WO2023052272A1 - Materials for electronic 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

materials for electronic devices

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

Electronic devices containing organic, organometallic and/or polymeric semiconductors are becoming increasingly important and are used in many commercial products for cost reasons and because of their performance. Examples are organic-based charge transport materials (e.g. triarylamine-based hole transporters) in copiers, organic or polymer light-emitting diodes (OLEDs or PLEDs) in 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 all in one advanced stage of development and may gain great importance in the future.

Electronic devices within the meaning of this invention are understood to mean organic electronic devices which contain organic semiconductor materials as functional materials. In particular, the electronic devices stand for electroluminescent devices such as OLEDs.

The construction of OLEDs in which organic compounds are used as functional materials is known to the person skilled in the art from the prior art. In general, OLEDs are electronic devices that have one or more layers that include organic compounds and emit light when a voltage is applied.

In electronic devices, especially OLEDs, there is a great need for performance data, especially lifespan, efficiency and improve 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 emissive, layer. In addition to these layers, they can also 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.

Hole transport layers and electron transport layers have a major impact on the performance of electronic devices.

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 for hole-transport layers or material for electron-transport layers, and lead to good properties there.

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

The present invention relates to a compound of the formula (1),

Formula (1) where the following applies to the symbols used:

X is the same or different on each occurrence of CR or N with the proviso that a maximum of two groups of X per cycle are N;

R' is identical or different on each occurrence, D, F, CI, Br, I, N(Ar ² ) ₂ , OAr', SAr', B(OR ¹ ) ₂ , CHO, C(=O)R ¹ , CN , C(=O)OR ¹ , C(=O)NR ¹ , Si(R ¹ ) ₃ , NO2, P(=O)(R ¹ ) ₂ , OSO2R ¹ , OR ¹ , S(=O)R ¹ , S(=O)2R ¹ , SR ¹ , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which can each be substituted by one or more R ¹ radicals, with the proviso that at least one or both R' comprise at least one N atom bonded to three carbon atoms, and only a maximum of one R' is N(Ar ² ) ₂ , with two groups bonded to the at least one N atom or the Ar ² in N (Ar ² ) ₂ are not connected or connected via a single bond.

Each time Ar ² occurs, identically or differently, is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted by one or more R ¹ radicals.

R is the same or different 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 , NO2, P(=O)(R ¹ ) ₂ , OSO2R ¹ , OR ¹ , S(= O) ^R1 , S (= 0) 2R ¹ , SR ¹ , 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, 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 are replaced by -R ¹ C=CR ¹ -, -C=C-, Si(R ¹ )2 , NR ¹ , CONR ¹ , C=O, C=S, -C(=O)O-, P(=O)(R ¹ ), -O-, -S-, SO or SO2 can be replaced, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R ¹ radicals, where two or more R radicals preferably bonded to the same cycle together form an aliphatic, heteroaliphatic , Aromatic or heteroaromatic ring system which can be substituted with one or more radicals R ¹ , and where two radicals R bonded to the same carbon, silicon, germanium or tin atom form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another can, which can be substituted with one or more radicals R ¹ ;

Ar' is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted by one or more radicals R ¹ ;

R ¹ is identical or different on each occurrence, H, D, F, I, B(OR ² )2, N(R ² )2, CHO, C(=O)R ² , CR ² =C(R ² )2 , CN, C(=O)OR ² , Si(R ² ) ₃ , NO2, P(=O)(R ² ) ₂ , OSO2R ² , SR ² , OR ² , S(=O)R ² , S( = O) ₂ R ² , 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, the alkyl, alkenyl - or alkynyl group can each be substituted by one or more radicals R ² and one or more CH2 groups in the above groups can be replaced by -R ² C=CR ² -, -C=C-, Si(R ² )2, C=O, C=S, -C(=O)O-, ^NR2 , ^CONR2 , P(=O)( ^R2 ), -O-, -S-, SO or SO2 can be replaced and one or more H atoms in the above groups can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each may be substituted by one or more R ² radicals, where two or more R ¹ radicals together can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system;

R ² is the same or different on each occurrence and is H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more H atoms can also be replaced by D or F; two or more substituents R ² can be linked to one another and form a ring.

An N atom bonded to three carbon atoms is understood to mean an N atom which has covalent bonds to three carbon atoms. It is, for example, the N atom of an -NR2 group, it also being possible for the radicals bonded to the nitrogen atom to be bridged to one another. The linkage is via a single bond, preferably with the formation of a five-membered ring, such as in the case of carbazoles.

An aryl group within the meaning of this invention contains 6 to 40 carbon atoms; a heteroaryl group within the meaning of this invention contains 5 to 40 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aryl group or heteroaryl group is either a simple aromatic cycle, ie benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc., or one fused (fused) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. understood. On the other hand, 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 within the meaning of this invention contains 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms in the ring system. A heteroaromatic ring system within the meaning of this invention contains 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms and at least one heteroatom in the ring system, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the context of this invention is to be understood as meaning a system which does not necessarily only contain aryl or heteroaryl groups, but also in which several aryl or heteroaryl groups a non-aromatic moiety (preferably less than 10% of the non-H atoms), such as e.g. B. a C, N or O atom or carbonyl group can be connected. Likewise, systems are to be understood here in which two or more aryl or heteroaryl groups are linked directly to one another, such as, for. B. biphenyl, terphenyl, bipyridine or phenylpyridine. For example, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. should also be understood as aromatic ring systems for the purposes of this invention, and also systems in which two or more aryl groups, for example are linked by a linear or cyclic alkyl group or by a Si ly I 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 linked directly to one another, for example biphenyl, terphenyl, quaterphenyl or bipyridine, and also fluorene or spirobifluorene.

An electron-rich heteroaromatic ring system is characterized in that it is a heteroaromatic ring system that does not contain any electron-deficient heteroaryl groups. An electron-deficient heteroaryl group is a six-membered-membered heteroaryl group containing at least one nitrogen atom or a five-membered-membered heteroaryl group containing at least two heteroatoms, one of which is a nitrogen atom and the other is oxygen, sulfur or a substituted nitrogen atom, to which groups further aryl or heteroaryl are attached - groups can be condensed. In contrast, electron-rich heteroaryl groups are five-membered-membered 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-membered heteroaryl groups can be fused. Thus, 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 referred to as an electron-rich heteroaromatic radical.

An electron-deficient heteroaromatic ring system is characterized as containing at least one electron-deficient heteroaryl group, and more preferably no electron-rich heteroaryl groups.

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

A cyclic alkyl, alkoxy or thioalkoxy group in the context of this invention is understood as meaning 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 carbon atoms, and in which individual H atoms or CH 2 groups are also substituted by the abovementioned groups can be, 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-diethyln- 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, pentynyl, hexynyl, heptynyl or octynyl. An alkoxy group OR ¹ having 1 to 40 carbon atoms is preferably 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, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy understood. A thioalkyl group SR ¹ having 1 to 40 carbon atoms is, 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, cycloheptylthio, 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 understood. In general, alkyl, alkoxy or thioalkyl groups according to the present invention can be straight-chain, branched or cyclic, it being possible for one or more non-adjacent CH2 groups to be replaced by the groups mentioned above; furthermore, one or more H atoms can also be replaced by D, F, Cl, Br, I, CN or NO2, preferably F, Cl or CN, particularly preferably F or CN.

Under an aromatic or heteroaromatic ring system with 5 - 60 aromatic ring atoms, preferably 5 - 40 aromatic Ring atoms, which can each be substituted by the abovementioned radicals or a hydrocarbon radical and which can be linked via any position on the aromatic or heteroaromatic, are understood to mean, in particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene , chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indenofluorene, cis or trans indenocarbazole, cis or trans Indolocarbazole, cis or trans monobenzoindenofluorene, cis or trans dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, 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, pyrazineimidazole, quinoxalineimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, Pyrimidine, benzpyrimidine, 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, fluorubine, 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, 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.

The wording that two or more radicals can form a ring system with one another is to be understood in the context of the present description, inter alia, as meaning that the two radicals are linked to one another by a chemical bond with formal splitting off 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 radicals is hydrogen, the second radical binds to the position to which the hydrogen atom was bonded, forming a ring. This should be illustrated by the following scheme:

The following formulas (2), (3) and (4) show further preferred embodiments:

formula (2) formula (3)

Formula (4) where the symbols used have the meanings given above for formula (1), with the following additionally applying:

Ar ¹ is identical or different on each occurrence, a bivalent aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which can be substituted by one or more radicals R ¹ ;

R' is the same or different on each occurrence 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 , NO2, P(=O)(R ¹ ) ₂ , OSO2R ¹ , OR ¹ , S(=O )R ¹ , S(═O) 2R ¹ , SR ¹ , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which can each be substituted by one or more R ¹ radicals; s is the same or different on each occurrence and is 0 or 1, where 0 means that the N is bonded directly to the basic structure and s in formula (4) is 1 at least once.

In this case, any two groups Ar ² and/or Ar ¹ and Ar ² can be linked to one another via a single bond, preferably with the formation of a five-membered ring as in a carbazole structure. In a preferred embodiment of the invention, a maximum of two symbols X per cycle stand for N, particularly preferably a maximum of one symbol X.

In a preferred embodiment, all X's are CR.

In a preferred embodiment, all Xs are CR, where R is H, D, F or CN.

In a preferred embodiment of the invention, the compound has no ring system fused to the triptycene.

Preferred embodiments of the compounds of the formulas (2), (3) and (4) are the following compounds of the formulas (2-1), (3-1) and (4-1):

Formula (2-1 )

Formula (4-1) where the symbols, if present, have the meanings given for formulas (2), (3) and (4).

The two groups Ar ² and/or Ar ¹ and Ar ² can be linked to one another, preferably via a single bond to form a carbazole structure.

The compounds of formulas (2) and (3) or their preferred embodiments may, depending on the substitution, a form a pair of enantiomers. The compound according to the invention is preferably present as a racemate, but it can also be present as a pure enantiomer.

In a preferred embodiment of the invention, a maximum of 5 groups R in the formulas (2), (3) and (4), preferably in the formulas (2-1), (3-1) and (4-1), are not H, F, CN or D, preferably a maximum of 2 groups R.

Particular preference is given to compounds of the formulas (2) and (3), particularly preferably (2-1) and (3-1).

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

In a preferred embodiment of the invention, R is selected identically or differently on each occurrence from the group consisting of H, D, F, CN, OR ¹ , a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon Atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the alkyl or alkenyl group may be substituted by one or more radicals R ¹ , but is preferably unsubstituted, and where one or more non-adjacent CH2 groups by O can be replaced, 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 ; two radicals R can also form an aliphatic, aromatic or heteroaromatic ring system with one another. R is particularly preferably selected identically or differently on each occurrence from the group consisting of H, F, CN, a straight-chain alkyl group having 1 to 6 carbon atoms, in particular having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, it being possible for each alkyl group to be substituted by one or more radicals R ¹ , but it 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 ¹ , preferably non-aromatic radicals R ¹ . R is very particularly preferably selected on each occurrence, identically or differently, from the group consisting of H or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which can be substituted by one or more radicals R ² , 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 R ¹ radicals. If R is a heteroaryl group, in particular triazine, pyrimidine or quinazoline, preference may also be given to aromatic or heteroaromatic radicals R ¹ on this heteroaryl group.

The groups R, if they represent an aromatic or heteroaromatic ring system, are preferably selected from the groups of the following formulas R-1 to R-163,

R-72 R-73 R-74

R-114 R-115 R-116 R-117

where R ¹ has the meanings given above, the dashed bond represents the bond to formula (1) and the following also applies: Ar ³ is identical or different on each occurrence, a bivalent aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, which can be substituted by one or more radicals R ¹ ;

A ¹ is identical or different on each occurrence, BR ¹ , C(R ¹ ) 2 , NR ¹ , 0 or S, preferably C(R ¹ ) 2 , NR ¹ , 0 or S;

A ² is, identically or differently on each occurrence, C(R ¹ )2, NR ¹ , O or S; p is 0 or 1, where p = 0 means that the group Ar ³ is not present and that the corresponding aromatic or heteroaromatic group is attached directly to a carbon atom or to a heteroatom such as nitrogen, wherein in the case of attachment to a Heteroatom for 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- 160p is 1; r is 0 or 1, where r=0 means that no group A ¹ is bonded to this position and radicals 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 of R-1 to R-163, where p is 0 and the dashed bond and an R ¹ for the bond to the aromatic or heteroaromatic group after R-1 until R-163 stands.

If the groups R-1 to R-163 mentioned above have several groups A ¹ , then all combinations from the definition of A ¹ are suitable for this. Preferred embodiments are then those in which one group A ¹ is C(R ¹ ) 2 , NR ¹ , O or S and the other group A ¹ is C(R ¹ ) ₂ or in which both groups A ¹ are S or 0 or in which both groups A ¹ are 0 or S.

When A ¹ is NR ¹ , the substituent R ¹ attached to the nitrogen atom is preferably aromatic or heteroaromatic Ring system with 5 to 24 aromatic ring atoms, which can also be substituted by one or more R ² radicals. In a particularly preferred embodiment, this substituent R ¹ is identical or different on each occurrence for an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 12 aromatic ring atoms, which has no fused aryl groups or heteroaryl groups in which two or more aromatic or heteroaromatic 6-ring groups are fused directly to one another, and which can each also be substituted by one or more R ² radicals. Particular preference is given to phenyl, biphenyl, terphenyl and quaterphenyl with linkage patterns as listed above for R-1 to R-35, it being possible for these structures to be substituted by one or more radicals R ¹ , but they are preferably unsubstituted.

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

In a further preferred embodiment of the invention, R ¹ is identical or different on each occurrence selected from the group consisting of H, D, F, CN, OR ² , a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, it being possible for the alkyl or alkenyl group to be substituted by one or more R ² radicals and for one or more non-adjacent CH2 groups to be replaced by O , or an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, each of which can be substituted by one or more radicals R ² ; two or more radicals R ¹ together can be aliphatic form a ring system. In a particularly preferred embodiment of the invention, R ¹ is identical or different on each occurrence selected from the group consisting of H, a straight-chain alkyl group having 1 to 6 carbon atoms, in particular having 1, 2, 3 or 4 carbon atoms, or one branched or cyclic alkyl group having 3 to 6 carbon atoms, where the alkyl group may be substituted by one or more radicals R ² , but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which is substituted by one or more R ² radicals may be substituted, but is preferably unsubstituted.

In a further preferred embodiment of the invention, R ² is the same or different on each occurrence of H, F, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which is linked to an alkyl group having 1 to 4 carbon atoms. Atoms may be substituted, but is preferably unsubstituted.

In a further preferred embodiment of the invention, all radicals R ¹ , if they represent an aromatic or heteroaromatic ring system, or R ² if they represent aromatic or heteroaromatic groups, are selected from the groups R-1 to R-163, which, however, then are each substituted accordingly with R ² or the groups mentioned for R ² .

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

In a preferred embodiment of the invention, one R' is selected from N(Ar ² )2 or the groups R-44 to R-74, R-143, R-146 to R-148, R-153 to R-163 with the Provided that in the groups R-45 to R-48, R-50 to R-52, R-54 to R-56, R-59 to R-61, R-63 to R-65, R-67 to R-69, R-143, R-146, R-161 to R-163 at least in A ¹ is NR ¹ . In a preferred embodiment of the invention, the Ar ² groups are then also selected from the groups R-1 to R-163, preferably R-1 to R-149 and R-153 to R-163, more preferably R-2 to R-149 and R-153 to R-163.

In a preferred embodiment of the invention, one R' is selected from N(Ar ² )2 or the groups R-44 to R-74, R-143, R-146 to R-148 with the proviso that in the groups R- 45 to R-48, R-50 to R-52, R-54 to R-56, R-59 to R-61, R-63 to R-65, R-67 to R-69, R-143, R-146 is at least in A ¹ NR ¹ , where R ¹ is then identical or different on each occurrence for H, D, F or CN. In a preferred embodiment of the invention, the groups Ar ² are then also selected from the groups R-1 to R-163, preferably R-1 to R-149 and R-153 to R-163, particularly preferably R-2 to R-149 and R-153 to R-163, where R ¹ is then particularly preferably identical or different on each occurrence for H, D, F or CN.

In a preferred embodiment, one R' is as defined in either of the preceding two paragraphs, while the other R' is selected from the groups R-1 to R-163, provided that when the other R' is N(Ar ² ) 2 is p in the groups R-44, R-49, R-53, R-57, R-58, R-62, R-66, R-70, R-71, R-152 to R-160 1 stands.

In a preferred embodiment, one R' does not include an electron-deficient heteroaryl group, preferably both R' do not include an electron-deficient heteroaryl group. Examples of electron-deficient heteroaryl groups are R-79 to R-113, R-144, R-145.

In a preferred embodiment, all R's do not comprise an electron-deficient heteroaryl group, more preferably all R's and at least one R', more preferably all R's and R's.

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

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

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

The compounds according to the invention can be prepared by synthesis steps known to those skilled in the art, such as, for. B. bromination, Suzuki coupling, Ullmann coupling, Heck reaction, Hartwig-Buchwald coupling, etc., are shown. A further subject of the present invention is therefore a process for the preparation of the compounds according to the invention, characterized by the following steps:

(A) Synthesis of the basic structure according to formula (1);

(B) Coupling of R' residues.

Starting from 9,10-dihydro-4-iodo-9,10[1',2']-benzoanthracene-1-yl-trifluoromethanesulfonic acid ester [1370032-72-6], the compounds according to the invention can be obtained by:

1 ) Suzuki couplings, with an aryl/heteroaryl boronic acid or ester ((H0)2B-Ar), followed by a ruthenium-catalyzed triflate bromide exchange according to Y. Imazaki et al., J. Am. Chem. Soc., 2012, 134, 14760 and again Suzuki coupling introducing an aryl amine:

Ar-Am: aryl amine

2) Suzuki coupling, with an aryl/heteroaryl boronic acid or ester ((HO)2B-Ar), followed by a ruthenium-catalyzed triflate bromide exchange, and finally a Buchwald-Hartwig amination or Ullmann coupling with a diaryl-zheterarylamine Ar1Ar2N-H:

being represented.

Formulations of the compounds according to the invention are required for the processing of the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes. These formulations can be, for example, solutions, dispersions or emulsions. It may be preferable to use mixtures of two or more solvents for this. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, 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, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenetole, 1,4 -Diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl) ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents. A further subject matter 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 a solvent, for example, in particular one of the abovementioned solvents or a mixture of these solvents. The preparation of such solutions is known to the person skilled in the art and is described, for example, in WO 2002/072714, WO 2003/019694 and the literature cited therein. However, the further compound can also be at least one further organic or inorganic compound which is also used in the electronic device, for example an emitting compound and/or a matrix material. This further connection 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 subject matter of the present invention is therefore the use of a connection according to the invention in an electronic device.

Yet another subject matter of the present invention is an electronic device containing at least one connection according to the invention.

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

An electronic device within the meaning of the present invention is a device which contains at least one layer which contains at least one organic compound. The component can also be inorganic Contain niche 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 field quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O -laser) and organic plasmon emitting devices, but preferably organic electroluminescent devices (OLEDs).

The device is particularly preferably an organic electroluminescent device comprising 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 other 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 (charge generation layers) and/or organic or inorganic p/n transitions. Likewise, interlayers can be introduced between two emitting layers, which have an exciton-blocking function, for example. However, it should be pointed out that each of these layers does not necessarily have to be present. In this case, the organic electroluminescence device can contain an emitting layer, or it can contain a plurality of emitting layers. If a plurality of emission layers are present, these preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, resulting overall in white emission, ie different emitting compounds which can fluoresce or phosphorescence are used in the emitting layers. Systems with three emitting layers are particularly preferred, with the three layers exhibiting blue, green and orange or red emission (the basic structure is described, for example, in WO 2005/011013). The organic electroluminescence device according to the invention can also be a tandem OLED, in particular for white-emitting OLEDs.

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

The organic electroluminescence device can contain an emitting layer or it can contain a plurality of 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 where the emission of light occurs through a spin-forbidden transition, e.g. B. a transition from a triplet excited state or a state with a higher spin quantum number, e.g. B. a quintet state. Suitable phosphorescent compounds (= triplet emitters) are, in particular, compounds which, when suitably excited, emit light, preferably in the visible range, and also at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80 included. All luminescent complexes with transition metals or lanthanides are considered to be preferred as phosphorescent compounds, particularly if they contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, indium, palladium, platinum, silver, gold or europium, particularly compounds containing indium, contain platinum or copper. In the context of the present invention, all luminescent indium, platinum or copper complexes are considered to be phosphorescent emitting compounds.

Examples of the emitters described above can be found in 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 2010/099852 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 2015/104045, WO 2015/12018/12015/ 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 are suitable as are used according to the prior art for phosphorescent OLEDs and as are known to the person skilled in the field of organic electroluminescence, and the person skilled in the art can use further phosphorescent complexes without any inventive step. It is also possible for a person skilled in the art, without any inventive activity, to use further phosphorescent complexes in combination with the compounds of the formula (1) in organic electroluminescent devices. 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 which contains one or more fluorescent emitting compounds.

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

A hole-transporting layer within the meaning of the present application is a layer with a hole-transporting function between the anode and the emitting layer.

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

If the compound of the formula (1) is used as a hole-transport material in a hole-transport layer, a hole-injection layer or an electron-blocking layer, the compound can be used as a pure material, ie in a proportion of 100%, in the hole-transport layer, or it can be used in combination with a or several other compounds can be used. In a preferred In this embodiment, the organic layer containing the compound of the formula (1) then additionally contains one or more p-type dopants. P-type dopants used in accordance with the present invention are preferably those organic electron acceptor compounds capable of oxidizing one or more of the other compounds in the mixture.

Particularly preferred embodiments of p-dopants are those in WO 2011/073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US 8057712, WO 2009/003417, WO 2009/003455 2011/120709, US 2010/0096600, WO 2012/095143 and DE 102012209523.

Particularly preferred p-dopants are quinodimethane compounds, azaindenofluorenediones, azaphenylenes, azatriphenylenes, h, metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or a metal of main group 3, and transition metal complexes, preferably complexes of Cu, Co, Ni , Pd, and Pt with ligands containing at least one oxygen atom as a binding site. Transition metal oxides are also preferred as dopants, preferably oxides of rhenium, molybdenum and tungsten, particularly preferably Re2O?, MoOs, WO3 and ReOs.

The p-type dopants are preferably present in a substantially homogeneous distribution in the p-type layers. This can e.g. B. be achieved by co-evaporation of the p-dopant and the hole transport material matrix.

Preferred p-dopants are in particular the following compounds:

In a further preferred embodiment of the invention, the compound of the formula (1) is used as a hole-transport material in combination with a hexaazatriphenylene derivative, as described in US 2007/0092755. The hexaazatriphenylene derivative is particularly preferably used here in a separate layer. In a further embodiment of the present invention, the compound of the formula (1) is used in an emitting layer as matrix material in combination with one or more emitting compounds, preferably phosphorescent compounds.

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

Correspondingly, the proportion of the emitting compound is between 0.1 and 50.0% by volume, preferably between 0.5 and 20.0% by volume, particularly preferably between 0.5 and 8.0% by volume for fluorescent ones emissive layers and between 3.0 and 15.0% by volume. for phosphorescent emitting layers.

An emitting layer of an organic electroluminescent device can also comprise systems that contain a multiplicity of matrix materials (mixed matrix systems) and/or a multiplicity of emitting compounds. In this case, too, the emitting compounds are usually 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 a single matrix material in the system can be lower than the proportion of a single emitting compound.

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

The mixed matrix systems can contain one or more emissive 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 mentioned below or the preferred matrix materials for fluorescent compounds, depending on which type of emitting compound is used in the mixed matrix system becomes.

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

Preferred embodiments of the various functional materials in the electronic device are listed below. 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 as meaning 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 fused ring system, more preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. An anthracene aromatic amine is understood to mean a compound in which a diarylamino group is attached directly to an anthracene group, preferably in the 9-position. An aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9, 10-positions or 1, 6-position are attached to the pyrene. 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 also the indenofluorene derivatives with fused aryl groups disclosed in WO 2010/012328. The pyrenearylamines disclosed in WO 2012/048780 and in WO 2013/185871 are also preferred. Also preferred are the benzoindenofluoreneamines disclosed in WO 2014/037077, the benzofluoreneamines disclosed in WO 2014/106522, the extended benzoindenofluorenes disclosed in WO 2014/111269 and in WO 2017/036574, the extended benzoindenofluorenes disclosed in WO 2017/028940 and in WO 2017/028941 Phenoxazines and the fluorine derivatives bonded to furan units or to thiophene units disclosed in WO 2016/150544. Furthermore, boron compounds according to WO2020208051, WO2015102118, WO2016152418, WO2018095397, WO2019004248, WO2019132040, US20200161552, WO2021089450 can be used.

Useful matrix materials, preferably for fluorescent compounds, include materials from different classes of substances. Preferred matrix materials are selected from the classes of oligoaryls (e.g. 2,2',7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthylanthracene), in particular the oligoaryls with fused aromatic groups, the oligoarylenevinylenes (e.g. DPVBi or spiro-DPVBi according to EP 676461) , the polypodal metal complexes (e.g. according to WO 2004/081017), the hole-conducting compounds (e.g. according to WO 2004/058911), the electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides etc. (e.g. according to WO 2005/084081 and WO 2005/084082 ), the atropisomers (for example according to WO 2006/048268), the boronic acid derivatives (for example according to WO 2006/117052) or the benzanthracenes (for example according to WO 2008/145239). Particularly preferred matrix materials are selected from the classes of oligoarylenes with naphthalene, anthracene, benzanthracene and/or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides and 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. Taking an oligoarylene is in the frame of the present invention means a compound in which at least three aryl or arylene groups are linked to one another. More preferred are the anracthene derivatives disclosed in WO 2006/097208, WO 2006/131192, WO 2007/065550, WO 2007/110129, WO 2007/065678, WO 2008/145239, WO 2009/100925, WO 2011/054442 and EP 1553154 the pyrene compounds disclosed in EP 1749809, EP 1905754 and US 2012/0187826, the benzanthracenylanthracene compounds disclosed in WO 2015/158409, the indenobenzofurans disclosed in WO 2017/025165 and the phenanthrylanthracenes disclosed in WO 2017/036573.

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

Suitable charge transport materials, as they can be used in the hole injection or hole transport layer or in the electron blocking layer or in the electron transport layer of the electronic component according to the invention, 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 used in these prior art layers.

The OLED according to the invention preferably comprises two or more different hole-transporting layers. The compound of the formula (1) can be used in one or more or in all of the hole-transporting layers. In a preferred embodiment, the compound of the formula (1) is used in exactly one or exactly two hole-transporting layers, and other compounds, preferably aromatic amine compounds, are used in the other hole-transporting layers present. Further compounds which, in addition to the compounds of the formula (1), are preferably used in hole-transporting layers of the OLEDs according to the invention are, in particular, indenofluorenamine derivatives (for example according to WO 06/122630 or WO 06/100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene Derivatives (e.g. according to WO 01/049806), amine derivatives with fused aromatics (e.g. according to US 5,061,569), the amine derivatives disclosed in WO 95/09147, monobenzoindenofluorenamines (e.g. according to WO 08/006449), dibenzoindenofluorenamines (e.g. 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 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), phenanthrene diarylamines (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), xanthendiarylamines (for example according to WO 2014/072017), and 9,10-dihydroanthracene spiro compounds with diarylamino groups according to WO 2015/086108.

The use of spirobifluorenes substituted by diarylamino groups in the 4-position as hole-transporting compounds is very particularly preferred, 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 Compounds, in particular the use of those compounds claimed and disclosed in WO 2012/034627.

All materials which are used as electron transport materials in the electron transport layer according to the prior art can be used as materials for the electron transport layer. Aluminum complexes, e.g. Alq3, 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 are particularly suitable. 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.

Preferred cathodes of the electronic component are metals with a low work function, metal alloys or multilayer structures made of different metals, e.g. B. alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Additionally suitable are alloys of an alkali or alkaline earth metal and silver, e.g. B. an alloy of magnesium and Silver. In the case of multilayer structures, in addition to the metals mentioned, other metals with a relatively high work function can also be used, e.g. B. Ag or Al, usually combinations of metals such. B. Ca / Ag, Mg / Ag or Ba / Ag can be used. It may also be advantageous to introduce a thin intermediate layer of high dielectric constant material between a metallic cathode and the organic semiconductor. Examples of suitable materials are alkali or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (e.g. LiF, l_i2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). It is also possible to use lithium quinolinate (LiQ) for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 nm.

Preferred anodes are high work function materials. Preferably, the anode has a work function greater than 4.5 eV versus vacuum. Firstly, metals with a high redox potential, e.g. B. Ag, Pt or Au. On the other hand, metal/metal oxide electrodes (e.g. Al/Ni/NiOx, Al/PtOx) can also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to allow the irradiation of the organic material (organic solar cell) or the emission of light (OLED, 0-laser). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Also preferred are conductively doped organic materials, in particular conductively doped polymers. In addition, the anode can also consist of two or more layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

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

All materials can be used in the further layers of the organic electroluminescent device according to the invention, such as they are usually used according to the state of the art. The person skilled in the art can therefore use all materials known for organic electroluminescent devices in combination with the compounds according to the invention of the formula (1) or the preferred embodiments set out above without any inventive step.

Also preferred is an organic electroluminescence device, characterized in that one or more layers are coated using a sublimation process. The materials are vapour-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.

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

Also preferred is an organic electroluminescent device, characterized in that one or more layers of solution, such as. B. by spin coating, or with any printing method, such as. B. screen printing, flexographic printing, offset printing, LITI (Light Induced Thermal Imaging, thermal transfer printing), ink-jet printing (ink jet printing) or nozzle printing. This requires soluble compounds, which are obtained, for example, by suitable substitution.

Hybrid processes are also 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 to organic electroluminescent devices containing the compounds according to the invention without any inventive step.

According to the invention, the electronic devices containing one or more compounds of the 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 distinguished by one or more of the following properties:

1 . The compounds according to the invention lead to long lifetimes.

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

3. The connections according to the invention result in low operating voltages.

The invention is explained in more detail by the examples below, without intending to limit it thereby. From the descriptions, the person skilled in the art can carry out the invention in the entire disclosed range and produce further compounds according to the invention without any inventive step and use these 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 metal complexes are also handled with the exclusion of light or under yellow light. The solvents and reagents can e.g. B. from Sigma-ALDRICH or ABCR. The respective information in square brackets or the numbers given for individual compounds relate to the CAS numbers of the compounds known from the literature. For compounds that may have multiple enantiomeric, diastereomeric, or tautomeric forms, one form is shown as representative.

Literature-known synthons LS:

A) Synthon synthesis S:

Example S1:

A well-stirred mixture of 52.8 g (100 mmol) LS2, 12.8 g (105 mmol) phenylboronic acid [98-80-6], 48.9 g (150 mmol) cesium carbonate anhydrous, 1.43 g (2 mmol) bis(triphenyphosphino)palladium dichloride, 100 g of glass beads (3 mm in diameter) and 400 ml of THF are stirred at 60° C. for 24 h. After the conversion is complete, it is sucked off while still hot over a Celite bed preslurried with THF, the filtrate is concentrated to dryness, the residue is taken up in 500 ml of dichloromethane (DCM), washed twice with 200 ml of water each time, once with 100 ml of sat. saline solution and dried over sodium sulfate. Desiccant is filtered off over a silica gel bed pre-slurried with DCM, the filtrate is slowly concentrated, the DCM is successively replaced with about 200 ml of methanol, the product which has crystallized out is filtered off with suction, washed with a little methanol and dried in vacuo. Yield: 44.5 g (93 mmol) 93%; Purity: approx. 97% according to ¹ H-NMR.

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Implementation analogous to Y. Imazaki et al, J. Am. Chem. Soc., 2012, 134, 14760.

A well-stirred mixture of 47.9 g (100 mmol) S1, 130.4 g (150 mmol) lithium bromide, 2.54 g (5 mmol) Cp*Ru(MeCN) ₃ OTf [113860-02-9], 100 g glass beads (3 mm diameter ) and 400 ml NMP is stirred at 100 °C for 40 h. After complete conversion, the glass beads are decanted off, the NMP is removed in vacuo, the residue is taken up in 500 ml of ethyl acetate (EA), washed twice with 300 ml of water each time, once with 200 ml of sat. saline and dried over magnesium sulfate. The desiccant is filtered off over a silica gel bed preslurried with EE, the filtrate is concentrated to dryness, the residue is stirred with 200 ml of hot methanol, the product is filtered off with suction, washed with a little methanol and dried in vacuo. Yield: 36.9 g (90 mmol) 90%; Purity: approx. 97% according to ¹ H-NMR.

The following connections can be represented analogously:

B) Synthesis of the compounds according to the invention

Example A1 :

Procedure analogous to A. G. Martinez et al, J. Chem. Soc., Perkin Trans. I, 1986, 1595. A solution of 51.2 g (100 mmol) S50 in a mixture of 500 ml THF, 200 ml methanol-D1 (H3C -OD) and 16.6 ml (120 mmol) triethylamine are mixed with 2 g palladium-carbon (5% by weight) and then stirred in an autoclave at 40° C. under 2 bar deuterium (D2) for 30 h. The reaction mixture is filtered through a Celite bed pre-slurried with THF, the filtrate is concentrated to dryness, the residue is taken up in 500 ml of DCM and washed twice with 200 ml of water each time, once with 200 ml of sat. saline solution and dried over sodium sulfate. Desiccant is filtered off over a silica gel bed pre-slurried with DCM, the filtrate is slowly concentrated, the DCM is successively replaced with about 150 ml of methanol, the product which has crystallized out is filtered off with suction, washed with a little methanol and dried in vacuo. Further purification is carried out by repeated hot extraction crystallization (customary organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) or chromatography and fractional sublimation or tempering in a high vacuum. Yield: 35.2 g (71 mmol) 71%; Purity: approx. 99.9% according to HPLC.

The following connections can be represented analogously:

Example A100:

A well-stirred mixture of 47.9 g (100 mmol) S1, 31.6 g (110 mmol) 9-phenyl-carbazol-3yl-boronic acid [854952-58-2], 25.5 g (110 mmol) tripotassium phosphate monohydrate, 1.16 ( 1 mmol) of tetrakis-triphenylphosphinopalladium(O), 500 ml of DMSO and 100 g of glass beads (3 mm in diameter) are stirred at 80° C. for 16 h. After complete conversion, the mixture is allowed to cool, decanted from the glass beads, and the DMSO is removed largely in vacuo, the residue treated with 300 ml of methanol and 200 ml of water, filtered off from the crude product, washed twice with 200 ml of methanol and dried in vacuo. The crude product is taken up in 300 ml DCM, filtered through a bed of silica gel pre-slurried with DCM, the filtrate is evaporated to dryness, the residue is stirred hot with 200 ml methanol, the crude product is filtered off and washed twice with 50 ml each time methanol and dried in vacuo. Further purification is carried out by repeated hot extraction crystallization (customary organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) or chromatography and fractionated sublimation or tempering in a high vacuum. Yield: 35.2 g (71 mmol) 71%; Purity: approx. 99.9% according to HPLC.

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Example A300:

A well-stirred mixture of 40.9 g (100 mmol) S200, 27.0 g (110 mmol) 4-biphenyl-phenylamine [32228-99-2], 19.2 g (200 mmol) sodium tert-butanolate, 304 mg (1.5 mmol) Tri-tert-butylphosphine [13716-12-6] (alternatively, other phosphines can be used, e.g. tricyclohexylphosphine, bis(tert-butyl)-2-biphenylphosphine, S-Phos, X-Phos, AmPhos,RuPhos, rac- BiNap, BrettPhos, AdBrettPhos etc.) and 224 mg (1 mmol) palladium(II) acetate and 500 ml toluene is refluxed for 16 h. Carbazoles can be reacted analogously, as a base, for example, CS2CO3 is preferably used instead of Na-Ot-Bu, as a solvent, o-xylene at 135 °C, as a catalyst, for example, preferably XanthPhos 2 mol %: palladium^I) acetate 1 mol % . After complete conversion is allowed to cool to about 80 ° C, adds 300 ml of water, separates the org. Phase off, washed twice with 300 ml of water, once with 200 ml of saturated saline solution and dried over magnesium sulfate. The desiccant is filtered off over a silica gel bed pre-slurried with toluene, washed with a little toluene, the filtrate is concentrated to dryness, the residue is stirred hot with 200 ml of methanol, the crude product is filtered off and washed twice with 50 ml of methanol each time and dries in vacuo. Further purification is carried out by repeated hot extraction crystallization (customary organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) or chromatography and fractionated sublimation or tempering in a high vacuum. Yield: 34.8 g (70 mmol) 70%; Purity: approx. 99.9% according to HPLC.

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Example A500:

A well-stirred mixture of 36.5 g (50 mmol) S305, 6.3 g (70 mmol) copper cyanide [544-92-3], 100 g glass beads (3 mm diameter) and 300 ml dimethylacetamide (DMAC) is heated to 160 °C for 24 h heated. It is sucked off while still hot over a bed of Celite which has been slurried with hot DMAC (dimethylacetamide), washed with 100 ml of hot DMAC and the filtrate is concentrated in vacuo. The residue is taken up in 500 ml DCM, 300 ml 10% ammonia solution are added, stirring is continued for 1 h, the organic phase is separated off and washed once with 100 ml 10% ammonia solution, three times with 100 ml each time water, once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The desiccant is filtered off through a bed of silica gel suspended in DCM, the filtrate is concentrated in vacuo, the distillate is substituted with ethanol and then concentrated to a volume of about 100 ml. The precipitated product is filtered off with suction, washed three times with 50 ml of ethanol each time and dried in vacuo. Further purification is carried out by repeated hot extraction crystallization (customary organic solvents or combinations thereof, preferably acetonitrile-DCM, 1:3 to 3:1 vv) or chromatography and fractional sublimation or tempering in a high vacuum. Yield: 22.9 g (33.5 mmol) 67%; Purity: approx. 99.9% according to HPLC.

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Example: Production of the OLEDs

1) Vacuum-processed devices:

OLEDs according to the invention and OLEDs according to the prior art are produced using a general method according to WO 2004/058911, which is adapted to the conditions described here (layer thickness variation, materials used).

The results of various OLEDs are presented in the following examples. Cleaned glass flakes (cleaning in a Miele laboratory dishwasher, Merck Extran cleaner), which are coated with structured ITO (indium tin oxide) with a thickness of 50 nm, are exposed to UV ozone for 25 minutes pretreated (UV ozone generator PR-100, company UVP). These coated glass flakes form the substrates on which the OLEDs are applied.

1a) Blue fluorescence OLED devices - BF:

The compounds of the present invention can be used in hole injection layer (HIL), hole transport layer (HTL) and electron blocking layer (EBL). All materials are thermally evaporated in a vacuum chamber. The emission layer (EML) always consists of at least one matrix material (host material, host material) SMB (see Table 1) and an emitting dopant (dopant, emitter) D, which is added to the matrix material or matrix materials by co-evaporation in a certain volume fraction is added. 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 by default. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) as a function of the luminance are calculated from current-voltage-luminance characteristics (IUL characteristics) assuming a Lambertian radiation characteristic and the service life. The EQE is specified in (%) and the voltage in (V) at a luminance of 1000 cd/m ² The service life is determined at an initial luminance of 10000 cd/m ² . The LT80 in (h) is the measured time in which the brightness has fallen to 80% of the initial brightness.

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 or in example BF15 A309 doped with 5% NDP-9, 20 nm

Hole transport layer (HTL), see Table 1

Electron blocking layer (EBL), see Table 1

Emission layer (EML), see Table 1

Electron transport layer (ETL), made of ETM1 :ETM2 (50%:50%), 30 nm

Electron injection layer (EIL) from ETM2, 1 nm

Aluminum cathode, 100 nm

Table 1: Structure of blue fluorescence OLED components

Table 2: Results Blue FITable 2: Results Blue Fluorescent OLED Devices

1 b) Phosphorescent OLED devices:

The compounds A according to the invention can be present in the hole injection layer (HIL); the hole transport layer (HTL), the electron blocking layer (EBL) and in the emission layer (EML) as matrix material (host material, host material) M (see Table 5) or A (see materials according to the invention). For this purpose, all materials are thermally vapor-deposited in a vacuum chamber. The emission layer always consists of at least one or more matrix materials M and a phosphorescent dopant Ir, which is admixed to the matrix material or matrix materials by co-evaporation in a certain proportion by volume. A specification such as M1 :M2:lr (55%:35%:10%) means that the material M1 accounts for 55% by volume, M2 for 35% by volume and Ir for 10% by volume in the layer present. Similarly, the electron transport layer can also consist of a mixture of two materials consist. The exact structure of the OLEDs can be found in Table 3. The materials used to fabricate the OLEDs are shown in Table 5.

The OLEDs are characterized by default. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) as a function of the luminance are calculated from current-voltage-luminance characteristics (IUL characteristics) assuming a Lambertian radiation characteristic and the service life. The specification of the EQE in (%) and the voltage in (V) takes place at a luminance of 1000 cd/m ² The service life is at an initial luminance of 1000 cd/m ² for blue and red, 10000 cd/m ² for green and yellow emitting components. The specification LT80 in (h) is the measured time in which the brightness falls to 80% of the initial brightness.

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 or in example GP3 A101 doped with 5% NDP-9, 20 nm

Hole transport layer (HTL), see Table 3

Electron blocking layer (EBL), see Table 3

Emission layer (EML), see Table 3

Hole Blocker Layer (HBL), see Table 3

Electron transport layer (ETL), made of ETMTETM2 (50%:50%), 30 nm

Electron injection layer (EIL) from ETM2, 1 nm

Aluminum cathode, 100 nm

Table 3: Structure of phosphorescence OLED components

Table 4: Results phosphorescent OLED devices

Table 5: Structural formulas of the materials used

Claims

patent claims

1. A compound of the formula (1),

Formula (1) where the following applies to the symbols used:

X is the same or different on each occurrence of CR or N with the proviso that a maximum of two groups of X per cycle are N;

R' is identical or different on each occurrence, D, F, CI, Br, I, N(Ar ² ) ₂ , OAr', SAr', B(OR ¹ ) ₂ , CHO, C(=O)R ¹ , CN , C(=O)OR ¹ , C(=O)NR ¹ , Si(R ¹ ) ₃ , NO2, P(=O)(R ¹ ) ₂ , OSO2R ¹ , OR ¹ , S(=O)R ¹ , S(=O)2R ¹ , SR ¹ , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which can each be substituted by one or more R ¹ radicals, with the proviso that at least one or both R 'comprise at least one N atom bonded to three carbon atoms, and only a maximum of one R 'stands for N (Ar ² ) ₂ , with two groups bonded to the at least one N atom or the Ar ² in N (Ar ² ) ₂ are not connected or are connected via a single bond;

Ar ² is identical or different on each occurrence and is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted by one or more R ¹ radicals; R is the same or different 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 , 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 with 1 to 20 carbon atoms or an alkenyl or alkynyl group with 2 to 20 carbon atoms or a branched or cyclic alkyl group 3 to 20 carbon 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 are replaced by -R ¹ C=CR ¹ -, -C =C-, Si( ^R1 ) ₂ , ^NR1 , ^CONR1 , C=O, C=S, -C(=O)O-, P(=O)( ^R1 ), -O-, -S -, SO or SO ₂ can be replaced, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which can each be substituted by one or more radicals R ¹ , with two or more preferably on radicals R bonded to the same cycle can together form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more radicals R ¹ , and where two radicals R bonded to the same carbon, silicon, germanium or tin atom form a monocyclic or can form a polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another, which can be substituted with one or more radicals R ¹ ;

Ar' is identical or different on each occurrence, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can be substituted by one or more radicals R ¹ ;

R ¹ is the same or different on each occurrence: H, D, F, I, B(OR ² ) ₂ , N(R ² ) ₂ , CHO, C(=O)R ² , CR ² =C(R ² ) ₂ , CN, C(=O) ^OR2 , Si( ^R2 ) ₃ , _NO2 , P(=O)( ^R2 ) ₂ , OSO2 _R2 , ^{SR2 , OR2} , S(=O) ^R2 , S(=O) ₂ R ² , 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, the alkyl -, Alkenyl or alkynyl group may each be substituted by one or more R ² radicals and one or more CH 2 groups in the above groups may be substituted by -R ² C=CR ² -, -C=C-, Si(R ² )2 , C=O, C=S, -C(=O)O-, NR ² , CONR ² , P(=O)(R ² ), -O-, -S-, SO or SO 2 can be replaced and where one or more H atoms in the groups mentioned above can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each of which can be replaced by one or more radicals R ² can be substituted, where two or more radicals R ¹ together can form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system;

R ² is the same or different on each occurrence and is H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more H atoms can also be replaced by D or F; two or more substituents R ² can be linked to one another and form a ring.

2. A compound according to claim 1, selected from the compounds of

formulas (2),

(3) or (4),

Formula (4) where the symbols used have the meanings given in claim 1, where the following also applies:

Ar ¹ is identical or different on each occurrence, a bivalent aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, which can be substituted by one or more radicals R ¹ ;

R' is the same or different on each occurrence 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 , NO ₂ , P(=O)(R ¹ ) ₂ , OSO ₂ R ¹ , OR ¹ , S (=O)R ¹ , S(=O) ₂ R ¹ , SR ¹ , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, preferably having 5 to 40 aromatic ring atoms, each substituted by one or more R ¹ radicals can; s is the same or different on each occurrence and is 0 or 1, where 0 means that the N is bonded directly to the basic structure and s in formula (4) is 1 at least once. A compound according to claim 1 or 2 selected from the compounds of formulas (2-1 ), (3-1 ) and (4-1 ),

35 Formula (4-1) wherein the symbols used have the meanings given in claim 2.

4. A method for preparing a compound according to one or more of claims 1 to 3, characterized by the following steps:

(A) Synthesis of the basic structure according to formula (1);

(B) Coupling of R' residues.

5. Oligomer, polymer or dendrimer comprising one or more compounds according to formula (1) according to one or more of claims 1 to 3, wherein the bond(s) to the oligomer, polymer or dendrimer can take place at any position in formula (1). (can).

6. Formulation containing at least one compound according to one or more of claims 1 to 3 and at least one further compound and/or at least one solvent.

7. Use of a compound according to one or more of claims 1 to 3 and or a formulation according to claim 6 in an electronic device.

8. Electronic device containing at least one compound according to one or more of claims 1 to 3 and/or at least one oligomer, polymer or dendrimer according to claim 5.

9. Electronic device according to claim 8, which is an organic electroluminescent device, characterized in that the device comprises an anode, cathode and at least one emitting layer, wherein at least one organic layer comprising an emitting layer, hole transport layer, electron transport layer, hole blocking layer, Electron-blocking layer or another functional layer may be, comprises at least one compound of formula (1).