R-186 for R several groups A 1 all combinations from the definition of A 1 Preferred embodiments are then those in which a group A 1 for C(R 1 )2, NR 1 , 0 or S and the other group A 1 for C(R 1 )2, NR 1 , 0 or S.

[0111] If A 1 for NR 1 the substituent R 1 which is bonded to the nitrogen atom, preferably represents an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 2 In a particularly preferred embodiment, this substituent R 1identical or different on each occurrence represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, and which in each case can also be substituted by one or more radicals R 2 Particularly preferred are phenyl, biphenyl, terphenyl and quaterphenyl with linkage patterns as listed above for R-1 to R-35, where these structures are substituted by one or more radicals R 1 may be substituted, but are preferably unsubstituted.

[0112] If A 1 for C(R 1 )2, the substituents R 1which are bonded to this carbon atom, preferably identically or differently on each occurrence, represent a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R 2 R is particularly preferably 1 represents a methyl group or a phenyl group. The radicals R 1 also form a ring system with each other, which leads to a spiro system.

[0113] In a preferred embodiment, it can be provided that at least one of the radicals R, R c or R d represents an aromatic or heteroaromatic ring system selected from structures of the formulas R-1 to R-186.

[0114] The groups of the formulas R-1 to R-186 presented above also represent preferred substituents R a , R b if they represent an aromatic or heteroaromatic ring system, in which case the radicals R 1 are to be replaced by radicals R. Preferably, therefore, it can be provided that at least one of the radicals R a and / or R b is selected from structures of formulas R-1 to R-186, wherein the radicals R shown in formulas R-1 to R-186 1 are to be replaced by R.

[0115] In a preferred embodiment, the group L in formula -(L) q -(Z)s bivalent, trivalent or tetravalent aromatic or heteroaromatic ring systems based on the groups R-1 to R-186, where p is 0 and the dashed bond represents the bond to the corresponding group and one, two or three R 1represents the bond to the aromatic or heteroaromatic group according to R-1 to R-186, where in this case the radicals R 1 by residues R c Preferably, the group L in formula -(L) q -(Z) S exactly one or two particularly preferred, especially preferably exactly one aromatic or heteroaromatic ring systems based on the groups R-1 to R-186.

[0116] In a further preferred embodiment of the invention, Ar' is identical or different on each occurrence and is an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, particularly preferably having 6 to 24 aromatic ring atoms and very particularly preferably having 6 to 13 aromatic ring atoms, which is in each case substituted by one or more radicals R 1 can be substituted.

[0117] In a further preferred embodiment of the invention, R 1identically or differently on each occurrence selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl group is in each case substituted with one or more radicals R 2 may be substituted by other than H, or an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, each substituted by one or more radicals R 2 may be substituted by other than H; two or more radicals R 1 together form an aliphatic ring system. In a particularly preferred embodiment of the invention, R 1identically or differently on each occurrence selected from the group consisting of H, D, a straight-chain alkyl group having 1 to 6 C atoms, in particular having 1, 2, 3 or 4 C atoms, or a branched or cyclic alkyl group having 3 to 6 C atoms, where the alkyl group is substituted with one or more radicals R 2 may be substituted, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each substituted by one or more radicals R 2 can be substituted by something other than H.

[0118] In a further preferred embodiment of the invention, R 2identically or differently on each occurrence, H, D, CN, F, an alkyl group having 1 to 4 C atoms or an aryl group having 6 to 10 C atoms, which may be substituted by an alkyl group having 1 to 4 C atoms, but is preferably unsubstituted. In a further preferred embodiment of the invention, all radicals R 1 , insofar as they represent an aromatic or heteroaromatic ring system, or R 2 as long as they represent aromatic or heteroaromatic groups selected from the groups R-1 to R-186, which, however, are then each substituted with R 2 , or the one at R 2 mentioned groups are substituted.

[0119] In a preferred embodiment of the invention, all aromatic or heteroaromatic groups of the radicals R, R a , R b , R c , R d , R 1 or R 2 selected from the corresponding groups R-1 to R-186.

[0120] In a preferred embodiment, the compounds according to the application are at least 50%, in particular at least 80%, particularly preferably completely (100%) deuterated. This means that in such a compound, the corresponding proportion of the hydrogen atoms contained in the undeuterated compound is replaced by D atoms. The undeuterated compound is the corresponding compound in which none of the hydrogen atoms contained is replaced by D, and which therefore does not contain any D. In a completely deuterated compound, all hydrogen atoms contained are replaced by D atoms. In the above paragraph, the term “hydrogen atoms” is to be understood as protium atoms. The above statements are to be understood in such a way that the compound according to the application, if it is partially deuterated, ieis not completely undeuterated and not completely deuterated, and is essentially a mixture of different isomers with respect to the isotopes protium and deuterium. Percentages of the degree of deuteration of the compound according to the application, as stated above, are therefore generally to be understood as average values ​​across the mixture of the various isotope isomers (isotopologues). Individual isotopologues are usually not isolated.

[0121] According to a preferred embodiment, part of the compound is completely undeuterated, and another part is largely or completely, preferably completely, deuterated. According to a preferred embodiment, at least one of the radicals R a and / or R ba group selected from N(Ar)2 or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, wherein this group is largely or completely deuterated, and the other parts of the compound of formula (1) are completely undeuterated. According to an alternative preferred embodiment of the invention, the above-described group which represents at least one of the radicals R a and / or R b is completely undeuterated, and the rest of the compound of formula (1 ) is largely or completely deuterated.

[0122] The alkyl groups in the compounds according to the application that are processed by vacuum evaporation preferably have no more than five carbon atoms, more preferably no more than four carbon atoms, and most preferably no more than one carbon atom. Also suitable for compounds that are processed from solution are compounds that are substituted by alkyl groups, especially branched alkyl groups, with up to 10 carbon atoms, or that are substituted by oligoarylene groups, for example ortho-, meta-, para-, or branched terphenyl or quaterphenyl groups.

[0123] The above-mentioned preferred embodiments can be combined with each other as desired within the limitations defined in claim 1. In a particularly preferred embodiment of the invention, the above-mentioned advantages occur simultaneously.

[0124] Examples of preferred compounds according to the embodiments listed above are the compounds listed in the following table. 5

[0125] 30

[0126] 5

[0127] 30

[0128]

[0129] The compounds of the invention can be prepared according to synthesis steps known to the person skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Heck reaction, Hartwig-Buchwald coupling, etc.

[0130] According to a preferred embodiment of the invention, the compound of formula (1) is prepared by constructing the basic structure, which carries a reactive group X, in a first step. X is preferably selected from halogen, in particular Cl and Br, with Br being preferred. X is preferably introduced via commercially available phenyl-1H-benzimidazole reactants, e.g., 1-(2-bromophenyl)-1H-benzimidazole (CAS: 1198007-13-4) or 7-bromo-1H-phenyl-1H-benzimidazole (CAS: 907205-47-4). This is shown in Scheme 1 and Scheme 2:

[0131] Alternatively, the group X can be introduced via the 11H-indolo[1,2-a]benzimidazol-11-one reactant, thus constructing the X-substituted backbone, as shown in Schemes 3 and 4. X-bearing reactants can then be preferred: 4-bromo-11H-indolo[1,2-a]benzimidazol-11-one (CAS: 2360432-42-2) or 6-bromo-11H-indolo[1,2-a]benzimidazol-11-one (CAS: 2360432-44-4).

[0132] Scheme 3

[0133] Scheme 4

[0134]

[0135] For polysubstituted compounds of formula (1 ), the reaction pathways and reactants according to Schemes 1 -4 can also be combined.

[0136] Aza derivatives, i.e. compounds that have a nitrogen atom instead of one or more carbon ring atoms in the basic structure, are synthesized analogously by also introducing the nitrogen via the reactants, e.g. 1-(3-bromo-4-pyridinyl)-1 H-benzimidazole (CAS: 1859695-97-8).

[0137] In a subsequent step of the preferred embodiment of the synthesis process for preparing a compound of formula (1 ), either (Scheme 5) an amino group is introduced into the position of the group X via a Hartwig-Buchwald coupling, or (Scheme 6) the group X is converted into a boronic acid group, and then this group is reacted in a Suzuki coupling with an aromatic or heteroaromatic compound carrying a halogen group.

[0138] Scheme 5

[0139] Scheme 6

[0140] Conversion into boronic acid or boronic acid ester Suzuki coupling

[0141] The basic structure is preferably prepared by reacting a benzimidazole with an 11 H-indolo [1,2-a] benzimidazol-11 -one compound, as shown in the examples.

[0142] The compounds suitable as starting materials for this purpose are often commercially available or can be prepared by methods known from the literature. Further derivatization of the basic structure can be achieved using known methods, as described above and below. Further information on the synthesis of the compounds of the invention can be found in the synthesis examples.

[0143] A further object of the present invention is therefore a process for preparing a compound of formula (1), which is characterized in that in a first step a heteroaromatic ketone compound is reacted with an N-phenyl-benzimidazole derivative to form a tertiary alcohol and in a second step a ring formation takes place with elimination of water, whereby a compound of formula (1) is obtained.

[0144] The resulting compound is preferably substituted by at least one reactive group, preferably a halogen group, particularly preferably Br or Cl, on one of its aromatic six-membered rings. Preferably, a substituent is introduced at the position of said reactive group in one or more further steps, in particular by Hartwig-Buchwald coupling or Suzuki coupling.

[0145] The heteroaromatic ketone compound is preferably a benzimidazole derivative with a fused keto-indene group. Preferably, in the reaction described above, the N-phenylbenzimidazole derivative is deprotonated at the C atom of the imidazole ring of the benzimidazole and reacted with the heteroaromatic ketone compound. The resulting tertiary alcohol is reacted under acidic conditions in a cyclization reaction to yield a compound with the basic structure of formula (1).

[0146] For processing the compounds of the invention from the liquid phase, for example by spin coating or printing processes, formulations of the compounds of the invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, Cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP,p-Cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butylmethyl ether, triethylene glycol butylmethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyloctanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents.

[0147] The present invention therefore further provides a formulation, in particular a solution, dispersion or emulsion, comprising at least one compound according to the invention and at least one further compound. The further compound can, for example, be a solvent, in particular one of the abovementioned solvents or a mixture of these solvents. The preparation of such solutions is known to the person skilled in the art and is described, for example, in WO 2002 / 072714, WO 2003 / 019694 and the literature cited therein. However, the further compound can also be at least one further organic or inorganic compound which is also used in the electronic device, for example an emitting compound and / or a matrix material. This further compound can also be polymeric.

[0148] The compounds of the invention are suitable for use in an electronic device, in particular in an organic electroluminescent device (OLED). Depending on the substitution, the compounds can be used in different functions and layers.

[0149] A further object of the present invention is therefore the use of a compound according to the invention in an electronic device.

[0150] A further subject of the present invention is an electronic device comprising at least one compound according to the invention.

[0151] The compounds according to the invention can be present, in particular when used, as a racemate or as a pure enantiomer.

[0152] An electronic device within the meaning of the present invention is a device that contains at least one layer containing at least one organic compound. The component can also contain inorganic materials or layers composed entirely of inorganic materials.

[0153] The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), dye-sensitized organic solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic photodiodes (OPDs), organic field quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic plasmon emitting devices, but preferably organic electroluminescent devices (OLEDs).

[0154] The device is particularly preferably an organic electroluminescent device comprising a cathode, an anode, and at least one emitting layer, wherein at least one organic layer, which may be an emitting layer, hole-transport layer, electron-transport layer, hole-blocking layer, electron-blocking layer, or another functional layer, comprises at least one compound according to the invention. The layer depends on the substitution of the compound.

[0155] In addition to these layers, the organic electroluminescent device may contain further layers, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers, and / or organic or inorganic p / n junctions. Interlayers, which, for example, have an exciton-blocking function, may also be inserted between two emitting layers. It should be noted, however, that not every one of these layers is necessarily required.

[0156] The organic electroluminescent device can contain one emitting layer or it can contain multiple emitting layers. If multiple emitting layers are present, these preferably have a total of multiple emission maxima between 380 nm and 750 nm, resulting in overall white emission, i.e., different emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. Particular preference is given to systems with three emitting layers, with the three layers exhibiting blue, green, and orange or red emission (the basic structure is described, for example, in WO 2005 / 011013). The organic electroluminescent device according to the invention can also be a tandem OLED, in particular for white-emitting OLEDs.

[0157] The compound of formula (1) is preferably used in an organic electroluminescent device comprising one or more phosphorescent emitters. The compound of the invention according to the embodiments listed above can be used in different layers, depending on the precise structure.

[0158] The organic electroluminescent device may contain one emitting layer, or it may contain multiple emitting layers, with at least one organic layer of the device containing at least one compound according to the invention. The compound according to the invention is preferably contained in an emitting layer of the device. Furthermore, the compound according to the invention may also be contained in an electron-transport layer and / or in a hole-blocking layer and / or in a hole-transporting layer and / or in an exciton-blocking layer.

[0159] The term "phosphorescent compound" typically refers to compounds in which the emission of light occurs through a spin-forbidden transition, e.g., a transition 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, compounds that, upon suitable excitation, emit light, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80.All luminescent complexes with transition metals or lanthanides are preferably considered phosphorescent compounds, especially if they contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, especially compounds containing indium, platinum, or copper. For the purposes of the present invention, all luminescent indium, platinum, or copper complexes are considered phosphorescent emitting compounds.

[0160] Examples of the emitters described above can be found for green and yellow emitters in applications US2025 / 002778A, US2024 / 425538A, US2024 / 349591 A, US2023 / 331757A, US2024 / 209013A, US2023 / 309374A, US2023 / 112032A, US2023 / 110705A, US2023 / 058719A, US2023 / 054166A, US2023 / 0225184A, US2023 / 203074A, US2022 / 0153769A, US2021 / 217969A, US2021 / 135130A, US2021 / 054010A, US2020 / 251666A, US2020 / 115406A, W02020 / 165064, US2019 / 280219A, US2018 / 0282356A, US2017 / 373259A, US2017 / 077425A, US2014 / 131676A, US2014 / 0231755A, US2010 / 0270916A, WO2010 / 028151, US2010 / 0244004, EP3623443A, EP4137551 A1, CN1 14106056A, WO2016 / 020516A1 and WO2015 / 192941 A1. Furthermore, for red emitters, examples of the emitters described above can be found in the publications and disclosures Adv. Mater. 2003, 15(11), 884; W02008 / 109824; US2010 / 0133524;

[0161] WO201 0 / 033550; US2012 / 0181511 ; US2015 / 0295198; US2015 / 0295199; US2016 / 0093808; US2018 / 097187; US2020 / 0127212 and US2020 / 0111977.

[0162] In general, all phosphorescent complexes as used according to the prior art for phosphorescent OLEDs and as known to the person skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art can use further phosphorescent complexes without inventive step. It is also possible for the person skilled in the art, even without inventive step, to use further phosphorescent complexes in combination with the compounds of formula (1) in organic electroluminescent devices. Since the compounds according to the invention can also have a high triplet energy level, depending on the substitution, it is also possible, in particular, to use them as matrix material for blue-phosphorescent emitters. Examples of such emitters are mentioned in the following publications and applications and listed in a table below (table with blue-phosphorescent metal complexes):

[0163] Adv. Mater. 2014, 26, 7116; Nat. Commun. 2014, 5, 5008; Adv. Opt. Mater. 2021, 9, 2100630; Nat. Commun. 2018, 9, 4990; Sungho Nam et al., Adv. Sei. 2021, 2100586; Eungdo Kim et al., Sei. Adv. 2022, 8, eabq1641 ; Nat. Photonics 2022, 16, 212; W02005 / 019373 A2;

[0164] WO201 1 / 073149 A1; WO2014 / 008982 A1; WO2015 / 000955 A1 ; US2016 / 072082 A; US2018 / 282357 A; US 2019 / 0119312 A; US 2022 / 115607 A; US 2022 / 298193 A; US 2022 / 271236 A.

[0165] According to the invention, it is also possible to use the compound of formula (1) in an electronic device containing one or more fluorescent emitting compounds.

[0166] In a preferred embodiment of the invention, the compounds of formula (1) are used as electron-transporting material. In this case, the compounds are preferably present in an electron-transport layer or a hole-blocking layer, or as an electron-conducting or bipolar host material in an emitting layer. Use as an electron-conducting or bipolar host material in an emitting layer is particularly preferred. Suitability as an electron-transporting material can be improved by the presence of appropriate groups, as described above.

[0167] An electron transport layer within the meaning of the present application is a layer with an electron-transporting function between the cathode and the emitting layer.

[0168] In the context of the present application, electron injection layers and hole blocking layers are understood to mean specific embodiments of electron transport layers. In the case of a plurality of electron transport layers between the cathode and the emitting layer, an electron injection layer is an electron transport layer that is directly adjacent to the cathode or is separated from it only by a single coating of the cathode. In the case of several electron transport layers between the cathode and the emitting layer, a hole blocking layer is the electron transport layer that is directly adjacent to the emitting layer on the cathode side. The OLED according to the invention preferably comprises two, three or four electron-transporting layers between the cathode and the emitting layer, of which preferably at least one, particularly preferably exactly one or two, contains a compound of the formula (1).

[0169] If the compound of formula (1) is used as an electron transport material in an electron transport layer, an electron injection layer or a hole blocking layer, the compound can be used as a pure material, ie in a proportion of 100% in the electron transport layer, or it can be used in combination with one or more other compounds.

[0170] In a preferred embodiment of the invention, the compounds of formula (1) are used as hole-transporting materials. In this case, the compounds are preferably present in a hole-transporting layer or an electron-blocking layer, or as hole-conducting or bipolar host material in an emitting layer. Particular preference is given to using them as hole-conducting or bipolar host material in an emitting layer. Their suitability as hole-transporting materials is improved by the presence of amino groups, as described above.

[0171] A hole transport layer in the sense of the present application is a layer with a hole transporting function between the anode and the emitting layer.

[0172] In a further embodiment of the present invention, the compound of formula (1) is used in an emitting layer as a matrix material in combination with one or more emitting compounds, wherein the emitting compounds may be fluorescent or phosphorescent, preferably phosphorescent.

[0173] In this case, the proportion of matrix material in the emitting layer is between 50.0 and 99.9 vol.%, preferably between 80.0 and 99.5 vol.%, particularly preferably between 92.0 and 99.5 vol.% for fluorescent emitting layers and between 85.0 and 97.0 vol.% for phosphorescent emitting layers.

[0174] Accordingly, the proportion of the emitting compound is between 0.1 and 50.0 vol.%, preferably between 0.5 and 20.0 vol.%, particularly preferably between 0.5 and 8.0 vol.% for fluorescent emitting layers and between 3.0 and 15.0 vol.% for phosphorescent emitting layers.

[0175] An emitting layer of an organic electroluminescent device can also comprise systems containing a plurality of matrix materials (mixed matrix systems) and / or a plurality of emitting compounds. In this case, too, the emitting compounds are generally those with the smaller proportion in the system, and the matrix materials are those with the larger proportion. In individual cases, however, the proportion of a single matrix material in the system may be lower than the proportion of a single emitting compound.

[0176] The compounds of formula (1) are preferably used as a component of mixed matrix systems. The mixed matrix systems preferably consist of two or three different matrix materials, particularly preferably of two different matrix materials. In this case, one of the two materials is preferably a material with hole-transporting properties and the other material is a material with electron-transporting properties. The compound of formula (1) is preferably the matrix material with electron-transporting properties. However, the desired electron-transporting and hole-transporting properties of the mixed matrix components can also be predominantly or completely combined in a single mixed matrix component, with the further mixed matrix component(s) fulfilling other functions.The two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, and most preferably 1:4 to 1:1. Mixed matrix systems are preferably used in phosphorescent organic electroluminescent devices. A source for more detailed information on mixed matrix systems is the application WO 2010 / 108579.

[0177] The mixed matrix systems can contain one or more emitting compounds, preferably one or more phosphorescent compounds. Mixed matrix systems are generally preferred for use in phosphorescent organic electroluminescent devices.

[0178] Particularly suitable matrix materials which can be used in combination with the compounds according to the invention as matrix components of a mixed matrix system are selected from the preferred matrix materials for phosphorescent compounds or the preferred matrix materials for fluorescent compounds mentioned below, depending on which type of emitting compound is used in the mixed matrix system.

[0179] Preferred phosphorescent compounds for use in mixed matrix systems are the same as those described above as generally preferred phosphorescent emitter materials.

[0180] Examples of preferred phosphorescent emitters are the compounds disclosed in the above-mentioned patent applications and publications.

[0181] Preferred green and yellow phosphorescent emitters are: 5

[0182] 30 Ċ

[0183] Preferred red phosphorescent emitters are:

[0184]

[0185] Preferred fluorescent emitting compounds are selected from DABNA derivatives and other boron derivatives, in particular according to WO 2020 / 208051, WO 2015102118, WO 2016 / 152418, WO 2018 / 095397, WO 2019 / 004248, WO 2019 / 132040, US 2020 / 0161552, and WO 2021 / 089450. Particularly preferred fluorescent emitters are the compounds shown in the following table: 5

[0186] 30 5

[0187] 30 5

[0188] 30

[0189]

[0190] Useful matrix materials for fluorescent compounds in the emitting layer, particularly in the case where the compounds according to the present application are not used in the emitting layer, include materials from various substance classes. Preferred matrix materials are then selected from the classes of oligoaryls (e.g., 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthylanthracene), in particular oligoaryls with fused aromatic groups, oligoarylenevinylenes (e.g., DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (e.g., according to WO 2004 / 081017), hole-conducting compounds (e.g., according to WO 2004 / 058911), electron-conducting compounds, especially ketones, phosphine oxides, sulfoxides, etc.(for example according to WO 2005 / 084081 and WO 2005 / 084082), the atropisomers (for example according to WO 2006 / 048268), the boronic acid derivatives (for example according to WO 2006 / 117052) or the benzanthracenes (for example according to WO 2008 / 145239). Particularly preferred matrix materials are selected from the classes of oligoarylenes with naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, the oligoarylenevinylenes, the ketones, the phosphine oxides and the sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes comprising anthracene, benzanthracene, benzophenanthrene and / or pyrene or atropisomers of these compounds. In the context of the present invention, an oligoarylene is understood to mean a compound in which at least three aryl or arylene groups are bonded together.Further preferred are the anthracene derivatives disclosed in WO 2006 / 097208, WO 2006 / 131192, WO 2007 / 065550, WO 2007 / 110129, WO 2007 / 065678, WO 2008 / 145239, WO 2009 / 100925, WO 2011 / 054442 and EP 1553154, the pyrene compounds disclosed in EP 1749809, EP 1905754 and US 2012 / 0187826, the benzanthracenylanthracene compounds disclosed in WO 2015 / 158409, the indenobenzofurans disclosed in WO 2017 / 025165 and the pyrene compounds disclosed in WO 2017 / 036573 disclosed phenanthryl-anthracenes.

[0191] Preferred matrix materials for phosphorescent compounds are, as well as compounds according to formula (1), aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g. according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triarylamines, carbazole derivatives, e.g. CBP (N,N-biscarbazolylbiphenyl) or WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176, indolocarbazole derivatives, e.g. B. according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, e.g. according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776, azacarbazole derivatives, e.g. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, e.g. according to WO 2007 / 137725, silanes, e.g. according to WO 2005 / 111172, azaboroles or boronic esters, e.g. according to WO 2006 / 117052, triazine derivatives, e.g. B.according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, diazasilole or tetraazasilole derivatives, e.g. according to WO 2010 / 054729, diazaphosphole derivatives, e.g. according to WO 2010 / 054730, bridged carbazole derivatives, e.g. B. according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080, triphenylene derivatives, e.g. according to WO 2012 / 048781, lactams, e.g. according to WO 2011 / 116865 or WO 2011 / 137951, or dibenzofuran derivatives, e.g. according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565. Likewise, another phosphorescent emitter, which emits at a shorter wavelength than the actual emitter, can be present in the mixture as a co-host, or a compound that does not participate, or does not participate to a significant extent, in charge transport, as described, for example, in WO 2010 / 108579.

[0192] Another possibility for improving the performance of electronic devices, particularly organic electroluminescent devices, is to use combinations of two or more host materials in the emission layer. For example, US Pat. No. 6,392,250 B1 discloses the use of a mixture consisting of an electron-transport material, a hole-transport material, and a fluorescent emitter in the emission layer of an OLED. US Pat. No. 6,803,720 B1 discloses the use of a mixture containing a phosphorescent emitter and a hole-transport and electron-transport material in the emission layer of an OLED.

[0193] Also preferred are material mixtures in the emitting layer which, in addition to the compound of formula (1) as host material, contain one, two, or three further compounds selected from host materials and emitter materials. The following compositions are particularly preferred in the emitting layer:

[0194] -compound of formula (1 ) as host, as well as another compound which is a triplet emitter;

[0195] -compound of formula (1 ) as host, further host compound, and further compound which is a triplet emitter;

[0196] Compound of formula (1 ) as host, further host compound, further compound which is a triplet emitter or sensitizer, and further compound which is a fluorescent emitter.

[0197] It is further preferred that the composition of the present invention, preferably present in an emitting layer of the electronic device, in addition to the electron-transporting material, which is preferably a compound according to formula (1), further contains at least one further, preferably hole-transporting host material, which may also be a compound according to formula (1) or may be a compound which does not correspond to formula (1).

[0198] Preferably, the at least one further host material is selected from the group of carbazole and triarylamine derivatives, more specifically biscarbazoles, bridged carbazoles, triarylamines, dibenzofuran-carbazole derivatives or dibenzofuran-amine derivatives, carbazolamines, and compounds containing a silicon and nitrogen-containing ring.

[0199] More preferably, the at least one further host material is selected from compounds of formula (h-1) or (h-2): where:

[0200] K Ar 4 or -L 5 -N(Ar 6 )2is;

[0201] Z A CR z or CR A or two adjacent groups Z A together form a condensed ring;

[0202] R A -L 3 -Ar 5 or -L 4 -N(Ar 6 )2 is;

[0203] R z is selected at each occurrence, identically or differently, from H, D, F, CI, Br, I, N(Ar 6 )2, N(R')2, OAr 6 , SAr 6, CN, NO2, OR', SR', COOR', C(=O)N(R')2, Si(R')3, B(OR')2, C(=O)R', P(=O)(R')2, S(=O)R', S(=O)2R', OSO2R', a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may each be substituted by one or more radicals R, where one or more non-adjacent CH2 groups may be replaced by Si(R')2, C=O, NR', O, S or CONR', or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R';

[0204] L 4 , L 5at each occurrence, identically or differently, are a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R';

[0205] L 3 a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R', where a radical R' is attached to L 3 with a remainder R z at which carbazole can form a ring;

[0206] Ar 4 an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R';

[0207] Ar 5at each occurrence, identically or differently, is an unsubstituted or substituted heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more R';

[0208] R z at each occurrence, the same or different, H, D, F, CI, Br, I, N(Ar 6 )2, N(R')2, OAr 6 , SAr 6, CN, NO2, OR', SR', COOR', C(=O)N(R')2, Si(R')3, B(OR')2, C(=O)R', P(=O)(R')2, S(=O)R', S(=O)2R', OSO2R', a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may each be substituted by one or more radicals R', where one or more non-adjacent CH2 groups may be replaced by Si(R')2, C=O, NR', O, S or CONR', or an aromatic or heteroaromatic ring system having 5 to 60 aromatic Ring atoms, preferably 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R', where two radicals R z can form a ring system together;

[0209] E is independently at each occurrence a single bond or a group C(R°)2;

[0210] R° is independently selected at each occurrence from a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be substituted by one or more radicals R'; x, y are independently selected from 0 or 1, wherein when x or y is 0, the corresponding group E is not present; and x + y = 1 or 2;

[0211] Ar 6 is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R", where two or more R" may together form an aromatic or heteroaromatic ring system;

[0212] R' at each occurrence, identical or different, is H, D, F, CI, Br, I, N(Ar)2, N(R")2, OAr 6 , SAr 6, CN, NO2, OR", SR", COOR", C(=O)N(R")2, Si(R")3, B(OR")2, C(=O)R", P(=O)(R")2, S(=O)R", S(=O)2R", OSO2R", a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may each be substituted by one or more radicals R", where one or more non-adjacent CH2 groups may be replaced by Si(R")2, C=O, NR", O, S or CONR", or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R", whereby two radicals R' together may also form a ring system;

[0213] R" at each occurrence, identical or different, H, D, F, CI, Br, I, N(R"')2, CN, NO 2IOR", SR, COOR", C(=O)N(R'")2, Si(R'")3, B(OR'")2, C(=O)R", P(=O)(R'")2, S(=O)R", S(=O)2R", OSO2R", a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may each be substituted by one or more radicals R", where one or more non-adjacent CH2 groups may be replaced by Si(R")2, C=O, NR", O, S or CONR", or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R", where two radicals R" together may also form a ring system;

[0214] R"' is, identically or differently at each occurrence, H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by D or F; two or more radicals R"' together may form a ring system. with the proviso that the compounds of the formulas (h-1) and (h-2) contain at least one group Z A include those for R A stands.

[0215] Preferably, L 4 , L 5 at each occurrence, identically or differently, a single bond or an aromatic or heteroaromatic ring system having 5 to 25, more preferably 5 to 20 and even more preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R'.

[0216] Preferably, L 3a single bond or an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, more preferably 5 to 20 and even more preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R', where a radical R' is attached to L 3 with a remainder R z at which carbazole can form a ring.

[0217] Preferably, the group Ar 5 an unsubstituted or substituted heteroaromatic ring system selected from the groups of formulas (Ar5-1) to (Ar5-6), where the dashed bond represents the bond to L 3 or Z A indicates; V CR v is, with the proviso that V is C when bonded to the group of formula (h-1 ) or (h-2); or two adjacent groups

[0218] V together form a condensed ring;

[0219] T CR Tis, with the proviso that T represents C when bonded to the group of formula (h-1) or (h-2), or two adjacent groups T together form a condensed ring;

[0220] M is an aromatic ring system having 6 to 40 aromatic ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R;

[0221] E 1 at each occurrence independently a single bond or a group C(R O )2; where R° has the same meaning as above;

[0222] R T ' R v is selected at each occurrence, identically or differently, from H, D, F, CI, Br, I, N(Ar 6 )2, N(R')2, OAr 6 , SAr 6, CN, NO2, OR', SR', COOR', C(=O)N(R')2, Si(R')3, B(OR')2, C(=O)R', P(=O)(R')2, S(=O)R', S(=O)2R', OSO2R', a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may each be substituted by one or more radicals R', where one or more non-adjacent CH2 groups may be replaced by Si(R')2, C=O, NR', O, S or CONR', or an aromatic or heteroaromatic ring system having 5 to 60 aromatic Ring atoms, preferably 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R', where two radicals R T together can form a ring system and two residues R v together can form a ring system; x 1 , y 1 are independently selected from 0 or 1, where if x1 or y 1 0, the corresponding group E 1 is not present; provided that x 1 + y 1 = 1 or 2; and where R' and Ar 6 have the same meaning as above.

[0223] According to a preferred embodiment, the at least one further host material is selected from compounds of formula (h-1-1) to (h-2-2):

[0224] Formula (h-1-3)

[0225] where the symbols have the same meaning as above and where the indices have the following meaning: x, y, x 1 ,y 1 have the same meaning as above; c, f independently represent 0, 1, 2, 3 or 4; d, e independently represent 0, 1, 2 or 3; g represents 0, 1, 2 or 3 when x 1 =0; or for 0, 1 or 2 if x 1 =1 ; h stands for 0, 1 , 2, 3 or 4 if y 1 =0; or for 0, 1 , 2 or 3, if y 1=1 ; k stands for 0, 1 , 2, 3 or 4 if x=0; or for 0, 1 , 2 or 3 if x=1 ; and

[0226] I stands for 0, 1, 2, or 3 if y=0; or for 0, 1, or 2 if y=1.

[0227] Particularly preferably, the at least one further host material is further selected from the compounds according to formula (H-1) and the preferred embodiments of this formula, according to the not yet published application PCT / EP2023 / 085990, see also below, from compounds of the above-mentioned formula (h-1 -3) and from compounds of the above-mentioned formula (h-1 -4).

[0228] According to an alternative preferred embodiment, the at least one further host material is selected from compounds of formula (h-3): where the following applies to the groups and indices that occur:

[0229] M H is selected from Si, Ge and Sn, where M H preferably Si;

[0230] A is a ring selected from mono- or polycyclic aliphatic, aromatic or heteroaromatic ring systems, each of which is substituted by one or more radicals R H can be substituted;

[0231] Y H stands, identically or differently on each occurrence, for a group selected from NR H-N2 , O and S, where Y H preferably NR H-N2 is; RH-MI , RH-M2 Sin d is selected at each occurrence, the same or different, from H, D, F, CI, Br, I, C(=O)R H , OSO2R H , COOR H , CON(R H )2, N(R H )2, straight-chain alkyl groups having 1 to 40 C atoms, branched or cyclic alkyl groups having 3 to 40 C atoms, alkenyl or alkynyl groups having 2 to 40 C atoms, where the groups are each substituted by one or more radicals R H may be substituted, and wherein one or more CH2 units in the above-mentioned groups are substituted by Si(R H )2, Ge(R H )2, Sn(R H)2, C=O, C=S, C=Se, C=NR H , P(=O)(R H ), SO, SO2, NR H , -O-, -S-, -COO- or -CONR H - may be replaced, and wherein one or more H atoms in the above-mentioned groups may be replaced by D, F, CI, Br, I, CN or NO2, and aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R H and aralkyl or heteroaralkyl groups having 5 to 60 aromatic ring atoms, each substituted by one or more radicals R H may be substituted, where R H-M1 and R H-M2 may be linked together and form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R H can be substituted;

[0232] RH-NI , RH-N2 Sind at each occurrence, identically or differently, is selected from H, D, F, straight-chain alkyl groups having 1 to 40 C atoms, branched or cyclic alkyl groups having 3 to 40 C atoms, each of which is substituted by one or more radicals R H may be substituted, and in which one or more H atoms may be replaced by D, F or CN, and aromatic or heteroaromatic ring systems with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R H may be substituted; and where: when n=m=1 , the radicals R H-N1 and R H-M1 and / or R H - N2 and R H - M2 linked together and form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system, each of which is linked to one or more radicals R H may be substituted; or if n = 2, two radicals R H-N1 and / or two residues R H - N2if present, be linked to one another and form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system, each of which is linked to one or more radicals R H can be substituted;

[0233] R H stands at each occurrence, identically or differently, for H, D, F, CI, Br, I, CHO, CN, C(=O)Ar H , P(=O)(Ar H )2, S(=O)Ar H , S(=O)2Ar H , N(R H ')2, N(Ar H )2, NO2, Si(R H ')3, B(OR H ')2, OSO2R H ', a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms, a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which is substituted by one or more radicals R H ' may be substituted, where one or more non-adjacent CH2 groups are substituted by R H C=CR H ', C=C, Si(R H )2, Ge(R H )2, Sn(R H')2, C=O, C=S, C=Se, P(=O)(R H ), SO, SO2, O, S or CONR H and wherein one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R H ' may be substituted, or an aryloxy group having 5 to 60 aromatic ring atoms, each substituted by one or more radicals R H ' may be substituted; where two radicals R H may be linked together and form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R H ' can be substituted;

[0234] Ar H is selected at each occurrence, identically or differently, from aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals RH ' may be substituted;

[0235] R H ' is selected, identically or differently at each occurrence, from H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more CH2 groups may be replaced by SO, SO2, O, or S, and where in each case one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms; n is 1 or 2; m is (2-n).

[0236] Furthermore, the disclosure of the not yet published application PCT / EP2023 / 085990 regarding preferred embodiments of the compounds of the above-mentioned formula (h-3), in particular pages 10-21 of PCT / EP2023 / 085990, is hereby fully incorporated into the disclosure of the present application.

[0237] Further preferred as hole-transporting host material, for use in combination with the compound according to the application, preferably in an emitting layer of the electronic device, are the compounds shown in the table on pages 22-28 of the not yet published application PCT / EP2023 / 085990.

[0238] Examples of preferred host materials suitable as the second host material in the composition are shown in the following table:

[0239]

[0240] 30

[0241] 5

[0242] 30

[0243] In the table above, n represents the number of D atoms in the respective compound. If n = 0, this means that the compound is non-deuterated; n = 1 means that in the respective compound, one H atom is replaced by a D atom. nmax represents the maximum number of D atoms possible in the respective compound. The maximum number nmax can vary from compound to compound; depending on the compound, nmax can take on the following values: 20, 24, 26, 28, 30, 31, 32, 34, 35, 36, 37, 38, and 40.

[0244] According to a further, likewise preferred, embodiment of the invention, the compound according to the invention is used as a hole-transporting host material (h-TMM). In this case, it is preferably used in the emitting layer in a mixture with another host material, which is preferably an electron-transporting host material (e-TMM).

[0245] Such eTMMs, which are preferably used in combination with a compound according to the invention, in particular in the emitting layer, are preferably selected from compounds of the formulas (eTMMIa), (eTMMIb), (eTMMIc), (eTMMId) and (eTMMIe), I b)

[0246] where the symbols and indices used in these formulas have the following meanings: X is the same or different at each occurrence CR 7 or N, with the proviso that not more than two X per cycle represent N;

[0247] W, W 1 are the same or different at each occurrence 0, S, C(R W )2 or N-Ar 5 ;

[0248] Ar 5 represents, identically or differently at each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is substituted by one or more radicals R 7 can be substituted;

[0249] R wis, on each occurrence, identically or differently, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more H atoms may be replaced by D, F, or CN, or an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which may be replaced by one or more substituents selected from D, F, CN, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where one or more H atoms of the alkyl group on the aromatic or heteroaromatic ring system may be replaced by D, F, or CN; the two radicals R w which bind to the same carbon atom also form a ring system with each other;

[0250] A is the same or different at each occurrence CR 7or N, where a maximum of two groups A per cycle stand for N and where A stands for C, if at this position L 2 is bound;

[0251] L 2 is at each occurrence, identically or differently, a single bond or an aromatic or heteroaromatic ring system with 5 to 24 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted;

[0252] L 3 is an aromatic ring system with 6 to 40 ring atoms or a heteroaromatic ring system with 5 to 40 ring atoms, which are linked to one or more radicals R 7 may be substituted; a3 is, at each occurrence, the same or different, 0, 1, 2, 3 or 4; b3 is, at each occurrence, the same or different, 0, 1, 2 or 3;

[0253] Ring B is derived from an aryl group having 6 to 20 ring atoms, which may be substituted with one or more substituents R#;

[0254] R# is, identically or differently at each occurrence, D, F, CN or an aromatic ring system with 6 to 24 ring atoms, which is substituted by one or more radicals R 6 can be substituted;

[0255] R 6 is the same or different at each occurrence: H, D, F, CN, Si(R 7 )s, Ge(R 7 )3, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 7 and wherein one or more non-adjacent CFh groups are substituted by Si(R 7 )2, C=O, NR 7 , O, S or CONR 7 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 ring atoms, each of which is substituted by one or more radicals R 7 can be substituted;

[0256] R 7is the same or different at each occurrence H, D, F, CI, Br, I, N(R 8 )2, CN, NO2, OR 8 , SR 8 , Si(R 8 )3, Ge(R 8 )3, B(OR 8 )2, C(=O)R 8 , P(=O)(R 8 )2, S(=O)R 8 , S(=O)2R 8 , OSO2R 8 , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 8 may be substituted, with one or more non-adjacent CFh groups being substituted by Si(R 8 )2, C=O, NR 8 , 0, S or CONR 8 may be replaced, or an aromatic or heteroaromatic ring system with 5 to 40 ring atoms, each of which is substituted by one or more radicals R 8 can be substituted;

[0257] R 8is, at each occurrence, identically or differently, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, in particular a hydrocarbon radical, having 1 to 20 C atoms, in which one or more H atoms may be replaced by F;

[0258] Particularly preferred are compounds of the following formula (eTMMIc*), Formula (eTMMIc*) where the symbols and indices used have the meanings given above and the compounds may also be partially or fully deuterated. Particularly preferred groups are Ar 5 identically or differently at each occurrence selected from phenyl, meta-biphenyl or N-carbazolyl, each of which can also be substituted by one or more radicals R 7 Furthermore, at least one and particularly preferably exactly one of the substituents which are attached to the N-carbazolyl group or to Ar 5are bonded, a triphenylsilyl group. The compound of formula (eTMMIc*) particularly preferably has a group Ar 5 which represents a phenyl group substituted in the meta position with a triphenylsilyl group.

[0259] Examples of specific suitable electron-transporting matrix materials for use in combination with a compound according to the invention as a hole-conducting host material are the compounds shown below:

[0260]

[0261]

[0262]

[0263] Preferably, the compound of formula (1) is used as host material in combination with a blue or green phosphorescent emitter, in particular with a blue phosphorescent emitter.

[0264] Furthermore, it is preferred that the at least one blue phosphorescent emitter is selected from platinum complexes. Preferably, the at least one blue phosphorescent emitter has a LUMO of -1.8 eV to -2.2 eV, and the at least one blue phosphorescent emitter preferably has a HOMO of -5.0 eV to -5.6 eV, as defined by quantum mechanical calculations. HOMO and LUMO are determined as indicated in section 2) of the patent examples.

[0265] Preferably, the energy of the lowest triplet state Ti of the at least one blue phosphorescent emitter is higher than 2.55 eV, more preferably >2.65 eV, even more preferably >2.75 eV, as defined by quantum mechanical calculations. Ti is determined as specified in section 2) of the patent examples.

[0266] Furthermore, it is preferred that the compound of formula (1) is used as the host material in a blue- or green-emitting layer. The layer is preferably a blue-phosphorescent or blue-hyperphosphorescent layer. Alternatively, it can also be a blue- or green-hyperfluorescent layer or a green-phosphorescent layer.

[0267] The compounds of the formula (Pt-1 ) according to the following definition are very suitable as blue phosphorescent metal complexes:

[0268] Formula (Pt-1) where: Y 1 Y 2 , Y 3 , Y 4 , Y 5 same or different at each occurrence for a group CR Y or N; or Y 1 -Y 2 and / or Y 3 -Y 4 or Y 4 -Y 5can form a condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms, each of which can also be substituted by one or more radicals R';

[0269] E 50 at each occurrence, the same or different for C(R co )2, NR N0 , 0 or S;

[0270] Ar 50 at each occurrence, identically or differently, is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may also be substituted by one or more radicals R';

[0271] Ar 51 , Ar 52 , Ar 53 identical or different represent a condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms, each of which may also be substituted by one or more radicals R';

[0272] R Y at each occurrence, identically or differently, represents a radical selected from H, D, F, CI, Br, I, CHO, CN, C(=O)Ar 6, P(=O)(Ar 6 )2, S(=O)Ar 6 , S(=O)2Ar 6 , N(R')2, N(Ar 6 )2, NO2, Si(R')3, B(OR')2, OSO2R', a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R', where one or more non-adjacent CH2 groups may be replaced by R'C=CR', C=C, Si(R')2, Ge(R')2, Sn(R')2, C=O, C=S, C=Se, P(=O)(R'), SO, SO2, O, S or CONR' and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R', and an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R', where two radicals R Ytogether form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R'; R co at each occurrence, identically or differently, represents a radical selected from H, D, a straight-chain alkyl group having 1 to 40 C atoms, which may be substituted by one or more radicals R', an aryl or heteroaryl group having 6 to 18 aromatic ring atoms, each of which may be substituted by one or more radicals R, where two radicals R c together can form an aliphatic, aromatic or heteroaromatic ring system which is substituted by one or more radicals R';

[0273] R N0at each occurrence, identically or differently, represents a radical selected from H, D, F, a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, each of which is substituted by one or more radicals R' and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R';

[0274] R' and Ar 6 have the same meaning as above.

[0275] Preferably, Ar 50 at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40, more preferably 5 to 30 and even more preferably 6 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R'.

[0276] Preferably, Ar 51 , Ar52 , Ar 53 identical or different for a condensed aryl or heteroaryl ring with 6 aromatic ring atoms, which may also be substituted by one or more radicals R'.

[0277] Preferably, R Yat each occurrence, identically or differently, represents H, D, F, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40, preferably 1 to 20 and more preferably 1 to 10 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40, preferably 3 to 20 and more preferably 3 to 10 C atoms, each of which may be substituted by one or more radicals R', where one or more non-adjacent CH2 groups may be replaced by R'C=CR', C=C, O or S and where one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30 and particularly preferably 5 to 18 aromatic ring atoms, each of which may be substituted by one or more radicals R' can be.

[0278] Preferably, R coat each occurrence, identically or differently, represents a radical selected from H, D, a straight-chain alkyl group having 1 to 10, preferably 1 to 6 and more preferably 1 to 3 C atoms, which may be substituted by one or more radicals R', an aryl or heteroaryl group having 6 to 18 and preferably 6 to 12 aromatic ring atoms, each of which may be substituted by one or more radicals R', where two radicals R co together can form an aliphatic, aromatic or heteroaromatic ring system which is substituted by one or more radicals R'.

[0279] Preferably, R N0 at each occurrence, identically or differently, represents a radical selected from an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30 and even more preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R'.

[0280] Examples of particularly suitable blue phosphorescent metal complexes are shown below:

[0281]

[0282] Suitable charge transport materials which can be used in the hole injection or hole transport layer or in the electron barrier layer or in the electron transport layer of the electronic component according to the invention are, in addition to the compounds of formula (1), for example those described in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials which are used in these layers according to the prior art.

[0283] In addition to suitably substituted compounds of the invention according to formula (1), all materials that are used in the prior art as hole-transport materials in the hole-transport layer can be used as materials for the hole-transport layer. Aromatic amine compounds can be used. Further compounds which are preferably used in hole-transporting layers of the OLEDs according to the invention are in particular indenofluorenamine derivatives (e.g. according to WO 2006 / 122630 or WO 2006 / 100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (e.g. according to WO 01 / 049806), amine derivatives with fused aromatics (for example according to US 5,061,569), the amine derivatives disclosed in WO 95 / 09147, monobenzoindenofluorenamines (for example according to WO 08 / 006449), dibenzoindenofluorenamines (for example according to WO 07 / 140847), spirobifluorenamines (for example according to WO 2012 / 034627 or WO 2013 / 120577),Fluorenamines (for example according to WO 2014 / 015937, WO 2014 / 015938, WO 2014 / 015935 and WO 2015 / 082056), spirodibenzopyranamines (for example according to WO 2013 / 083216), dihydroacridine derivatives (for example according to WO 2012 / 150001), spirodibenzofurans and spirodibenzothiophenes (for example according to WO 2015 / 022051, WO 2016 / 102048 and WO 2016 / 131521), phenanthrenedarilamines (for example according to WO 2015 / 131976), spirotribenzotropolones (for example according to WO 2016 / 087017), spirobifluorenes with meta-phenyldiamine groups (for example according to WO 2016 / 078738), spirobisacridines (for example according to WO 2015 / 158411), xanthene diarylamines (for example according to WO 2014 / 072017), and 9,10-dihydroanthracene spiro compounds with diarylamino groups according to WO 2015 / 086108.

[0284] Very particular preference is given to the use of spirobifluorenes substituted by diarylamino groups in the 4-position as hole-transporting compounds, in particular the use of those compounds claimed and disclosed in WO 2013 / 120577, and the use of spirobifluorenes substituted by diarylamino groups in the 2-position as hole-transporting compounds, in particular the use of those compounds claimed and disclosed in WO 2012 / 034627.

[0285] The OLED according to the invention preferably comprises two or more different electron-transporting layers. The compound of formula (1) can be used in none, in one or more, or in all electron-transporting layers. In a preferred embodiment, the compound of formula (1) is used in exactly one or exactly two electron-transporting layers, and other compounds are used in the other electron-transporting layers present. Further compounds that can be used in addition to the compounds of formula (1) are all materials that are used according to the prior art as electron-transport materials in the electron-transport layer. Particularly suitable are aluminum complexes, e.g. Alq5, zirconium complexes, e.g. Zrq4, lithium complexes, e.g.Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives, and phosphine oxide derivatives. Other suitable materials are derivatives of the aforementioned compounds, as disclosed in JP 2000 / 053957, WO 2003 / 060956, WO 2004 / 028217, WO 2004 / 080975, and WO 2010 / 072300.

[0286] The device is structured, contacted and finally sealed accordingly (depending on the application) to exclude harmful influences from water and air.

[0287] In the further layers of the organic electroluminescent device according to the invention, all materials commonly used in the prior art can be used. Therefore, without inventive effort, the skilled person can use all materials known for organic electroluminescent devices in combination with the compounds according to the invention according to formula (1) or the preferred embodiments described above.

[0288] Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using a sublimation process. The materials are sublimated in vacuum sublimation systems at an initial pressure of less than 10' 5 mbar, preferably less than 10' 6 mbar. However, it is also possible that the initial pressure is even lower, for example less than 10' 7mbar. Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation. The materials are sublimated at a pressure between 10' 5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured.

[0289] Also preferred is an organic electroluminescent device characterized in that one or more layers are produced from solution, such as by spin coating, or by any printing process, such as screen printing, flexographic printing, offset printing, LITI (Light Induced Thermal Imaging, thermal transfer printing), inkjet printing, or nozzle printing. Soluble compounds are required for this, which are obtained, for example, by suitable substitution.

[0290] Furthermore, hybrid processes are possible, in which, for example, one or more layers are applied from solution and one or more further layers are vapor-deposited.

[0291] These processes are generally known to the person skilled in the art and can be applied by him without inventive step to organic electroluminescent devices containing the compounds according to the invention.

[0292] According to the invention, the electronic devices containing one or more compounds of formula (1) can be used in displays, as light sources in lighting applications and as light sources in medical and / or cosmetic applications (e.g. light therapy).

[0293] The compounds according to the invention and the organic electroluminescent devices according to the invention are characterized by one or more of the following properties: 1. The compounds according to the invention lead to long lifetimes.

[0294] 2. The compounds according to the invention lead to high efficiencies, in particular to a high EQE.

[0295] 3. The compounds according to the invention result in low operating voltages.

[0296] 4. Electronic devices, in particular organic electroluminescent devices containing compounds according to the invention, in particular as matrix material, have a very high color purity.

[0297] The properties mentioned under points 2 and 4 are particularly preferred.

[0298] The invention is further illustrated by the following examples, without intending to limit it. From these descriptions, one skilled in the art can practice the invention within the entire disclosed scope and, without inventive step, prepare further compounds according to the invention and use them in electronic devices or apply the method according to the invention.

[0299] Patent examples:

[0300] Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased from Sigma-Aldrich or ABCR, for example. The respective information in square brackets or the numbers given for individual compounds refer to the CAS numbers of the known compounds.

[0301] 1) Synthesis of compounds according to formula (1) Synthesis of intermediate 2 a) Intermediate 1

[0302] CAS: 2622-60-8 (9.7 g, 50 mmol) is placed in a flask purged with dry nitrogen, and dry tetrahydrofuran (500 mL) is added. The contents of the flask are stirred and cooled to -50 °C. N-Butyllithium (2.5 M in hexane, 21.0 mL, 53 mmol) is placed in a dropping funnel and then added dropwise over 15 minutes to the stirred mixture at -50 °C. The resulting solution is stirred at -50 °C for 1 hour. CAS: 138479-49-9 (11.0 g, 50 mmol) is added to the mixture as a solid in one portion, the suspension is stirred, and warmed to room temperature for 1 hour. The mixture is stirred at room temperature for 24 hours and then poured into a mixture of ice and water (500 mL). The resulting suspension is evaporated at 40 °C / 150 mbar to remove the organic solvents from the mixture.The contents of the flask are transferred to a beaker equipped with a magnetic stirrer, the suspension is stirred, and adjusted to pH 7.0 with 2M hydrochloric acid solution. The suspension is stirred at pH 7.0 for 1 hour. The solid is separated by vacuum filtration and washed with water (3 x 50 mL) to obtain 18.3 g of solid. The solid is stirred in acetone (200 mL) under reflux for 20 minutes and then cooled. The solid is separated by vacuum filtration and slurried in chloroform (200 mL) at 60 °C for 1 hour. Then, heptane (200 mL) is added and the mixture is evaporated at 40 °C / 325 mbar to remove 150 mL of the chloroform-enriched distillate. The solid is collected by vacuum filtration and dried overnight in a vacuum oven at 40 °C to obtain Intermediate 1 as an off-white powder (12.9 g, 62%). b) Intermediate 2.

[0303] Trifluoromethanesulfonic acid (207 mL) is placed in a flask, and Intermediate 1 (20.7 g, 50 mmL) is added in portions over 30 minutes. The mixture is stirred under dry nitrogen for 1 hour to obtain a solution. The contents are then heated at 115 °C for 14 hours. The mixture is then cooled to room temperature and then further cooled in an ice / water bath. The mixture is slowly added in a steady stream to stirred ice (2 kg). The pH of the resulting suspension is adjusted to 7.5 with 2N sodium hydroxide solution. The suspension is stirred for 2 hours, the precipitate is separated by vacuum filtration, and the solid is washed with water (3 x 100 mL). The solid is dried in a vacuum oven at 35 °C for 48 hours to obtain a crude solid (20.9 g).The solid is suspended in dichloromethane (100 mL), treated with alumina (activated, neutral, Brockmann activity I, 0.05-0.15 mm, 50 g), and the slurry is evaporated in vacuo. It is purified by alumina column chromatography and then recrystallized from toluene. The precipitate is collected by vacuum filtration and dried overnight in a vacuum oven at 40 °C to afford the target compound as white crystals (5.2 g, 26%).

[0304] Synthesis of Intermediate 4 a) Intermediate 3

[0305] CAS: 1198007-13-4 (9.6 g, 35 mmol) is placed in a flask purged with dry nitrogen. Dry tetrahydrofuran (175 mL) is added via cannula. The contents of the flask are stirred to obtain a clear solution, which is then cooled to -70 °C in a liquid nitrogen-acetone bath. 2M lithium diisopropylamide solution (in THF / heptane / ethylbenzene) (21.0 mL, 42 mmol) is transferred to the dropping funnel and then added dropwise to the stirred mixture at -70 °C. The resulting solution is stirred at 70 °C for 4 hours. CAS: 138479-49-9 (7.7 g, 35 mmol) is added in one portion, the suspension is stirred at -70 °C for 1 hour, and then warmed to room temperature. The mixture is stirred overnight at room temperature and then poured into a mixture of ice and water (500 ml). The resulting suspension is evaporated at 40 °C / 150 mbar to remove the organic solvents from the mixture.The contents of the flask were transferred to a beaker, the suspension was stirred, and adjusted to pH 7.0 with 2M hydrochloric acid solution. The suspension was stirred at pH 7.0 for 1 hour. The solid was collected by vacuum filtration and washed with water (3 x 50 mL). 22.2 g of crude solid was obtained. The solid was stirred under reflux in acetone (200 mL) for 20 minutes and then cooled to room temperature. The precipitate was collected, dried, and subsequently recrystallized from a dichloromethane / heptane mixture. The precipitate was again collected and dried overnight in a vacuum oven at 40 °C to obtain intermediate 3 as an off-white powder (9.6 g, 56%). b) Intermediate 4.

[0306] Trifluoromethanesulfonic acid (85 mL) was placed in a flask, and intermediate 3 (8.4 g, 17 mmol) was added in portions over 10 minutes. The mixture was stirred for 15 minutes under dry nitrogen. The contents were then heated to 50 °C for 92 hours. The mixture was allowed to cool to room temperature and then further cooled in an ice-water bath. The mixture was added slowly and in a steady stream to stirred ice (750 g). The pH of the resulting suspension was adjusted to 7.5 with 2N sodium hydroxide solution. The suspension was stirred for 2 hours, the precipitate was removed by vacuum filtration, and washed with water (3 x 100 mL). The solid was dried in a vacuum oven at 35 °C for 24 hours to obtain 8.1 g of a crude solid. The solid was purified by alumina column chromatography using ethyl acetate / heptane as eluent.The precipitate from the main fraction was then recrystallized from dichloromethane / heptane. The target compound was obtained as a white crystalline solid (68 mg, 1%).

[0307] Alternative synthesis route to Intermediate 4 a) Intermediate 5

[0308] CAS: 2622-60-8 (3.00 g, 15.4 mmol) is placed in a flask purged with dry argon. Dry tetrahydrofuran (75 mL) is added via cannula. The contents of the flask are stirred to obtain a clear solution, which is then cooled to -70 °C in a liquid nitrogen / acetone bath. 2M lithium diisopropylamide solution (in THF / heptane / ethylbenzene) (9.2 mL, 18.4 mmol) is transferred to the dropping funnel and then added dropwise to the stirred mixture at -70 °C. The resulting solution is stirred at 70 °C for 4 hours. CAS: 2360432-42-2 (4.6 g, 15.4 mmol) is added in one portion, the suspension is stirred at -70 °C for 1 hour, and then warmed to room temperature. The mixture is stirred overnight at room temperature and then poured into a mixture of ice and water (500 ml). The mixture is adjusted to pH 7.0 with 3M hydrochloric acid solution and stirred for 1 hour.The resulting suspension was evaporated at 40 °C / 150 mbar to remove the organic solvents from the mixture. The solid was collected by vacuum filtration and washed with water (3 x 50 mL), ethanol, and heptane. The solid was dried overnight in a vacuum oven at 40 °C to afford intermediate 5 as an off-white powder (5.7 g, 11.4 mmol, 74%). b) Intermediate 4.

[0309] Trifluoromethanesulfonic acid (50 mL) was placed in a flask under argon and purged for 10 minutes with an argon stream. Intermediate 5 (5.00 g, 9.97 mmol) was added in portions. The contents were then heated to 115 °C for 60 hours. The mixture was allowed to cool to room temperature and then slowly added to an ice / water mixture. The pH of the resulting suspension was adjusted to 7.5 with 2N sodium hydroxide solution. The precipitate was removed by vacuum filtration and washed with water (3 x 50 mL). The crude product was purified by silica gel column chromatography using dichloromethane as the solvent. The product of the main fraction was triturated with ethyl acetate. The target compound was obtained as a light yellow solid (1.50 g, 3.09 mmol, 31%).

[0310] Synthesis of compound 2

[0311] Connection 2

[0312] CAS: 18628-07-4 (140 mg; 0.42 mmol) is dissolved in dry o-xylene (2.00 ml) and dry tetrahydrofuran (2.00 ml) in a heated, argon-purged, closed vessel and cooled with an ice bath. Methylmagnesium chloride is added dropwise as a 3 molar solution in THF (0.15 ml; 0.46 mmol), and the mixture is stirred for 2 hours. The solution is then drawn into a syringe and added dropwise under ice cooling to a previously argon-saturated suspension of intermediate 4 (200 mg; 0.42 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (Mo-Phos, CAS: 742103-27-1) (11.9 mg; 0.03 mmol), and allylpalladium(II) chloride dimer (3.1 mg; 0.01 mmol) in o-xylene (4.00 ml). The mixture is stirred under ice cooling for 30 min, then the cooling is removed and heated to 120°C. The mixture is stirred at this temperature overnight. The next day, Mo-Phos (11.9 mg; 0.03 mmol) and allylpalladium(I l)chloride dimer (3.1 mg; 0.01 mmol) are added again and the temperature is increased to 160°C.The mixture is stirred at this temperature for 3 days. After cooling to room temperature, the mixture is separated by column chromatography using silica gel as the column material and heptane / THF as the eluent, and the product is purified. Product fractions are collected and purified again by column chromatography. Compound 2 (10 mg, 0.01 mmol, 3%) is obtained as a white solid.

[0313] Synthesis of further compounds

[0314] Intermediate 4 can also be used for the synthesis of, for example, compound 1 and compound 3 by well-known borylation, Pd-

[0315] Cross-coupling reactions (ie Suzuki and Buchwald-Hartwig) and

[0316] Ullmann reactions are used:

[0317] Connection 3

[0318] 2) General method for calculating the parameters: The energy levels of molecular orbitals (highest occupied molecular orbital HOMO, lowest unoccupied molecular orbital LUMO) as well as the energies of the excited states (lowest excited triplet state Ti, lowest excited singlet state Si) are determined using quantum mechanical calculations. The Gaussian16 program package (Rev. B.01) is used in all quantum chemical calculations. The neutral singlet ground state is optimized at the B3LYP / 6-31 G(d) level. HOMO and LUMO values ​​are determined at the B3LYP / 6-31 G(d) level for the ground state energy optimized with B3LYP / 6-31 G(d). TD-DFT singlet and triplet excitations (vertical excitations) are then calculated using the same method (B3LYP / 6-31 G(d)) and the optimized ground-state geometry. The default settings for SCF and gradient convergence are used.For structures containing heavy metal atoms, the calculation is performed analogously to the one described above, with the difference that the basis set "LanL2DZ" is used for the metal atom and "6-31 G(d)" as the basis set for the ligands. The HOMO and LUMO values ​​in eV derived from the quantum chemical calculation are additionally scaled by the following factors: HOMO_corr = 0.90603 * HOMO (in eV) - 0.84836 LUMO_corr = 0.99687 * LUMO (in eV) - 0.72445.

[0319] These values, HOMO_corr and LUMO_corr, are to be regarded as HOMO and LUMO energy levels of the materials, respectively, for the purposes of this application.

[0320] The lowest triplet state Ti is defined as the energy of the triplet state with the lowest energy, resulting from the described quantum chemical calculation. The lowest excited singlet state Si is defined as the energy of the excited singlet state with the lowest energy, resulting from the described quantum chemical calculation.

[0321] 3) Use and properties of compounds according to formula (1) Compound 1, compound 2 and compound 3 can be used as host and / or blocking materials with high T1 value in blue phosphorescent and hyperphosphorescent OLEDs.

[0322] For example, compound 1 achieves good performance data when used as an electron-transporting host material in combination with a hole-transporting host material and a blue-emitting compound.

[0323] The spiro-BimBim core structure of compounds 1, 2, and 3 has a higher T1 energy than the spiro-bifluorene core structure well-known in OLED materials. It also has a higher T1 energy than the previously published spiro-Bim-fluorene core structure (see below). By combining this core structure with substituents with short conjugation lengths or an extension of the conjugated system, such as CAS 28890-99-5 (see above in compound 3), host materials with particularly high T1 energies, such as compound 3, can be obtained. High T1 energies help avoid processes that reduce efficiency in blue-phosphorescent and hyperphosphorescent OLEDs (energy confinement).

[0324] 3) Synthesis of further compounds according to the application

[0325] In analogy to the syntheses described above, the following compounds can be synthesized and used as materials in OLEDs.

Claims

Patent claims 1 . A compound containing one or more units according to formula (1 ), Formula (1) where the symbols are: W is C or Si; X a is the same or different at each occurrence N or CR a , where at most two of the groups X a per ring represents N; X b is the same or different at each occurrence N or CR b , where at most two of the groups X b per ring represents N; R a , R bis, identically or differently on each occurrence, H, D, F, CI, Br, I, OAr, SAr, N(R)2, N(Ar)2, B(OR)2, B(R)2, B(Ar)2, CHO, C(=O)R, CR=C(R)2, CN, C(=O)OR, C(=O)NR, C(R)3, Si(R)3, Si(Ar)3, Ge(R)3, NO2, P(=O)(R)2, P(Ar)2, P(R)2, OSO2R, OR, S(=O)R, S(=O)2R, SR, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group each with one or several radicals R other than H, where one or more non-adjacent CH2 groups can be replaced by -RC=CR-, -CEC-, Si(R)2, CONR, NR, C=O, C=S, -C(=O)O-, P(=O)(R), -O-, -S-, SO or SO2, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which can be substituted by one or more radicals R other than H, or a transition metal complex, in particular of platinum, where two radicals Ra , R b also form a ring with each other; Ar is, at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R other than H, wherein two radicals Ar which bond to the same Si atom, N atom, P atom or B atom may also be bridged to one another by a single bond or a bridge selected from B(R), C(R)2, Si(R)2, C=O, C=NR, C=C(R)2, O, S, S=O, SO2, N(R), P(R) and P(=O)R; R is the same or different at each occurrence: H, D, F, CI, Br, I, OAr', SAr', N(R 1 )2, N(Ar')2, B(OR 1 )2, B(R 1 )2, B(Ar')2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , C(R 1 ) 3I Si(R 1 )3, Si(Ar')3, Ge(R 1 )3, NO2, P(=O)(R 1 )2, P(Ar')2, P(R 1 )2, OSO2R 1 , OR1 , S(=O)R 1 , S(=O)2R 1 , SR 1 , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted by other than H, where one or more non-adjacent CH2 groups are substituted by -R 1 C=CR 1 -, -C=C-, Si(R 1 )2, CONR 1 , NR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), -O-, -S-, SO or SO2, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted by other than H, or a transition metal complex, in particular of platinum, where two radicals R may also be substituted others form a ring; Ar' is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is substituted by one or more radicals R 1 may be substituted by other than H, whereby two radicals Ar' which are bonded to the same Si atom, N atom, P atom or B atom may also be bonded by a single bond or a bridge selected from B(R 1 ), C(R 1 )2, Si(R 1 )2, C=O, C=NR 1 , C=C(R 1 )2, 0, S, S=O, SO2, N(R 1 ), P(R 1 ) and P(=O)R 1 , be bridged together; R 1 is the same or different at each occurrence H, D, F, CI, Br, I, N(R 2 )2, B(OR 2 ) 2I B(R 2 ) 2I CHO, C(=O)R 2 , CR 2 =C(R 2 )2, CN, C(=O)OR 2 , C(R 2 )3, Si(R 2 )3, Ge(R 2 )3, NO2, P(=O)(R 2 )2, P(R 2 )2, OSO2R 2 , SR 2, S(=O)R 2 , S(=O)2R 2 , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 2 may be substituted by other than H and wherein one or more CH2 groups in the above-mentioned groups are replaced by -R 2 C=CR 2 -, -C^C-, Si(R 2 )2, NR 2 , C=O, C=S, -C(=O)O-, CONR 2 , P(=O)(R 2 ), -S-, SO or SO2 and where one or more H atoms in the above-mentioned groups can be replaced by D, F, CI, Br, I, CN or NO2, an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 2may be substituted by other than H, or a transition metal complex, in particular of platinum, where two or more radicals R 1 can form a ring with each other; R 2 is, identically or differently at each occurrence, H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms may be replaced by D or F; two or more substituents R 2 form a ring with each other.

2. Compound according to claim 1, characterized in that the compound corresponds to the following formula (2): Formula (2) where the symbols R a , R b and W, have the meanings previously set out in claim 1 and at least one of the radicals R a and / or R brepresents a group selected from N(Ar)2 or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R other than H, and preferably at least one of the radicals R a and / or R b represents a group selected from a heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R other than H.

3. A compound according to claim 1 or 2, characterized in that at least one of the groups R a and / or R b represents a group selected from structures of the formula -(L) q -(Z) S , where L is, identically or differently at each occurrence, a bivalent, trivalent or tetravalent aromatic or heteroaromatic ring system having 6 to 40 aromatic ring atoms, each of which is substituted by one or more radicals R cmay be substituted by other than H; q is 0 or 1, where q = 0 means that the group L is not present and that the corresponding aromatic or heteroaromatic group is directly bonded to the associated atom, for example a carbon atom, where the group Z is selected from structures of the formulas (Z-1) to (Z-19), Formula (Z-10) Formula (Z-1 1) Formula (Z-12) Formula (Z-19) where W has the meaning set out in claim 1, the dashed bond represents the bond to the group L or, in the case of q=0, to the spiro skeleton according to formula (1), s is 1, 2 or 3, where in the case of q=0 the index s is 1, and the following applies to the other symbols: X c is the same or different at each occurrence N, CR C or, in the event that at this point this group binds to another group, C, where at most two of the group X c per ring represents N; Xd is the same or different at each occurrence N or CR d , where at least one group X d stands for N; Y is chosen from C(R C )2, Si(R c )2, C=O, P(O)R C , PR C , NR C or BR C , 0 or S; Y 1 stands for 0, S, NR d or C(R d )2; R c , R d is the same or different at each occurrence H, D, F, CI, Br, I, OAr', SAr', N(R 1 )2, N(Ar')2, B(OR 1 )2, B(R 1 )2, B(Ar')2, CHO, C(=O)R 1 , CR 1 =C(R 1 )2, CN, C(=O)OR 1 , C(=O)NR 1 , C(R 1 ) 3I Si(R 1 )3, Si(Ar')3, Ge(R 1 )3, NO2, P(=O)(R 1 ) 2I P(Ar')2, P(R 1 )2, OSO2R 1 , OR 1 , S(=O)R 1 , S(=O)2R 1 , SR 1, a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group is each substituted by one or more radicals R 1 may be substituted by other than H, where one or more non-adjacent CH2 groups are substituted by -R 1 C=CR 1 -, -C=C-, Si(R 1 )2, CONR 1 , NR 1 , C=O, C=S, -C(=O)O-, P(=O)(R 1 ), -O-, -S-, SO or SO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which is substituted by one or more radicals R 1 may be substituted by other than H, two residues may be selected from residues R c and R d also form a ring with each other, where R 1 has the meaning given in claim 1.

4. A compound according to claim 3, characterized in that the group Z in formula (L) q -(Z) s is selected from structures of formulas (Z-20) to (Z-44), Formula (Z-34) Formula (Z-35) Formula (Z-36) Formula (Z-37) where the dashed bond represents the bond to the group L or, in case q= 0, to the spiro skeleton according to formula (1 ) and the symbols Y 1 , R c and R d have the meanings given in claim 3.

5. A compound according to claim 3 or 4, characterized in that the compound corresponds to at least one of the following formulas (3-1) to (3-8): Formula (3-1) Formula (3-2) where the symbols R a and R bhave the meanings previously set out in claim 1, the symbols q, s, L and Z have the meanings previously set out in claim 3 or 4.

6. A compound according to one or more of claims 3 to 5, characterized in that the compound corresponds to at least one of the following formulas (4-1) to (4-16): where the symbols R a and R b have the meanings previously set out in claim 1, the symbols q, s, L and Z have the meanings previously set out in claim 3 or 4.

7. A compound according to one or more of claims 3 to 6, characterized in that the group -(L) q - in formula-(L) q -(Z) s a structure of the formula -(L c )0- such that at least one of the groups R a and / or R b represents a group chosen from Structures of the formula -(L C) O -(Z) S , where the index o is 0, 1 , 2, 3, 4 or 5, where o = 0 means that the group L c is not present and that the corresponding aromatic or heteroaromatic group is directly bonded to the corresponding atom, for example a carbon atom, and the residue L c is chosen from structures of the formulas (L c -1 ) to (L c -14 Formula (L c -11) Formula (L c -12) Formula (L c -13) Formula (L c -14) where the dashed bonds represent the attachment points and the other symbols are: X c is the same or different at each occurrence N, CR C or, in the case that at this point this group binds to another group, C; Y c is chosen from C(R C )2, NR C , 0 or S, where R chas the meaning given in claim 3, wherein the structure of the formula -(L c )0- for the index s =1 in formula -( L c )o-(Z)s is bivalent, for s=2 trivalent and for s=3 tetravalent.

8. Connection according to claim 7, characterized in that the Group L c is chosen from structures of the formulas (L c -14) to (L c -29) Formula (L c -26) Formula (L c -27) Formula (L c -28) Formula (L c -29) where the dashed bonds represent the attachment points, the symbols R c and X c has the meaning given in claim 3 and the following applies to the other symbols: i is 1 or 2; and j is 0, 1 or 2.

9. A compound according to one or more of claims 7 or 8, characterized in that the group L c is selected from Structures of the formulas (L c -30) to (Lc -41 ) Formula (L c -33) Formula (L c -34) where the dashed bonds represent the attachment points and R c has the meaning given in claim 3.

10. A compound according to one or more of claims 1 to 9, characterized in that R, R c and R d is selected at each occurrence, identically or differently, from the group consisting of H, D, F, CN, OR 1 , a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherein the alkyl group is in each case substituted with one or more radicals R 1 may be substituted by other than H and wherein one or more non-adjacent CH2 groups may be replaced by 0, and an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R 1can be substituted by something other than H.

11. A compound according to one or more of claims 2 to 10, characterized in that the compound of formula (2) according to Claim 2, wherein exactly one radical selected from the radicals R a and R b represents a group selected from structures of the formula - -(L)q-(Z) S , where q is 0 or 1, L is either absent or equal to carbazole, which reacts with residues R c is substituted, in particular formula (L c -25), s is 1, and Z is formula (Z-22); and wherein the further radicals are selected from the radicals R a and R b are H or D, preferably H.

12. A compound according to one or more of claims 3 to 11, characterized in that it corresponds to formula (1).

13. A process for preparing a compound according to one or more of claims 1 to 12, characterized in that in a first step a heteroaromatic ketone compound is reacted with an N-phenylbenzimidazole derivative to form a tertiary alcohol and in a second step a ring formation takes place with elimination of water, whereby a compound of formula (1) is obtained.

14. Use of a compound according to one or more of claims 1 to 12 in an electronic device.

15. Electronic device comprising at least one compound according to one or more of claims 1 to 12.

16. Electronic device according to claim 15, which is an organic electroluminescent device, characterized in that the device comprises an anode, a cathode and at least one emitting layer, wherein at least one organic layer, which may be an emitting layer, hole transport layer, electron transport layer, hole blocking layer, electron blocking layer or another functional layer, comprises at least one compound according to one or more of claims 1 to 12.

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