WO2024240725A1 - Tris[1,2,4]triazolo[1,5-a:1',5'-c:1'',5''-e][1,3,5]triazine derivatives for use in organic electroluminescent devices - Google Patents

Abstract

The present invention relates to compounds that are suitable for use in electronic devices, and to electronic devices, more particularly organic electroluminescent devices, containing these compounds.

Description

TRIS[1,2,4]TRIAZOLO[1,5-A:r,5 ^, -C:1",5"-E][1,3,5]TRIAZINE DERIVATIVES FOR USE IN ORGANIC ELECTROLUMINESCENT DEVICES

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.

Electronic devices containing organic, organometallic and/or polymer semiconductors are becoming increasingly important, and are used in many commercial products for reasons of cost and performance. Examples include organic-based charge transport materials (e.g. triarylamine-based hole transporters) in copiers, organic light-emitting diodes (OLEDs) in indicators and display devices, or organic photoreceptors in copiers. Organic solar cells (O-SC), organic field-effect transistors (O-FET), organic thin-film transistors (O-TFT), organic switching elements (O-IC), organic optical amplifiers and organic laser diodes (O-lasers) are at an advanced stage of development and may become very important in the future.

Electronic devices in the sense of this invention are understood to be organic electronic devices which contain organic semiconductor materials as functional materials. In particular, the electronic devices are electroluminescent devices such as OLEDs.

The structure of OLEDs in which organic compounds are used as functional materials is known to those skilled in the art. In general, OLEDs are understood to be electronic devices that have one or more layers that comprise organic compounds and emit light when a voltage is applied.

In electronic devices, especially OLEDs, there is a great need to improve the performance data, especially lifetime, efficiency and operating voltage. No satisfactory solution has yet been found for these aspects.

Electronic devices usually comprise a cathode, an anode and at least one functional, preferably emitting layer. In addition to these layers, they can 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.

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 material of electron transport layers and/or as host materials, and which lead to good properties there.

Surprisingly, it has been found that certain tristriazolotriazines, described in more detail below, solve this problem and are well suited for use in electronic devices, in particular OLEDs. The OLEDs in particular have a long service life, high efficiency and low operating voltage. These compounds and electronic devices, in particular organic electroluminescent devices, which contain these compounds are therefore the subject of the present invention.

Formel (1) wobei für die verwendeten Symbole gilt: R ist bei jedem Auftreten gleich oder verschieden H, D, F, Cl, Br, I, OAr‘, SAr‘, B(OR¹)2, CHO, C(=O)R¹, CR¹=C(R¹)2, CN, C(=O)OR¹, C(=O)NR¹, Si(R¹)3, Ge(R¹)3, NO2, P(=O)(R¹)2, OSO2R¹, OR¹, S(=O)R¹, S(=O)2R¹, SR¹, eine geradkettige Alkylgruppe mit 1 bis 20 C-Atomen oder eine Alkenyl- oder Alkinylgruppe mit 2 bis 20 C- Atomen oder eine verzweigte oder zyklische Alkylgruppe mit 3 bis 20 C-Atomen, wobei die Alkyl-, Alkenyl- oder Alkinylgruppe jeweils mit einem oder mehreren Resten R¹ substituiert sein kann, wobei eine oder mehrere nicht benachbarte CH2-Gruppen durch -R¹C=CR¹- , -C≡C-, Si(R¹)2, CONR¹, C=O, C=S, -C(=O)O-, P(=O)(R¹), -O-, -S-, SO oder SO2 ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 60 aromatischen Ring- atomen, bevorzugt mit 5 bis 40 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R¹ substituiert sein kann; wobei falls R und zugehörige Reste mindestens ein aromatisches Ringsystem, umfassend mindestens ein Stickstoffatom mit drei Einfachbindungen umfassen, für jedes dieser aromatischen Ring- systeme gilt, dass jedes Stickstoffatom mit drei Einfachbindungen Teil mindestens eines Fünfrings ist und/oder Teil eines Sechsrings, umfassend mindestens ein weiteres Heteroatom oder eine C=O- Gruppe, ist; mit der Maßgabe, dass mindestens ein R ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 60 aromatischen Ring- atomen ist und mit der Maßgabe, dass nicht alle drei R gleichzeitig für eine Phenylgruppe stehen; The present invention relates to a compound according to formula (1),

Formula (1) where the following applies to the symbols used: R is, identically or differently on each occurrence, H, D, F, Cl, Br, I, OAr', SAr', B(OR ¹ )2, CHO, C(=O)R ¹ , CR ¹ =C(R ¹ )2, CN, C(=O)OR ¹ , C(=O)NR ¹ , Si(R ¹ )3, Ge(R ¹ )3, NO2, P(=O)(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, where the Alkyl, alkenyl or alkynyl group can each be substituted by one or more radicals R ¹ , where one or more non-adjacent CH2 groups can be replaced by -R ¹ C=CR ¹ - , -C≡C-, Si(R ¹ )2, CONR 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, which can each be substituted by one or more radicals R ¹ ; where if R and associated radicals comprise at least one aromatic ring system comprising at least one nitrogen atom with three single bonds, for each of these aromatic ring systems, each nitrogen atom with three single bonds is part of at least one five-membered ring and/or part of a six-membered ring comprising at least one further heteroatom or a C=O group; with the proviso that at least one R is an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms and with the proviso that not all three R simultaneously represent a phenyl group;

Ar' is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms which may be substituted by one or more radicals R ¹ , where two or more R ^1s may together form an aromatic or heteroaromatic ring system;

R ¹ is, identically or differently on each occurrence, H, D, F, I, B(OR ² )2, CHO, C(=O)R ² , CR ² =C(R ² ) ₂ , CN, C(=O)OR ² , Si(R ² ) ₃ , Ge(R ² ) ₃ , NO ₂ , P(=O)(R ² ) ₂ , OSO2R ² , SR ² , S(=O)R ² , S(=O) ₂ R ² , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted with one or more radicals R ² can be substituted and where one or more CH2 groups in the abovementioned groups can be replaced by -R ² C=CR ² -, -C=C-, Si(R ² )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 abovementioned groups can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ² , where two or more radicals R ¹ can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system with one another;

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 R ² substituents may be linked to one another to form a ring.

An aryl group in the sense of this invention contains 6 to 40 C atoms; a heteroaryl group in the sense 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 at least 5. The heteroatoms are preferably selected from N, 0 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 aromatic ring systems.

An aromatic ring system in the sense of this invention contains 6 to 60 C atoms, preferably 6 to 40 C atoms in the ring system. A heteroaromatic ring system in the sense of this invention contains 1 to 60 C atoms, preferably 1 to 40 C atoms and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the sense of this invention is to be understood as a system which does not necessarily only contain aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be connected by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as a C, N or O atom or carbonyl group. This also 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 in the sense 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 and 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.

An electron-rich heteroaromatic ring system is characterized by the fact that it is a heteroaromatic ring system that does not contain any electron-poor heteroaryl groups. An electron-poor heteroaryl group is a six-membered ring heteroaryl group with at least one nitrogen atom or a five-membered ring heteroaryl group with at least two heteroatoms, one of which is a nitrogen atom and the other is oxygen, sulfur or a substituted nitrogen atom, where further aryl or heteroaryl groups can be condensed onto each of these groups. 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 condensed. Examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene or indenocarbazole. An electron-rich heteroaryl group is also called an electron-rich heteroaromatic residue.

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

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 for 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.

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. In the context of the present invention, an aliphatic hydrocarbon radical or an alkyl group or an alkenyl or alkynyl group which can contain 1 to 40 C atoms and in which individual H atoms or CH2 groups can also be substituted by the abovementioned groups, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, 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-methylcyclohexyl, 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 and 1-(n-Decyl)-cyclohex-1-yl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, cyclooctadienyl, ethynyl, propynyl, butynyl, pentinyl, Hexynyl, heptynyl or octynyl understood. Among an alkoxy group OR ¹ with 1 to 40 carbon atoms, preference is given to methoxy, trifluoromethoxy, 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, pentafluoroethoxy and 2,2,2-trifluoroethoxy. A thioalkyl group SR ¹ with 1 to 40 carbon atoms includes, in particular, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, Cyclohexylthio, n-heptylthio, cycloheptyl-thio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, Cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, Ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. In general, alkyl, alkoxy or thioalkyl groups according to the present invention can be straight-chain, branched or cyclic, where one or more non-adjacent CH2 groups can be replaced by the abovementioned groups; furthermore, one or more H atoms can also be replaced by D, F, CI, Br, I, CN or NO2, preferably D, F, CI or CN, particularly preferably D, F or CN.

Weiterhin soll unter der oben genannten Formulierung aber auch ver- standen werden, dass für den Fall, dass einer der beiden Reste Wasser- stoff darstellt, der zweite Rest unter Bildung eines Rings an die Position, an die das Wasserstoffatom gebunden war, bindet. Dies soll durch das folgende Schema verdeutlicht werden:

Dabei bedeutet Teil eines Fünfrings für ein Stickstoffatom, dass dieses Stickstoffatom mit vier weiteren Atomen einen Fünfring bildet, wie bei- spielsweise im Carbazol. Im Falle eines Sechsrings ist das Stickstoffatom Teil eines Sechsrings, wie beispielsweise bei Dibenzo[1,4]oxazin. In einer bevorzugten Ausführungsform ist in allen R und den zugehörigen Gruppen, wenn diese ein Stickstoffatom mit drei Einfachbindungen enthält, jedes Stickstoffatom mit drei Einfachbindungen mindestens Teil eines Fünfrings. An aromatic or heteroaromatic ring system with 5 - 60 aromatic ring atoms, preferably 5 - 40 aromatic ring atoms, which can be substituted by the above-mentioned radicals or a hydrocarbon radical and which can be linked to the aromatic or heteroaromatic via any position, is understood to mean in particular groups which are 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, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, Phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, Anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1 ,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1 ,2,3-oxadiazole, 1, 2,4-oxadiazole, 1 ,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole diazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole or groups derived from combinations of these systems. These groups can also be deuterated. The phrase that two or more residues can form a ring system with one another is to be understood in the context of the present description to mean, among other things, that the two residues are linked to one another 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 bound, forming a ring. This is illustrated by the following scheme:

In this context, part of a five-membered ring for a nitrogen atom means that this nitrogen atom forms a five-membered ring with four other atoms, as in carbazole, for example. In the case of a six-membered ring, the nitrogen atom is part of a six-membered ring, as in dibenzo[1,4]oxazine, for example. In a preferred embodiment, all R and the associated groups, if they contain a nitrogen atom with three single bonds, contains, each nitrogen atom with three single bonds is at least part of a five-membered ring.

In a preferred embodiment of the invention, the groups R do not contain any substituted or unsubstituted amino groups. The group R therefore preferably does not contain any triarylamino groups, but can contain, for example, carbazole groups, i.e. heteroaryl groups that contain nitrogen.

In a preferred embodiment, at least one R comprises an aromatic or heteroaromatic ring system having 9 to 60 aromatic ring atoms, preferably 10 to 40 aromatic ring atoms, very particularly preferably 12 to 30 aromatic ring atoms.

In a preferred embodiment, R and the associated groups do not comprise fused aryl groups.

In a preferred embodiment of the invention, at least two substituents R are identical. Preferred embodiments of the invention are thus compounds in which two substituents R are identical and the third substituent R is different from the other substituents R, and compounds in which all three substituents R are identical.

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

In a preferred embodiment of the invention, R is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, OR ¹ , a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl or alkenyl group may each be substituted by one or more radicals R ¹ , but is preferably unsubstituted, and where one or several non-adjacent CH2 groups can be replaced by 0, or an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ¹ . Particularly preferably, R is selected on 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 can be substituted in each case by one or more radicals R ¹ , but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which can be substituted in each case by one or more radicals R ¹ , preferably non-aromatic radicals R ¹ . Most preferably, R is selected, identically or differently on each occurrence, from the group consisting of H, D, CN or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , preferably non-aromatic radicals R ¹ . Most preferably, all radicals R are selected, identically or differently on each occurrence, from an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 18 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , preferably non-aromatic radicals R ¹ .

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

The groups R, when they represent an aromatic or heteroaromatic ring system, are preferably selected from the groups of the following formulas R-1 to R-184,

wobei R¹ die oben genannten Bedeutungen aufweist, die gestrichelte Bindung die Bindung zum Triazolotriazin in Formel (1 ) darstellt und weiterhin gilt:

where R ¹ has the meanings given above, the dashed bond represents the bond to the triazolotriazine in formula (1 ) and furthermore:

Ar ³ is at each occurrence, identically or differently, a bivalent aromatic or heteroaromatic ring system with 6 to 18 aromatic tic ring atoms, each of which may be substituted by one or more radicals R ¹ ;

A ¹ is, identically or differently at each occurrence, BR ¹ , C(R ¹ )2, C=O, NR ¹ , 0 or S, where A ¹ in the formulas R-150, R-151 and R-152 stands for BR ¹ , C=O, NR ¹ , 0 or S;

A ² is, identically or differently on 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 bonded directly to the associated atom, for example a carbon atom or to a heteroatom such as a 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 equal to 1; r is 0 or 1 , where r = 0 means that no group A ¹ is bonded at this position and residues R ¹ are bonded to the corresponding carbon atoms instead.

In a preferred embodiment, Ar ³ comprises divalent aromatic or heteroaromatic ring systems based on the groups R-1 to R-184, where p is 0 and the dashed bond and an R ¹ represent the bond to the aromatic or heteroaromatic group after R-1 to R-184.

If the abovementioned groups R-1 to R-184 have several groups A ¹ for R, all combinations from the definition of A ¹ are possible. Preferred embodiments are then those in which one group A ¹ stands for C(R ¹ ) 2, NR ¹ , 0 or S and the other group A ¹ stands for C(R ¹ ) ₂ , NR ¹ , 0 or S.

If A ¹ is 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 represented by one or more radicals R ² can be substituted. In a particularly preferred embodiment, this substituent R ¹ is the same or different on each occurrence and represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, and which can each 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 can be substituted by one or more radicals R ¹ , but are preferably unsubstituted.

If A ¹ is C(R ¹ ) 2 , the substituents R ¹ which are bonded to this carbon atom are preferably identical or different on each occurrence and 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 may also be substituted by one or more radicals R ² . R ¹ is very particularly preferably a methyl group or a phenyl group. The radicals R ¹ can also form a ring system with one another, resulting in a spiro system.

In a further preferred embodiment of the invention, Ar' is the same 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 may in each case be substituted by one or more radicals R ¹ .

In a further preferred embodiment of the invention, R ¹ is the same or different on each occurrence and is selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl or alkenyl group may each be substituted by one or more radicals R ² , or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, each of which is substituted by one or more radicals R ² can be substituted; two or more radicals R ¹ can form an aliphatic ring system with one another. In a particularly preferred embodiment of the invention, R ¹ is the same or different on each occurrence and is 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 can be substituted by one or more radicals R ² , but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which can be substituted by one or more radicals R ² .

In a further preferred embodiment of the invention, R ² is the same or different on each occurrence and is 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 ,} insofar as they represent aromatic or heteroaromatic groups, are selected from the groups R-1 to R-184, which are then each substituted accordingly with R ² , or the groups mentioned under R ² .

In a preferred embodiment of the invention, all aromatic or heteroaromatic groups of the radicals R, R ¹ or R ² are selected from the corresponding groups R-1 to R-184.

In a preferred embodiment, the compounds 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 have been exchanged for D. The undeuterated compound is the corresponding compound in which the deuterium has been exchanged for hydrogen and which therefore contains no D. In a fully deuterated compound, all H are exchanged for D.

The alkyl groups in compounds according to the invention which are processed by vacuum evaporation preferably have no more than five C atoms, particularly preferably no more than 4 C atoms, very particularly preferably no more than 1 C atom. For compounds which are processed from solution, compounds which are substituted with alkyl groups, in particular branched alkyl groups, with up to 10 C atoms or which are substituted with oligoarylene groups, for example ortho-, meta-, para- or branched terphenyl or quaterphenyl groups, are also suitable.

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

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

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

The 2,6,10-triaryl/heteroaryl-tris[1,2,4]triazolo[1,5-a:1',5'-c:1",5"-e][1,3,5]triazines according to the invention can be prepared starting from 2,6,10-trichloro-tris[1,2,4]triazolo[1,5-a:1',5'-c:1",5"-e][1,3,5]triazine [879612-44-9] by Suzuki coupling with aryl/heteroaryl-boronic acids or their esters or by SN2Ar reaction with Grignard or organolithium compounds (Scheme 1). Typical catalyst systems for the Suzuki coupling are known combinations of palladium compounds and preferably electron-rich phosphines such as SPhos, XPhos, RuPhos, AdaPhos etc., as well as alkali-alkaline earth carbonates, phosphates, hydroxides as typical bases and DMSO, DMF, DMAc, NMP, THF, dioxane as solvents (Lömi) for single-phase reactions or mixtures of water with THF, dioxane, glyme, alcohols, toluene etc. Alternative coupling processes such as Negish, Yamamoto, Grignard cross coupling can also be used. are used. If mixtures of aryl/heteroarylboronic acids or their esters or Grignard or organolithium compounds are used, mixed products can be obtained with respect to the R radical, which can be separated chromatographically. Alternatively, the synthesis of mixed compounds can also be carried out by consecutive coupling steps, whereby the dichloroaryl/heteroaryl or the chlorodiaryl/heteroaryl intermediates can be isolated or further reacted in situ.

The 2,6, 10-tri-N-carbazolyl-tris[1,2,4]triazo lo[1,5- a:1',5'-c:1",5"-e][1,3,5]triazines according to the invention can be prepared starting from 2,6, 10-trichlorotris-[1,2,4]triazolo[1,5-a:1',5'-c:1",5"-e][1,3,5]triazine [879612-44-9] by Buchwald-Hartwig coupling or by SN2Ar reaction with carbazoles (Scheme 2). The reactions with indenocarbazoles, indolocarbazoles, etc. can be carried out analogously. Typical catalyst systems for the Buchwald-Hartwig coupling are known combinations of palladium compounds and preferably electron-rich phosphines, such as tri-tert-butyl-, tri-cyclohexyl-phosphine, BINAP, SPhos, XPhos, RuPhos, AdaPhos etc., typical bases are alcoholates, alkali-alkaline earth carbonates, phosphates and as Solvents THF, dioxane, toluene, DMSO, DMF, DMAc, NMP can be used. For the SN2-Ar reaction, BuLi, NaH, K2CO3, CS2CO3, K3PO4 in dipolar aprotic solvents such as DMSO, DMF, DMAc, NMP, etc. are used.

Scheme 2: Buchwald-Hartwig coupling or SN2-Ar reaction:

The coupling reactions according to Schemes 1 and 2 can also be carried out consecutively, whereby the mixed aryl/heteroaryl/N-carbazolyl-substituted compounds according to the invention are obtained. Furthermore, alcoholates or cyanide can also be used as nucleophiles in the above-mentioned SN2-Ar reaction and thus the corresponding ethers or nitriles can be obtained.

Alternatively, the compounds of the invention can be prepared by the processes described in the literature starting from the corresponding nitriles or carboxamides (e.g. R. Hojo et al., J. Mater. Chem. C, 2022, 10, 13871 or T. Rieth et al., Molecules 2020, 25, 5761).

A further object of the present invention is therefore a process for preparing the compounds according to the invention, characterized by the following steps: (A) synthesis of the basic skeleton according to formula (1 ) which contains, instead of the radicals R, a reactive leaving group, for example F, CI, Br, I, boronic acid or a boronic acid ester, tosylate or mesylate;

(B) Introduction of the groups R by coupling reactions.

Another object of the present invention is an oligomer, polymer or dendrimer comprising one or more compounds according to formula (1).

For processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes, formulations of the compounds according to the invention are required. These formulations can be, for example, solutions, dispersions or emulsions. It may be preferable 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, phenetol, 1,4-diisopropylbenzene, di-benzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, di- ethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetra-ethylene 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.

A further subject of the present invention is therefore 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 be, for example, a solvent, in particular one of the above-mentioned 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. 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.

The compounds according to 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.

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

Yet another object of the present invention is an electronic device comprising at least one compound according to the invention.

The compounds according to the invention can be present, in particular when used, as a racemate or as a pure enantiomer. The formation of enantiomers is possible, for example, if the radicals R are selected such that rotation around the bond of R to the tristriazolotriazine is hindered and atropisomers are thereby formed.

An electronic device in the sense of the present invention is a device which contains at least one layer containing at least one organic compound. The component can also contain inorganic nic materials or layers that are made entirely of inorganic materials.

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).

The device is particularly preferably an organic electroluminescent device comprising a cathode, anode and at least one emitting layer, wherein at least one organic layer, which can 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.

In addition to these layers, the organic electroluminescent device can 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 can also be introduced between two emitting layers, which, for example, have an exciton blocking function. It should be noted, however, that not all of these layers necessarily have to be present. The organic electroluminescent device can contain one emitting layer, or it can contain several emitting layers. If several emitting layers are present, these preferably have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, ie different emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. Systems with three emitting layers are particularly preferred, with the three layers showing 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.

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

The organic electroluminescent device can contain one emitting layer, or it can contain several emitting layers, with at least one layer containing at least one compound according to the invention. Furthermore, the compound according to the invention can also be used in an electron transport layer and/or in a hole blocking layer and/or in a hole transport layer and/or in an exciton blocking layer.

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 emit light, preferably in the visible range, when suitably excited and also contain at least one atom of 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 regarded as phosphorescent compounds, in particular if they contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, indium, palladium, platinum, silver, gold or europium, in particular compounds which contain indium, platinum or copper. In the context of the present invention, all luminescent indium, platinum or copper complexes are regarded as phosphorescent emitting compounds.

Examples of the emitters described above can be found in the applications WO 00/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373, US 2005/0258742, WO 2009/146770, WO 2010/015307, WO 2010/031485, WO 2010/054731, WO 2010/054728, WO 2010/086089, WO 2010/099852, WO 2010/102709, WO 2011/032626, WO 2011/066898, WO 2011/157339, WO 2012/007086, WO 2014/008982, WO 2014/023377, WO 2014/094961, WO 2014/094960, WO 2015/036074, WO 2015/104045, WO 2015/117718, WO 2016/015815, WO 2016/124304, WO 2017/032439, WO 2018/011186, WO 2018/041769, WO 2019/020538, WO 2018/178001, WO 2019/115423 and WO 2019/158453. In general, all phosphorescent complexes as used according to the prior art for phosphorescent OLEDs and as known to the person skilled 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 to use further phosphorescent complexes in combination with the compounds of the formula (1) in organic electroluminescent devices without inventive step. Since the compounds according to the invention can also have a high triplet energy depending on the substitution, it is also possible in particular to use them as matrix material for blue phosphorescent emitters. Further examples are listed in a table below. 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.

In a preferred embodiment of the invention, the compounds of the formula (1) are used as electron-transporting material. In this case, the compounds are preferably contained in an electron-transport layer or a hole-blocking layer or an electron-conducting or bipolar host material. Use in an electron-transport layer is particularly preferred.

An electron transport layer in the sense of the present application is a layer with an electron-transporting function between the cathode and the emitting layer.

In the context of the present application, electron injection layers and hole blocking layers are understood to mean certain 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 directly borders the cathode or is only separated from it 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 directly borders 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, contain a compound of the formula (1).

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. 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, where the emitting compounds can be fluorescent or phosphorescent, preferably phosphorescent.

The proportion of matrix material in the emitting layer in this case 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.

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.

An emitting layer of an organic electroluminescent device can also comprise systems that contain a large number of matrix materials (mixed matrix systems) and/or a large number of emitting compounds. In this case too, the emitting compounds are generally those that have the smaller proportion in the system and the matrix materials are those that have the larger proportion in the system. In individual cases, however, the proportion of an individual matrix material in the system can be lower than the proportion of an individual emitting compound.

Preferably, the compounds of formula (1) are 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. Preferably, in this case, one of the two materials is 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, even 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.

The mixed matrix systems can contain one or more emitting compounds, preferably one or more phosphorescent compounds. In general, mixed matrix systems are preferably used in phosphorescent organic electroluminescent devices.

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.

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

Examples of phosphorescent compounds are listed below.

Preferred fluorescent emitting compounds are selected from the class of arylamines. In the context of the present invention, an arylamine or an aromatic amine is understood to mean a compound which contains three substituted or unsubstituted aromatic or heteroaromatic ring systems which are bonded directly to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a condensed ring system, particularly preferably with at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. An aromatic anthraceneamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. An aromatic anthracene diamine is a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9- and 10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously, in which the diarylamino groups are bonded to the pyrene preferably in the 1-position or 1,6-position. Further preferred emitting compounds are indenofluorenamines or fluorenediamines, for example according to WO 2006/108497 or WO 2006/122630, benzoindenofluorenamines or fluorenediamines, for example according to WO 2008/006449, and dibenzoindenofluorenamines or diamines, for example according to WO 2007/140847, and the indenofluorene derivatives with condensed aryl groups disclosed in WO 2010/012328. Likewise preferred are the pyrenearylamines disclosed in WO 2012/048780 and in WO 2013/185871. Also preferred are the benzoindenofluorenamines disclosed in WO 2014/037077, the benzofluorene- amines, the extended benzoindenofluorenes disclosed in WO 2014/111269 and in WO 2017/036574, the phenoxazines disclosed in WO 2017/028940 and in WO 2017/028941 and the fluorine derivatives bound to furan units or thiophene units disclosed in WO 2016/150544. Furthermore, boron compounds 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 are used.

Useful matrix materials, preferably for fluorescent compounds, include materials from different substance classes. Preferred matrix materials are selected from the classes of oligoaryls (e.g. 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthyl-anthracene), 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, in particular ketones, phosphine oxides, sulfoxides etc. (for example according to WO 2005/084081 and WO 2005/084082), atropisomers (for example according to WO 2006/048268), 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 which include 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 connected to one another. 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 derivatives disclosed in EP 1749809, EP 1905754 and US 2012/0187826. compounds, the benzanthracenyl-anthracene compounds disclosed in WO 2015/158409, the indeno-benzofurans disclosed in WO 2017/025165 and the phenanthryl-anthracenes disclosed in WO 2017/036573.

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 the charge transport, as described, for example, in WO 2010/108579.

Another possibility to improve the performance of electronic devices, especially organic electroluminescent devices, improve the emission layer is to use combinations of two or more host materials in the emission layer. For example, US 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 6,803,720 B1 discloses the use of a mixture containing a phosphorescent emitter and a hole and an electron transport material in the emission layer of an OLED.

Therefore, it is further preferred that the composition of the present invention further contains at least one hole-transporting host material in addition to the electron-transporting material.

Preferably, the at least one hole-transporting 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 and carbazolamines.

wobei: More preferably, the at least one hole-transporting host material is selected from compounds of the formula (h-1) or (h-2):

where:

K is Ar ⁴ or -L ⁵ -N(Ar)2;

Z is CR ^z or CR ^A ; or two adjacent Z groups together form a fused ring; RA is -L ³ -AC ⁵ or -L ⁴ -N(Ar)2;

R ^z is selected on each occurrence, identically or differently, from H, D, F, CI, Br, I, N(Ar) ₂ , N(R') ₂ , OAr, SAr, CN, NO ₂ , 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) ₂ R', OSChR', 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 can each be substituted by one or more radicals R, where one or more non-adjacent CH2 groups can be replaced by Si(R')2, C=O, NR', O, S or CONR', or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, each of which can be substituted by one or more radicals R';

L ⁴ , L ⁵ are, identically or differently on each occurrence, 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';

L ³ is 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' on L ³ can form a ring with a radical R ^z on the carbazole;

Ar ⁴ 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';

Ar ⁵ is, identically or differently at each occurrence, an unsubstituted or substituted heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more R'; R ^z is, identically or differently on each occurrence, H, D, F, CI, Br, I, N(Ar)2, N(R') ₂ , OAr, SAr, CN, NO ₂ , 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) ₂ R', OSO ₂ R', 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 are substituted by Si(R')2, C=O, NR', O, S or CONR', or is 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 together may also form a ring system;

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

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 R' radicals; 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;

Ar is, identically or differently at each occurrence, 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;

R' is, identically or differently at each occurrence, H, D, F, CI, Br, I, N(Ar) ₂ , N(R“)2, OAr, SAr, 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) ₂ R“, OSO2R“, a straight-chain alkyl group having 1 to 20 carbon atoms or a 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 can each be substituted by one or more radicals R", where one or more non-adjacent CH2 groups can 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, which can each be substituted by one or more radicals R", where two radicals R' together can also form a ring system;

R“ is, identically or differently on each occurrence, H, D, F, CI, Br, I, N(R“')2, 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 are replaced by Si(R“')2, C=O, NR"', O, S or CONR'", or is 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;

R"' is on each occurrence, identically or differently, H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which one or more H atoms can be replaced by D or F; two or more radicals R"' together can form a ring system. with the proviso that the compounds of the formulae (h-1) and (h-2) comprise at least one group Z which stands for R ^A. Preferably, L ⁴ , L ⁵ are, identically or differently on each occurrence, 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'.

Preferably, L ³ is a 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 can be substituted by one or more radicals R', where a radical R' on L ³ can form a ring with a radical R ^z on the carbazole.

wobei die gestrichelte Bindung die Anbindung an L³ oder Z anzeigt; Preferably, the group Ar ⁵ is an unsubstituted or substituted heteroaromatic ring system selected from the groups of formulas (Ar5-1) to (Ar5-6),

where the dashed bond indicates the attachment to L ³ or Z;

V is CR ^v , with the proviso that V is C when it is bonded to the group of formula (h-1 ) or (h-2); or two adjacent groups

V together form a condensed ring;

T is CR ^T , with the proviso that T is C when bonded to the group of formula (h-1) or (h-2), or two adjacent groups T together form a fused ring;

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;

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

R ^T ' R ^v is selected on each occurrence, identically or differently, from H, D, F, CI, Br, I, N(Ar) ₂ , N(R') ₂ , OAr, SAr, CN, NO ₂ , 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) ₂ R', OSChR', 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 can each be substituted by one or more radicals R', where one or more non-adjacent CH2 groups can be replaced by Si(R')2, C=O, NR', O, S or CONR', or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, each of which can be substituted by one or more radicals R', where two radicals R ^T together can form a ring system and two radicals R ^v together can form a ring system; x ¹ , y ¹ are independently selected from 0 or 1, wherein when x ¹ or y ¹ is 0, the corresponding group E ¹ is not present; with the proviso that x ¹ + y ¹ = 1 or 2; and wherein R' and Ar have the same meaning as above.

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

wobei die Symbole die gleiche Bedeutung wie oben haben und wobei die Indices die folgende Bedeutung haben: x, y, x¹,y¹ haben die gleiche Bedeutung wie oben; c, f stehen unabhängig für 0, 1 , 2, 3 oder 4; d, e stehen unabhängig für 0, 1 , 2 oder 3; g steht für 0, 1 , 2 oder 3, wenn x¹=0; oder für 0, 1 oder 2, wenn x¹=1 ; h steht für 0, 1 , 2, 3 oder 4, wenn y¹=0; oder für 0, 1 , 2 oder 3, wenn y¹=1 ; k steht für 0, 1 , 2, 3 oder 4, wenn x=0; oder für 0, 1 , 2 oder 3, wenn x=1 ; und

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 stand for 0, 1 , 2, 3 or 4; d, e independently stand for 0, 1 , 2 or 3; g stands for 0, 1 , 2 or 3 if 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

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

Examples of hole-transporting host materials suitable as a second host material in the composition are shown in the following table:

Furthermore, it is preferred that the at least one blue phosphorescent metal complex is selected from platinum complexes. Preferably, the at least one blue phosphorescent metal complex has a LUMO of -1.8 eV to -2.2 eV, and the at least one blue phosphorescent metal complex preferably has a HOMO of -5.0 eV to -5.6 eV, as defined by quantum mechanical calculations.

Preferably, the energy of the lowest triplet state Ti of the at least one blue phosphorescent metal complex is higher than 2.55 eV, more preferably >2.65 eV, even more preferably >2.75 eV, as defined by quantum mechanical calculations.

As mentioned above, the energy levels of molecular orbitals, such as the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), the lowest triplet state Ti or the lowest excited singlet state Si of materials are determined using quantum mechanical calculations. To calculate organic substances without metals, a geometry optimization is first carried out using the "Ground State/Semi-empirical/Default Spin/AM1 /Charge O/Spin Singlet" method. An energy calculation is then carried out based on the optimized geometry. The "TD-SCF/DFT/Default Spin/B3PW91" method with the "6-31 G(d)" basis set (Charge 0, Spin Singlet) is used. For metal-containing compounds, the geometry is optimized using the "Ground State/Hartree-Fock/Default Spin/LanL2MB/Charge O/Spin Singlet" method. The energy calculation is carried out analogously to the method described above for the organic substances, with the difference that the "LanL2DZ" basis set is used for the metal atom and the "6-31 G(d)" basis set is used for the ligands. The energy calculation yields the HOMO energy level HEh or LUMO energy level LEh in Hartree units. From this, the HOMO and LUMO energy levels calibrated using cyclic voltammetry measurements are determined in electron volts as follows:

HOMO(eV) = ((HEh*27.212)-0.9899)/1 .1206

LUMO(eV) = ((LEh*27.212)-2.0041)/1.385 For the purposes of this application, these values are to be regarded as HOMO or LUMO energy levels of the materials.

The lowest triplet state Ti is defined as the energy of the triplet state with the lowest energy resulting from the quantum chemical calculation described.

The lowest excited singlet state Si is defined as the energy of the excited singlet state with the lowest energy resulting from the quantum chemical calculation described.

The method described here is independent of the software package used and always gives the same results. Examples of commonly used programs for this purpose are 'GaussianO9W' (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.).

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

where:

Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ on each occurrence, identically or differently, represent a group CR ^Y or N; or Y ¹ -Y ² and/or Y ³ -Y ⁴ or Y ⁴ -Y ⁵ can form a condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms, which in each case can also be substituted by one or more radicals R'; E ⁵⁰ stands for C(R ^C0 )2, NR ^N0 , 0 or S, identically or differently at each occurrence;

Ar ⁵⁰ is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R';

Ar ⁵¹ , Ar ⁵² , Ar ⁵³ are the same or different and represent a condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms, which may each also be substituted by one or more radicals R';

R ^Y on each occurrence, identically or differently, represents a radical selected from H, D, F, CI, Br, I, CHO, CN, C(=O)Ar, P(=O)(Ar) ₂ , S(=O)Ar, S(=O) ₂ Ar, N(R') ₂ , N(Ar) 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 in each case one or more non-adjacent CH2 groups are substituted 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 can be replaced by D, F, CI, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which can be substituted by one or more R' radicals, and an aryloxy group having 5 to 60 aromatic ring atoms, which can be substituted by one or more R' radicals, where two R ^Y radicals together can form an aliphatic, aromatic or heteroaromatic ring system, which can be substituted by one or more R'radicals;

R ^co on 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';

R ^N0 on 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';

R‘ and Ar have the same meaning as above.

Preferably, Ar ⁵⁰ is, identically or differently on each occurrence, 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'.

Preferably, Ar ⁵¹ , Ar ⁵² , Ar ⁵³ are the same or different and represent a condensed aryl or heteroaryl ring having 6 aromatic ring atoms, which may each also be substituted by one or more radicals R'.

Preferably, R ^Y on each occurrence is identical or different and 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 R' radicals, 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 R' radicals.

Preferably, R ^co on 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 may form an aliphatic, aromatic or heteroaromatic ring system which is substituted by one or more radicals R'.

Preferably, R ^N0 on 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'.

■ Examples of particularly suitable blue phosphorescent metal complexes are shown below:

■

¹⁰ c ”

30

35

Preferably, the at least one fluorescent emitter in the composition has a peak emission wavelength between 420-550 nm, preferably between 420-470 nm.

Preferred fluorescent emitters are emitters selected from the emitter classes mentioned above.

Preferably, the at least one fluorescent emitter has a full width at half maximum (FWHM) < 50 nm, preferably FWHM < 40 nm, more preferably FWHM < 30 nm. The method for determining the FWHM is described in the experimental part below.

Preferably, the at least one fluorescent emitter has a LIIMO of -2.1 eV to -2.5 eV, preferably from -2.2 eV to -2.4 eV, as defined by quantum chemical calculations. Preferably, the at least one fluorescent emitter has a HOMO of -4.8 eV to -5.2 eV, preferably from -4.9 eV to -5.1 eV, as defined by quantum chemical calculations.

Preferably, the energy of the lowest singlet state Si of the fluorescent emitter is 2.65 eV to 2.9 eV, preferably 2.7 to 2.8 eV, more preferably 2.7 to 2.75 eV, as defined by quantum mechanical calculations.

Examples of suitable fluorescent emitters are given below.

Suitable charge transport materials, as 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 in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials as used in these layers according to the prior art.

All materials that are used according to 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. Other compounds that are preferably used in hole transport 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 (eg 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), phenanthrenediarylamines (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), xanthenediarylamines (for example according to WO 2014/072017), and 9,10-dihydroanthracene spiro compounds with diarylamino groups according to WO 2015/086108.

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 which are 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 which are claimed and disclosed in WO 2012/034627.

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. Other compounds that can be used in addition to the compounds of formula (1) are all materials that are used according to the state of the art as electron transport materials in the electron transport layer. Particularly suitable are aluminum complexes, e.g. Alqs, 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.

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

In the further layers of the organic electroluminescent device according to the invention, all materials can be used as are usually used according to the prior art. The person skilled in the art can therefore, without inventive step, 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.

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

Also preferred is an organic electroluminescent device, characterized in that one or more layers are coated using the OVPD (Organic Vapour Phase Deposition) method or with the aid of carrier gas sublimation. The materials at a pressure between 10' ⁵ mbar and 1 bar. A special case of this process is the OVJP (Organic Vapour Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured.

Also preferred is an organic electroluminescent device, characterized in that one or more layers are produced from solution, such as by spin coating, or using any printing method, such as screen printing, flexographic printing, offset printing, LITI (light induced thermal imaging, thermal transfer printing), ink-jet printing or nozzle printing. Soluble compounds are required for this, which are obtained, for example, by suitable substitution.

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.

These methods 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.

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).

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 service lives. 2. The compounds according to the invention lead to high efficiencies, in particular to a high EQE.

3. The connections according to the invention lead to low operating voltages.

The invention is explained in more detail by the following examples, without intending to restrict it thereby. From the descriptions, the person skilled in the art can carry out the invention in the entire disclosed area and, without inventive step, produce further compounds according to the invention and use them in electronic devices or apply the method according to the invention.

Examples:

Unless otherwise stated, the following syntheses are carried out under a protective gas atmosphere in dried solvents. The solvents and reagents can be obtained 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 compounds known from the literature.

B) Synthesis of synthons S and compounds B: Example S1 :

Variant 1 : Grignard coupling

Carrying out the procedure analogously to D. Bhattacharyya et al., Org. Lett. 2021 , 23, 869, using LS1 instead of 2,4,6-trichloro-1,3,5-triazine. Batch: 30.4 g (100 mmol) LS1, 10.5 ml (100 mmol) bromobenzene, 24.3 g (100 mmol) magnesium. The crude product is purified chromatographically (Torrent column machine from A. Semrau). Yield: 26.1 g (76 mmol) 76%; purity: approx. 97% according to ¹ H-NMR. If the reactant LS1 is reacted consecutively with two or three equivalents of the Grignard compound, the corresponding di- or triaryl-tris-triazolotriazines can be obtained. If mixtures of aryl bromides are used to synthesize triaryl-tris-triazolotriazines, the resulting product mixture can also be separated into pure components by chromatography. Organolithium compounds can also be used as an alternative to Grignard compounds.

Variant 2: Suzuki clutch

A well-stirred solution of 30.4 g (100 mmol) LS1, 12.2 g (100 mmol) phenylboronic acid [98-80-6], 27.6 g (200 mmol) potassium carbonate, 423 mg (0.5 mmol) XPhos Pd G3 [564483-18-7], 100 g glass beads (3 mm) and 500 ml DMSO is stirred for approx. 16 h at 80 °C (TLC control for complete conversion). The DMSO is largely removed in vacuo, the residue is taken up in a mixture of 500 ml dichloromethane (DCM) and 200 ml ethyl acetate (EE) and filtered through a filter paper pre-treated with DCM. elutriated silica gel. The crude product is further purified by chromatography (Torrent column machine from A. Semrau).

Yield: 25.3 g (74 mmol) 76%; Purity: about 97% according to ¹ H-NMR.

Procedure analogous to S1, variant 2, using 34.6 g (100 mmol) S1 and 19.8 g (100 mmol) 3-biphenylboronic acid [5122-95-2]. The crude product is purified chromatographically (Torrent column machine from A. Semrau). Yield: 31.0 g (67 mmol) 67%; purity: approx. 97% according to 1H-NMR.

Carry out analogously to S1, variant 2, using 46.4 g (100 mmol) S100 and 23.8 g (120 mmol) 2-biphenylboronic acid [4688-76-0]. The crude product is purified by chromatography (Torrent column machine from A. Semrau) and/or repeated hot extraction crystallization (usual organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) and fractional sublimation or annealing under high vacuum. Yield: 35.0 g (60 mmol) 60%; purity: approx. 99.9% according to HPLC.

Procedure analogous to S1, variant 2, use of 9.1 g (30 mmol) LS1 and 20.7 g (100 mmol) ß-([1,1'-biphenyl]-3-yl-2,2',3',4,4',5,5',6,6'-c/9)-boronic acid [2368221-45-6]. The crude product is purified by chromatography (Torrent column machine from A. Semrau) and/or repeated hot extraction crystallization (usual organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) and fractional sublimation or annealing under high vacuum. Yield: 13.1 g (19 mmol) 63%; purity: approx. 99.9% according to HPLC.

If boronate esters are used in the above reactions, K3PO4 x H2O is used instead of K2CO3.

Cl The following connections can be represented analogously.

Cl

A well-stirred mixture of 16.7 g (100 mmol) LS1, carbazole [86-74-8], 24.0 g (100 mmol) sodium hydride [7646-69-7] and 100 g glass beads (3 mm diameter) in 300 ml dimethyl sulfoxide (DMSO) is stirred at 40 °C until hydrogen evolution has ceased. Then, with good stirring, a solution of 30.4 g (100 mmol) LS1 in 200 ml warm DMSO is added, the temperature is slowly increased to 60-100 °C and stirring is continued until complete conversion (approx. 8 h, DC control). The reaction mixture is allowed to cool and poured into 1500 ml of ice water, filter off the precipitated solid, wash it three times with 100 ml of water each time, three times with 100 ml of ethanol each time and dry in a vacuum. The crude product is purified chromatographically (Torrent column machine from A. Semrau). Yield: 26.5 g (61 mmol) 61%; Purity: approx. 97% according to ¹ H-NMR.

Procedure analogous to S200, use of 43.5 g (100 mmol) S200 and 27.7 g (110 mmol) 3-phenyl-9H-carbazole [103012-26-6]. The crude product is purified chromatographically (Torrent column machine from A. Semrau). Yield: 41.5 g (65 mmol) 65%; Purity: approx. 97% according to 1H-NMR.

Carrying out the procedure analogously to S200, using 64.2 g (100 mmol) of S300 and 24.3 g (100 mmol) of 2-phenyl-9H-carbazole [88590-00-5]. The crude product is purified by chromatography (Torrent column machine from A. Semrau) and/or repeated hot extraction crystallization (usual organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) and fractional sublimation or. Annealing in high vacuum. Yield: 41.5 g (65 mmol) 65%; Purity: approx.

99.9% by HPLC.

The following compounds can be prepared analogously by adjusting the stoichiometry of the reactants.

Example B600:

A well-stirred mixture of 46.4 g (100 mmol) S100 and 5.4 g (110 mmol) sodium cyanide and 100 g glass beads (3 mm diameter) in 300 ml DMSO is stirred for 18 h at 140 °C (TLC control). The reaction mixture is allowed to cool, poured into 1500 ml ice water while stirring well, the precipitated solid is filtered off with suction, washed three times with 100 ml water each time, three times with 100 ml ethanol each time and dried in a vacuum. The crude product is purified by chromatography (Torrent column machine from A. Semrau) and/or repeated hot extraction crystallization (usual organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) and fractional sublimation or annealing under high vacuum. Yield: 30.9 g (68 mmol) 68%; Purity: approx. 99.9% according to HPLC.

The following compounds can be prepared analogously by adjusting the stoichiometry of the reactants.

Example: Production of OLEDs

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

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

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

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

The OLEDs have the following layer structure: Substrate

Hole injection layer (HIL) made of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm Hole transport layer (HTL), made of HTM1, 180 nm Electron blocking layer (EBL), see Table 1 Emission layer (EML), see Table 1 Hole blocking layer (HBL), see Table 1 Electron transport layer (ETL), see Table 1 Electron injection layer (EIL) made of ETM2, 1 nm Cathode made of aluminum, 100 nm Table 1: Structure of blue fluorescent OLED components

b) Phosphoreszenz-OLED-Bauteile: Table 2: Results of blue fluorescence OLED devices

b) Phosphorescent OLED components:

The compounds B according to the invention can be used in the hole blocking layer (HBL), the electron transport layer (ETL) and in the emission layer (EML) as electron-conducting matrix material (host material) (eTMM). For this purpose, all materials are thermally vapor-deposited in a vacuum chamber. The emission layer always consists of at least one or more matrix materials M and a phosphorescent dopant Ir, which is mixed into the matrix material or materials by co-evaporation in a certain volume proportion. A specification such as M1:M2:lr (55%:35%:10%) means that the material M1 is in a volume proportion of 55%, M2 in a volume proportion of 35% and Ir in a volume fraction of 10% in the layer. Analogously, the electron transport layer can also consist of a mixture of two materials. The exact structure of the OLEDs can be found in Table 3. The materials used to manufacture the OLEDs are shown in Table 5.

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

The OLEDs have the following layer structure:

substrate

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

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

Electron blocking layer (EBL), see Table 3 Emission layer (EML), see Table 3 Hole blocking layer (HBL), see Table 3 Electron transport layer (ETL), see Table 3 Electron injection layer (EIL) made of ETM2, 1 nm Cathode made of aluminum, 100 nm

Table 3: Structure of phosphorescent OLED components

Table 4: Results of phosphorescent OLED devices

Table 5: Structural formulas of the materials used

Claims

patent claims 1 . Compound according to formula (1 ),

where the symbols used are: R is, identically or differently on each occurrence, H, D, F, CI, Br, I, OAr', SAr', B(OR ¹ ) ₂ , CHO, C(=O)R ¹ , CR ¹ =C(R ¹ ) ₂ , CN, C(=O)OR ¹ , C(=O)NR ¹ , Si(R ¹ ) ₃ , Ge(R ¹ ) ₃ , NO ₂ , P(=O)(R ¹ ) ₂ , OSO ₂ R ¹ , OR ¹ , S(=O)R ¹ , S(=O) ₂ R ¹ , SR ¹ , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group can each be substituted by one or more radicals R ¹ , where one or more non-adjacent CH ₂ groups can be replaced by -R ¹ C=CR ¹ -, - CEC-, Si(R ¹ ) ₂ , CONR ¹ , C=O, C=S, -C(=O)O-, P(=O)(R ¹ ), -O-, -S-, SO or SO ₂ , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ring atoms, which can each be substituted by one or more radicals R ¹ ; wherein if R and associated radicals comprise at least one aromatic ring system comprising at least one nitrogen atom with three single bonds, for each of these aromatic ring systems, each nitrogen atom with three single bonds is part of at least one five-membered ring and/or part of a six-membered ring comprising at least one further heteroatom or a C=O group; with the proviso that at least one R is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and that not all three R simultaneously represent a phenyl group; Ar' is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms which may be substituted by one or more radicals R ¹ , where two or more R ^1s may together form an aromatic or heteroaromatic ring system; R ¹ is, identically or differently on each occurrence, H, D, F, I, B(OR ² )2, CHO, C(=O)R ² , CR ² =C(R ² ) ₂ , CN, C(=O)OR ² , Si(R ² ) ₃ , Ge(R ² ) ₃ , NO ₂ , P(=O)(R ² ) ₂ , OSO2R ² , SR ² , S(=O)R ² , S(=O) ₂ R ² , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl, alkenyl or alkynyl group is each substituted with one or more radicals R ² can be substituted and wherein one or more CH2 groups in the abovementioned groups can be replaced by -R ² C=CR ² -, -C=C-, Si(R ² )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 abovementioned groups can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ² , where two or more radicals R ¹ can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system with one another; 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 R ² substituents may be linked to one another to form a ring. 2. A compound according to claim 1, characterized in that in all R and the associated groups, each nitrogen atom with three single bonds is at least part of a five-membered ring. 3. A compound according to claim 1 or 2, characterized in that groups R do not contain any substituted or unsubstituted amino groups. 4. A compound according to one or more of claims 1 to 3, characterized in that at least one R comprises an aromatic or heteroaromatic ring system having 9 to 60 aromatic ring atoms. 5. A compound according to one or more of claims 1 to 4, characterized in that at least two of the substituents R are identical. 6. Compound according to one or more of claims 1 to 5, characterized in that R is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, OR ¹ , a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl or alkenyl group can each be substituted by one or more radicals R ¹ and where one or more non-adjacent CH2 groups can be replaced by O, or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which can each be substituted by one or more radicals R ¹ . 7. A compound according to one or more of claims 1 to 6, characterized in that R is selected on each occurrence, identically or differently, from an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R ¹ . 8. Compound according to one or more of claims 1 to 7, characterized in that R ¹ is selected, identically or differently on each occurrence, from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the alkyl or alkenyl group may in each case be substituted by one or more radicals R ² , or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R ² ; two or more radicals R ¹ can form an aliphatic ring system with one another. 9. A compound according to one or more of claims 1 to 8, characterized in that the compound is at least 50% deuterated. 10. A process for preparing a compound according to one or more of claims 1 to 9, characterized by the following steps: (A) Synthesis of the basic framework according to formula (1 ), which contains reactive leaving groups instead of the groups R; (B) Introduction of the groups R by coupling reactions. 11. Oligomer, polymer or dendrimer comprising one or more compounds according to formula (1) according to one or more of claims 1 to 9. 12. Formulation comprising at least one compound according to one or more of claims 1 to 9 and at least one further compound and/or at least one solvent. 13. Use of a compound according to one or more of claims 1 to 9 and/or a formulation according to claim 12 in an electronic device. 14. Electronic device comprising at least one compound according to one or more of claims 1 to 9 and/or at least one oligomer, polymer or dendrimer according to claim 11. 15. Electronic device according to claim 14, 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 can 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 9.