EP4121432A1

EP4121432A1 - Heteroaromatic compounds for organic electroluminescent devices

Info

Publication number: EP4121432A1
Application number: EP21711248.1A
Authority: EP
Inventors: Philipp Stoessel
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2020-03-17
Filing date: 2021-03-15
Publication date: 2023-01-25
Also published as: KR20220154774A; US20230157170A1; CN115298187A; WO2021185712A1

Abstract

The invention relates to heteroaromatic compounds which are suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing said compounds.

Description

Heteroaromatic compounds for organic electroluminescent devices

The present invention relates to heteroaromatic compounds for use in electronic devices, in particular in organic electroluminescent devices, as well as electronic devices, in particular organic ones

Electroluminescent devices containing these heteroaromatic compounds.

In organic electroluminescent devices, phosphorescent organometallic complexes or fluorescent compounds are often used as emitting materials. In general, there is still a need for improvement in the case of electro-luminescent devices.

From WO 2010/104047 A1 and WO 2019/132506 A1, polycyclic compounds are known that can be used in organic electroluminescent devices. Compounds according to the present invention are not disclosed. Furthermore, anti-aromatic properties of compounds are described by Wang et al., In Nature Communications | 8: examined in 1948. However, the use of these compounds in organic electroluminescent devices is not disclosed by Wang et al. described.

In general, there is still a need for improvement with these heterocyclic compounds, for example for use as emitters, in particular as fluorescent emitters, in particular with regard to the service life, the color purity, but also with regard to the efficiency and the operating voltage of the device.

The object of the present invention is therefore to provide compounds which are suitable for use in an organic electronic device, in particular in an organic electroluminescent device, and which lead to good device properties when used in this device, and to provide the corresponding electronic device . In particular, it is the object of the present invention to provide connections which lead to a long service life, good efficiency and low operating voltage.

Furthermore, the compounds should have excellent processability, and the compounds should in particular show good solubility.

Another object of the present invention can be seen in providing compounds which are suitable for use in a phosphorescent or fluorescent electroluminescent device, in particular as an emitter. In particular, it is an object of the present invention to provide emitters which are suitable for red, green or blue electroluminescent devices.

Furthermore, especially when used as emitters in organic electroluminescent devices, the compounds should lead to devices which have excellent color purity.

A further object of the present invention can be seen in providing compounds which are suitable for use in a phosphorescent or fluorescent electroluminescent device, in particular as a matrix material. In particular, it is an object of the present invention to provide matrix materials which are suitable for red, yellow and blue phosphorescent electroluminescent devices.

Furthermore, especially when used as matrix materials or as hole transport materials in organic electroluminescent devices, the compounds should lead to devices which have excellent color purity.

A further object can be seen in providing electronic devices with excellent performance as inexpensively as possible and of constant quality Furthermore, the electronic devices should be able to be used or adapted for many purposes. In particular, the performance of the electronic devices should be maintained over a wide temperature range.

Surprisingly, it has been found that certain compounds described in more detail below solve this problem, are very suitable for use in electroluminescent devices and lead to organic electroluminescent devices which have very good properties, in particular with regard to service life, color purity, efficiency and operating voltage show. These connec tions and electronic devices, in particular organic electroluminescent devices, which hold such compounds ent, are therefore the subject of the present invention

The present invention relates to a compound comprising at least one structure of the formula (I), preferably a compound according to the formula (I),

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

Z is on each occurrence, identically or differently, N or B;

W ¹ , W ² , W ³ , W ⁴ stand on each occurrence, identically or differently, for N or CR, where at least one W ¹ , W ² , W ³ , W ⁴ per ring is N preferably one W ¹ , W ² , W ³ , W ⁴ per ring is N and one W ¹ , W ² , W ³ , W ⁴ per ring is CR;

X ¹ stands on each occurrence, identically or differently, for N, CR ^a or CAr, preferably for CR ^a, with the proviso that not more than two of the groups X ¹ , X ² in one cycle are N;

X ² stands on each occurrence, identically or differently, for N, CR ^b or CAr, preferably for CR ^b, with the proviso that not more than two of the groups X ¹ , X ² in one cycle are N;

X ³ stands on each occurrence, identically or differently, for N, CR ^C or CAr, preferably for CR ^C, with the proviso that not more than two of the groups X ³ , X ⁴ in one cycle are N;

X ⁴ stands on each occurrence, identically or differently, for N, CR ^d , CAr or C, if a ring system is formed by a bond with a group X ⁴ ^{, preferably for CR d} or C with the proviso that not more than two of the groups X ³ , X ⁴ in a cycle represent N;

Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R, here the group Ar can form a ring system with at least one group Ar, R or another group ;

R, R ^a , R ^b , R ^c , R ^d is on each occurrence, identically or differently, H, D, OH, F, CI, Br, I, CN, N0 ₂ , N (Ar ') ₂ , N (R ¹ ) ₂ , C (= 0) Ar ', C (= 0) R ¹ , C (= 0) OAr', C (= 0) OR ¹ , C (= 0) N (Ar ') ₂ , C (= 0) N (R ¹ ) ₂ , C (Ar ') ₃ , C (R ¹ ) ₃ , Si (Ar') ₃ , Si (R ¹ ) ₃ , B (Ar ') ₂ , B (R ¹ ) ₂ , P (= 0) (Ar ') ₂ , P (= 0) (R ¹ ) ₂ , P (Ar') ₂ , P (R ¹ ) ₂ , S (= 0) Ar ', S (= 0) R ¹ , S (= 0) ₂ Ar ', S (= 0) ₂ R ¹ , OS0 ₂ Ar', OS0 ₂ R ¹ , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or an alkenyl - Or alkynyl group with 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 20 carbon atoms, the alkyl, alkoxy, Thioalkoxy, alkenyl or alkynyl groups can each be ^{substituted by one or more radicals R 1} , one or more non-adjacent CF groups by R ¹ C = CR ¹ , CEC, Si (R ¹ ) ₂ , C = 0, C = S, C = Se, C = NR ¹ , -C (= 0) 0-, -C (= 0) NR ¹ -, NR ¹ , P (= 0) (R ¹ ), -0-, -Se -, -S-, SO or SO2 can be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which ^{can be substituted by one or more radicals R 1} , or an aryloxy or heteroaryl oxy group with 5 to 60 aromatic ring atoms which can be substituted by one or more radicals R ^1; two radicals R, R ^a , R ^b , R ^c , R ^{d can} also form a ring system with one another or with a further group;

Ar 'is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which ^{can be substituted by one or more radicals R 1} , two radicals Ar' attached to the same C atom, Si atom , N atom, P atom or B atom bond, also through a single bond or a bridge, selected from B (R ¹ ), C (R ¹ ) ₂ , Si (R ¹ ) ₂ , C = 0, C = NR ¹ , C = C (R ¹ ) ₂ , O, S, S = 0, S0 ₂ , N (R ¹ ), P (R ¹ ) and P (= 0) R ¹ , be bridged to one another;

R 1 is on each occurrence, identically or differently, H, D, F, CI, Br, I,

CN, NO2, N (Ar ”) ₂ , N (R ² ) ₂ , C (= 0) Ar”, C (= 0) R ² , C (= 0) OAr ”, C (= 0) OR ² , P (= 0) (Ar ”) ₂ , P (Ar”) ₂ , B (Ar ”) ₂ , B (R ² ) ₂ , C (Ar”) ₃ , C (R ² ) ₃ , Si (Ar ” ) ₃ , Si (R ² ) ₃ , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms or an alkenyl group with 2 up to 40 carbon atoms, each of which ^{can be substituted by one or more radicals R 2} , where one or more non-adjacent CFh groups are represented by - e, C = NR ² , -C (= 0) 0- or SO2 can be replaced and one or more H atoms can be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic rings Ring atoms, which can be substituted by one or more radicals R ² , or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which ^{can be substituted by one or more radicals R 2} , or an aralkyl or heteroaralkyl group with 5 to 60 aromatic ring atoms which can be substituted by one or more radicals R ² , or a combination of these systems; two or more, preferably adjacent, radicals R ¹ here can form a ring system with one another, while one or more radicals R ¹ can form a ring system with a further part of the compound;

Ar ”is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which ^{can be substituted by one or more radicals R 2} ; two radicals Ar” attached to the same carbon atom, Si atom , N atom, P atom or B atom bond, also through a single bond or a bridge, selected from B (R ² ), C (R ² ) ₂ , Si (R ² ) ₂ , C = 0, C = NR ² , C = C (R ² ) ₂ , 0, S, S = 0, S0 ₂ , N (R ² ), P (R ² ) and P (= 0) R ² , be bridged to one another;

R ² is on each occurrence, identically or differently, selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical with 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, in which a or more H atoms can be replaced by D, F, CI, Br, I or CN and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, two or more, preferably adjacent, substituents R ² with one another form a ring system.

The groups W ¹ and W ⁴ are preferably N and the groups W ² and W ³ are CR.

In a further embodiment, the groups W ¹ and W ^{4 are} preferably CR and the groups W ² and W ³ are N. Furthermore, it can be provided in formula (I) that the groups W ¹ and W ^{3 are} N and the groups W ² and W ^{4 are} CR.

For the purposes of this invention, an aryl group contains 6 to 40 carbon atoms; For the purposes of this invention, a heteroaryl group contains 2 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, 0 and / or S. Here, under an aryl group or heteroaryl group, either a simple aromatic cycle, that is benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc., or a fused (fused) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc., understood. In contrast, aromatics linked by a single bond, such as biphenyl, are not referred to as an aryl or heteroaryl group, but as an aromatic ring system.

An electron-poor heteroaryl group in the context of the present invention is a heteroaryl group which has at least one heteroaromatic six-membered ring with at least one nitrogen atom. Further aromatic or heteroaromatic five-membered rings or six-membered rings can also be fused onto this six-membered ring. Examples of electron-poor heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine,

Triazine, quinoline, quinazoline, or quinoxaline.

For the purposes of this invention, an aromatic ring system contains 6 to 60 carbon atoms in the ring system. A heteroaromatic ring system for the purposes of this invention contains 2 to 60 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 understood to mean a system that does not necessarily contain only aryl or heteroaryl groups, but also contains several aryl - Or heteroaryl groups through a non-aromatic unit, such as. B. a C, N or O atom can be connected. For example, systems should also such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. are understood as aromatic ring systems for the purposes of this invention, and also systems in which two or more aryl groups, for example by a short Alkyl group are connected. The aromatic ring system is preferably selected from fluorene, 9,9'-spirobifluorene, 9,9-diarylamine or groups in which two or more aryl and / or fleteroaryl groups are linked to one another by single bonds.

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 20 carbon atoms, and in which individual H atoms or CF groups are also substituted by the above-mentioned 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, neo-pentyl, Cyclopentyl, n-hexyl, neo-hexyl, cyclohexyl, n-heptyl, cyclo-heptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl , Cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl understood. An alkoxy group having 1 to 40 carbon atoms 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, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy understood. A thioalkyl group with 1 to 40 carbon atoms includes, in particular, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio,

1-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, cyclothiothio, octenylthynyl, butthiothiothio, propenylthio, cycloheptenynyl, butthiothiothio, octoheptenynyl, ethenylthio, ethenylthio , Hexinylthio, heptinylthio or octinylthio understood. In general, alkyl, alkoxy or thioalkyl groups according to the present invention can be straight-chain, branched or cyclic, with one or several non-adjacent CF groups can be replaced by the above-mentioned groups; furthermore, one or more H atoms can also be replaced by D, F, CI, Br, I, CN or NO2, preferably F, CI or CN, more preferably F or CN, particularly preferably CN.

Under an aromatic or heteroaromatic ring system with 5-60 or 5 to 40 aromatic ring atoms, which can be substituted by the above-mentioned radicals and which can be linked via any positions on the aromatic or fleteroaromatic, who in particular means groups that are derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, tetrahydropyrene trans-indenofluoren, cis- or trans-indenocarbazole, cis- or trans -indolocarbazole, truxes, isotruxes, spirotruxes, spiroisotruxes, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, pyrenzothiophene, dibenzothiophene 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, pyrazine imidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, benzo-thiazole, 1,3-isothiazole, phenanthoxazole, thiazole, pyridazine, flexaazatriphenylene, benzopyridazine, pyrimidine, benz pyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyren, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5 -Diazapyren, 4,5,9,10-tetra- azaperylene, 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 formulation that two or more radicals can form a ring with one another is to be understood in the context of the present description, inter alia, to mean that the two radicals are linked to one another by a chemical bond with formal elimination of two hydrogen atoms. This is illustrated by the following scheme.

Furthermore, the abovementioned formulation is also intended to mean that in the event that one of the two radicals is hydrogen, the second radical binds to the position to which the hydrogen atom was bound to form a ring. This should be made clear by the following scheme:

In a preferred embodiment, the compounds according to the invention can comprise a structure of the formulas (IIIa), (Mb), (IIc) and / or (IIId); the compounds according to the invention can particularly preferably be selected from the compounds of the formulas (IIIa), (Mb ), (llc) and / or (Md),

35 Formula (llc) where Z, X ¹ , X ² , X ³ , X ⁴ , R, R ^a , R ^b , R ^c and R ^{d have} the meanings given above, in particular for formula (I), and the following applies to the other symbols:

Y ¹ is on each occurrence, identically or differently, a bond, N (Ar '), N (R ¹ ), B (Ar'), B (R ¹ ), P (= 0) (Ar '), P (= 0 ) (R ¹ ), C (= 0), C (Ar ') ₂ , C (R ¹ ) ₂ , Si (Ar') ₂ , Si (R ¹ ) ₂ , 0, S, Se, S = 0, S0 ₂ , C (= 0) N (Ar '), C (= 0) N (R ¹ ), P (Ar') or P (R ¹ ), - (O) CC (O) -, -N ( Ar ') - C (0) -, - (R ¹ ) ₂ CC (R ¹ ) ₂ -, - (R ¹ ) C = C (R ¹ ) -

, an aryl or heteroaryl group with 5 to 40 aromatic ring atoms, where the aryl or heteroaryl group bonds to the other parts of the structure via two adjacent and interconnected carbon atoms and ^{can be substituted with one or more radicals R 1} , preferably (Ar '), N (R ¹ ), B (Ar'), B (R ¹ ),

P (= 0) (Ar '), P (= 0) (R ¹ ), C (= 0), C (Ar') ₂ , C (R ¹ ) ₂ , Si (Ar ') ₂ , Si (R ¹ ) ₂ , 0, S,

Se, S = 0, S0 ₂ , C (= 0) N (Ar '), C (= 0) N (R ¹ ), P (Ar') or P (R ¹ ), - (O) C-C (O) -, -N (Ar ') - C (0) -, - (R ¹ ) ₂ CC (R ¹ ) ₂ -, - (R ¹ ) C = C (R ¹ ) -, particularly preferably a bond , N (Ar '), N (R ¹ ), B (Ar'), B (R ¹ ), P (= 0) (Ar '), P (= 0) (R ¹ ), C (= 0) , C (Ar ') ₂ , C (R ¹ ) ₂ , Si (Ar') ₂ , Si (R ¹ ) ₂ , 0, S, Se, S = 0 or

S0 ₂ , especially preferably C (R ¹ ) ₂ , Si (R ¹ ) ₂ , O, S, N (Ar ') or B (Ar'), where the symbols R ¹ and Ar 'have the meaning given in claim 1 ; is 0, 1 or 2, preferably 0 or 1; p is 0 or 1, where p = 0 means that the group Y ¹ does not exist; k is 0 or 1, where k = 0 if p = 1.

Structures of the formulas (IIIa) and / or (IIc) are preferred here. The group Y1 can represent an aryl or fleteroaryl group with 5 to 40 aromatic ring atoms, this group bonding to the other parts of the structure via two adjacent and interconnected carbon atoms. Accordingly, these neighboring carbon atoms are directly connected to one another via a bond, the carbon atoms being formally sp ² hybridized, that is to say forming a double bond. Here, these two carbon atoms together with the group Z form a ring with 7 ring atoms.

It can preferably be provided that in formula (I) and / or (IIIa) to (IIId) no more than three, preferably no more than two groups X ¹ , X ² , X ³ and X ^{4 represent} N, particularly preferably all Groups X ¹ , X ² , X ³ and X ^{4 represent} CR ^a , CR ^b , CR ^C or CR ^d , or, if the groups X ⁴ form a ring system through a bond, represent C.

In a further preferred embodiment it can be provided that the compounds according to the invention comprise a structure of the formulas (purple) to (II Iv), it being possible for the compounds according to the invention to be particularly preferably selected from the compounds of the formulas (purple) to (IIIv),

Formula (purple)

Formula (llld) Formula (lllg)

Formula (lllj) Formula (lllp) Formula (IIIv) where the symbols Z, R, R ^a , R ^b , R ^c and R ^{d have} the meanings given above, in particular for formula (I), the symbol Y ¹ and the Indices k and j have the meanings given above, in particular for formulas (lla) to (lld), and the following applies to the other symbols and indices:

Y ² , Y ³ , is on each occurrence, identically or differently, a bond N (Ar '), N (R ¹ ), B (Ar'), B (R ¹ ), P (= 0) (Ar '), P (= 0) (R ¹ ), C (= 0), C (Ar ') ₂ , C (R ¹ ) ₂ , Si (Ar') ₂ , Si (R ¹ ) ₂ , O, S, Se, S = 0, S0 ₂ , C (= 0) N (Ar '),

C (= 0) N (R ¹ ), P (Ar ') or P (R ¹ ), preferably a bond N (Ar'), N (R ¹ ), B (Ar '), B (R ¹ ), P (= 0) (Ar '), P (= 0) (R ¹ ), C (= 0), C (Ar') ₂ , C (R ¹ ) ₂ , Si (Ar ') ₂ , Si (R ¹ ) ₂ , 0, S, Se, S = 0 or S0 ₂ , particularly preferably C (R ¹ ) ₂ , Si (R ¹ ) ₂ , 0, S, N (Ar ') or B (Ar'), where the symbols R ¹ and Ar 'have the meaning set out in claim 1; and m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

Structures / compounds of the formula (lilac), (lllb), (Ille), (lllh), (lllj), (III I), (I I Im), (Hin), (llls), (lllu) are preferred here.

The sum of the indices k, j, m and n in structures / compounds of the formulas (purple) to (IIIv) is preferably at most 10, preferably at most 8, particularly preferably at most 6 and particularly preferably at most 4.

Furthermore, it can be provided, inter alia, in formulas (purple) to (IIIv) and / or the preferred embodiments of these formulas set out below that the groups Y ² and Y ^{3 are} identical.

In addition, it can be provided, inter alia, in formulas (purple) to (IIIv) and / or the preferred embodiments of these formulas set out below that the groups Y ² and Y ^{3 are} different.

In a preferred development of the present invention it can be provided that at least two ^or ^{at least two radicals R, R a} , R ^b , R ^c , R d with the further groups to which the two radicals R, R ^a , R ^b , R ^c , R ^d bond to form a condensed ring, the two radicals R, R ^a , R ^b , R ^c , R ^d forming at least one structure of the formulas (RA-1) to (RA-12)

Formula RA-1 Formula RA-2 Formula RA-3

Formula RA-7 Formula RA-8 Formula RA-9

Formula RA-10 Formula RA-11 Formula RA-12 where R ^{1 has} the meaning set out above, the dashed bonds represent the attachment points via which the two radicals R, R ^a , R ^b , R ^c , R ^d bond, and the other symbols have the following meanings:

Y ⁴ is on each occurrence, identically or differently, C (R ¹ ) 2,

(R ¹ ) ₂ CC (R ¹ ) ₂ , (R ¹ ) C = C (R ¹ ), NR ¹ , NAr ', 0 or S, preferably C (R ¹ ) ₂ , (R ¹ ) ₂ CC (R ¹ ) _2I (R ¹ ) C = C (R ¹ ), O, or S; R ^e is on each occurrence, identically or differently, F, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or an alkenyl or alkynyl group with 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy group or thioalkoxy group with 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group can each be ^{substituted by one or more radicals R 2} , one or more non-adjacent CH ₂ groups being replaced by e, C = NR ² , -C (= 0) 0-, - or S0 ₂ can be replaced, or an aromatic or 0 heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which ^{can be substituted by one or more radicals R 2} , or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which can be replaced by a or more radicals R ² can be substituted; two residues ^

R ^e also form a ring system with one another or a radical R ^e with a radical R ^{1 or with another group;} s is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, particularly preferably 0, 1 or 2; 0 t is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3, or 4, particularly preferably 0, 1 or 2; v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 0, 1, 2, 3, or 4.5, particularly preferably 0, 1 or 2.

In a preferred embodiment of the invention, the at least two radicals R, R ^a , R ^b , R ^c , R ^{d form one} with the further groups to which the two radicals R, R ^a , R ^b , R ^c , R ^d bond fused ring, where the two radicals R, R ^a , R ^b , R ^c , R ^d preferably form at least one of the structures of the formulas (RA-1a) to (RA-4f) 5

Formula RA-4a F l RA 4b

Formula RA-4d Formula RA-4e Formula RA-4f where the dashed bonds represent the attachment points via which the two radicals R, R ^a , R ^b , R ^c , R ^d bond, the index m 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the symbols R ¹ , R ² , R ^e and the indices s, and t are those previously, in particular for formula (I) and / or formulas (RA-1) to (RA- 12) have the meaning set out above.

It can also be provided that the at least two radicals R, R ^a , R ^b , R ^c , R ^d , the structures of the formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) form and form a condensed ring, represent radicals R, R ^a , R ^b , R ^c , R ^d from adjacent groups X ¹ , X ² , X ³ , X ⁴ or represent radicals R, each of bond adjacent carbon atoms, these carbon atoms preferably being connected via a bond

In a further preferred embodiment, at least two radicals R, R ^a , R ^b , R ^c , R ^{d form} a condensed ring with the other groups to which the two radicals R, R ^a , R ^b , R ^c , R ^{d bond} , wherein the two radicals R, R ^a , R ^b , R ^c , R ^{d form} structures of the formula (RB)

Formula RB where R ^{1 has} the meaning given above, in particular for formula (I), the dashed bonds represent the attachment points via which the two radicals R, R ^a , R ^b , R ^c , R ^d bond, the index m 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y ^{5 is} C (R ¹ ) 2, NR ¹ , NAr ', BR ¹ , BAr',

Is 0 or S, preferably C (R ¹ ) 2, NAr 'or O.

It can be provided here that the at least two radicals R, R ^a , R ^b , R ^c , R ^{d form} the structures of the formula (RB) and form a condensed ring, radicals R ^a , R ^b , R ^c , R ^d from adjacent groups X ¹ , X ² , X ³ , X ⁴ represent or represent radicals R which each bond to adjacent carbon atoms, these carbon atoms preferably being connected to one another via a bond.

The compounds particularly preferably comprise at least one structure of the formulas (IV-1) to (IV-36), the compounds are particularly preferably selected from compounds of the formulas (IV-1) to (IV-36), the compounds at least one condensed Have ring Formula (IV-7) Formula (IV-8) Formula (IV-15) Formula (IV-16) Formula (IV-23) Formula (IV-24) Formula (IV-31) Formula (IV-32) Formula (IV-35) Formula (IV-36) where the symbols Z, R, R ^a , R ^c and R ^{d have} the meanings given above, in particular for formula (I), the symbol Y ¹ and the indices k and j have the meanings given above, in particular for formulas (IIIa) to (IIId), the symbols Y ² and Y ^{3 have} the meanings given above, in particular for formulas (purple) to (IIIv), the symbol o for the attachment points of the condensed ring and the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

Structures / compounds of the formula (IV-2), (IV-4), (IV-6), (IV- 12), (IV-16), (IV-20), (IV-22), ( IV-24), (IV-30), (IV-34) are preferred.

The compounds particularly preferably comprise at least one structure of the formulas (V-1) to (V-22), the compounds are particularly preferably selected from compounds of the formulas (V-1) to (V-22), the compounds at least one condensed Have ring Formula (V- 7) Formula (V-8) where the symbols Z, R, R ^a , R ^c and R ^{d have} the meanings given above, in particular for formula (I), the symbol Y ¹ and the indices k and j have the meanings given above, in particular for formulas (lla) to (lld ) have mentioned meanings, the symbols Y ² and Y ^{3 have} the meanings given above, in particular for formulas (purple) to (IIIv), the symbol o stands for the attachment points of the condensed ring and the index m 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

Structures / compounds of the formula (V-1), (V-4), (V-5), (V-7), (V-10), (V-12), (V-15), ( V-16), (V-21) are preferred. The condensed ring is preferred, in particular in formulas (IV-1) to (IV-36) and / or (V-1) to (V-22), by at least two radicals R, R ^a , R ^b , R ^c , R ^d and the other groups to which the two radicals R, R ^a , R ^b , R ^c , R ^d bond, the at least two radicals R, R ^a , R ^b , R ^c , R ^d having structures of the formulas (RA-1) to (RA-12) and / or the formula (RB), preferably structures of the formulas (RA-1) to (RA-12).

It can preferably be provided that the compounds have at least two condensed rings, at least one condensed ring being formed by structures of the formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) and another ring is formed by structures of the formulas (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB), the compounds having at least one structure of the formulas (VI-1 ) to (VI-22), preferably the compounds are selected from the compounds of the formulas (VI-1) to (VI-22),

where the symbols Z, R, R ^a , R ^c and R ^{d have} the meanings given above, in particular for formula (I), the symbol Y ¹ and the indices k and j have the meanings given above, in particular for formulas (lla) to (lld ) have given meanings, the symbols Y ² and Y ^{3 have} the meanings given above, in particular for formula (purple) to (II Iv), the symbol o stands for the attachment points.

Structures / compounds of the formula (VI-1), (VI-4), (VI-5), (VI- 7), (VI-10), (VI-12), (VI-15), ( VI-16), (VI-19) preferred.

In particular in the formulas (IV-1) to (IV-36), (V-1) to (V-22) and / or (VI-1) to (VI-22) the sum of the indices k, j and m preferably 0, 1,

2 or 3, particularly preferably 1 or 2.

It can be provided here that the formulas (VI-1) to (VI-22) have at least two condensed rings, the condensed rings being the same and the two radicals R, R ^a , R ^b , R ^c , R ^d formed part can be represented by at least one structure of the formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f).

Furthermore, it can be provided that the formulas (VI-1) to (VI-22) have at least two condensed rings, wherein the condensed rings are different and the two radicals R, R ^a , R ^b , R ^c , R ^d formed part can each be represented by at least one structure of the formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f).

In addition, it can be provided that the formulas (VI-1) to (VI-22) have at least two condensed rings, wherein the condensed rings are different and one of the two condensed rings has a part formed by two radicals R, which is through at least one of the structures of the formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) can be represented and one of the two fused rings is formed by two radicals R, R ^a , R ^b , R ^c , R ^{d has} formed part which can be represented by one of the structures of the formula (RB). Furthermore, it can be provided that the substituents R, R ^a , R ^b , R ^c , R ^d and R ^e , R ¹ and R ² according to the above formulas with the ring atoms of the ring system to which the R, R ^a , R ^b , R ^c , R ^d and R ^e , R ¹ and R ² bond, do not form a condensed aromatic or heteroaromatic ring system. This includes the formation of a condensed aromatic or heteroaromatic ring system with possible substituents R ¹ and R ² , which can be bonded to the radicals R, R ^a , R ^b , R ^c , R ^d , R ^e and R ^1.

If two radicals, which can in particular be selected from R, R ^a ,

R ^b , R ^c , R ^d , R ^e , R ¹ and / or R ² form a ring system with one another, this can be mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic. The radicals which form a ring system with one another can be adjacent, ie these radicals are bonded to the same carbon atom or to carbon atoms that are directly bonded to one another, or they can be further apart. Furthermore, the ring systems provided with the substituents R, R ^a , R ^b , R ^c , R ^d , R ^e R ¹ and / or R ^{2 can} also be connected to one another via a bond, so that ring closure can thereby be brought about. In this case, each of the corresponding binding sites is preferably provided with a substituent R, R ^a , R ^b , R ^c , R ^d , R ^e , R ¹ and / or R ² .

According to a preferred embodiment, a compound according to the invention is characterized by at least one of the structures according to formula (I), (IIIa) to (IIId), (purple) to (IIIv), (IV-1) to (IV-36), (V- 1) to (V-22) and / or (VI-1) to (VI-22) can be displayed. Compounds according to the invention, preferably comprising structures according to formula (I), (IIIa) to (IIId), (purple) to (IIIv), (IV-1) to (IV-36), (V-1) to (V -22) and / or (VI-1) to (VI-22) have a molecular weight of less than or equal to 5000 g / mol, preferably less than or equal to 4000 g / mol, particularly preferably less than or equal to 3000 g / mol, especially preferably less or equal to 2000 g / mol and very particularly preferably less than or equal to 1200 g / mol.

Furthermore, preferred compounds according to the invention are distinguished by the fact that they can be sublimed. These compounds generally have a molar mass of less than approx. 1200 g / mol. Preferred aromatic or heteroaromatic ring systems R, R ^a , R ^b , R ^c , R ^d , Ar 'and / or Ar are selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which can be linked via the 1-, 2-, 3- or 4-position, spirobifluoren, which can be linked via the 1-, 2-, 3- or 4-position, naphthalene, in particular 1- or 2-linked naphthalene, indole, benzofuran, benzothiophene, carbazole, which via the 1-, 2-, 3-, 4- or 9-position, dibenzofuran, 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 can, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, whichever Partly with one or more radicals R ¹ or R can be substituted.

It can preferably be provided that at least one substituent R, R ^a , R ^b , R ^c , R ^d, identically or differently on each occurrence, is selected from the group consisting of H, D, a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 20 carbon atoms or an aromatic or heteroaromatic ring system selected from the groups of the following formulas Ar-1 to Ar-75, where the substituents R, R ^a , R ^b , R ^c , R ^{d are} preferably either a ring according to the Structures of the formulas (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB) or the substituents R, R ^a , R ^b , R ^c , R ^{d are} identical or different is selected on each occurrence from the group consisting of F1, D or an aromatic or heteroaromatic ring system selected from the groups of the following formulas Ar-1 to Ar-75, and / or the group Ar 'is selected identically or differently on each occurrence from the groups of the following formulas Ar-1 to Ar-75,

 where R ^{1 has} the meanings given above, the dashed line

Binding represents the connection point and the following still applies:

Ar ¹ is on each occurrence, identically or differently, a bivalent aromatic or heteroaromatic ring system with 6 to 18 aromatic ring atoms, which can in each case be substituted ^{by one or more radicals R 1;}

A is on each occurrence, identically or differently, C (R ¹ ) 2, NR ¹ , 0 or S; p is 0 or 1, where p = 0 means that the group Ar ¹ does not exist and that the corresponding aromatic or heteroaromatic group is bonded directly to HetAr; q is 0 or 1, where q = 0 means that no group A is bonded to this position and radicals R ^{1 are} bonded to the corresponding carbon atoms instead.

If the above-mentioned groups for Ar have several groups A, then all combinations from the definition of A come into consideration. Preferred embodiments are then those in which one group A is NR ¹ and the other group A is C (R ¹ ) 2 or in which both groups A are NR ¹ or in which both groups A are 0. If A stands for NR ¹ , the substituent R ¹ which is bonded to the nitrogen atom preferably stands 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.} In a particularly preferred embodiment, this substituent R ^{1 is the} same or different on each occurrence for an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, in particular with 6 to 18 aromatic ring atoms, which has no condensed aryl groups and which has no condensed heteroaryl groups , in which two or more aromatic or heteroaromatic 6-ring groups are fused directly to one another, and which in each case can also be substituted ^{by one or more radicals R 2.} Phenyl, biphenyl, terphenyl and quaterphenyl with Ver knüpfungsmustern, as listed above for Ar-1 to Ar-11, these structures can be substituted by one or more radicals R ² ^{instead of R 1} , but are preferably unsubstituted. Triazine, pyrimidine and quinazoline are also preferred, as listed above for Ar-47 to Ar-50, Ar-57 and Ar-58, it being possible for these structures to be substituted by one or more radicals R ² ^{instead of R 1.}

Preferred substituents R, R ^a , R ^b , R ^c , R ^d and R ^{e are} described below.

In a preferred embodiment of the invention, R, R ^a , R ^b , R ^c , R ^d, identically or differently on each occurrence, are selected from the group consisting of H, D, F, CN, NO 2, Si (R ¹ ) 3, B (OR ¹ ) 2, a straight-chain alkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, where the alkyl group ^{can be substituted by one or more radicals R 1} , or an aromatic table or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ring atoms, which can in each case be substituted ^{by one or more radicals R 1.}

In a further preferred embodiment of the invention, the substituent R, R ^a , R ^b , R ^c , R ^{d is} identical or different on each occurrence selected from the group consisting of F1, D, F, a straight-chain alkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, it being possible for the alkyl group to be substituted in ^{each case by one or more radicals R 1} , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ring atoms, which can in each case be substituted ^{by one or more radicals R 1.}

It can also be provided that at least one substituent R, R ^a , R ^b , R ^c , R ^d, identically or differently on each occurrence, is selected from the group consisting of H, D, an aromatic or heteroaromatic ring system with 6 to 30 aromatic rings Ring atoms, which can be substituted by one or more radicals R ¹ , or a group N (Ar ') 2. In a further preferred embodiment of the invention, the substituents R either form a ring according to the structures of the formulas (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB) or R is the same or selected differently on each occurrence from the group consisting of H, D, an aromatic or heteroaromatic ring system with 6 to 30 aromatic ring atoms, which ^{can be substituted by one or more radicals R 1} , or a group N (Ar) 2. Particularly preferred is the substituent R,

R ^a , R ^b , R ^c , R ^d, identically or differently on each occurrence, selected from the group consisting of Fl or an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, preferably with 6 to 18 aromatic ring atoms, particularly preferably with 6 to 13 aromatic ring atoms, each of which can be substituted ^{by one or more radicals R 1.}

In a preferred embodiment of the invention, R ^e, identically or differently on each occurrence, is selected from the group consisting of a straight-chain alkyl group with 1 to 20 carbon atoms or a branched or cyclic alkyl group with 3 to 20 carbon atoms, the alkyl group in each case may be substituted by one or more radicals R ¹ , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, preferably with 5 to 40 aromatic ones Ring atoms, each of which can be substituted ^{by one or more radicals R 1.}

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

In a preferred embodiment of the invention, R ^{e is} selected identically or differently at each occurrence from the group consisting of a straight-chain alkyl group with 1 to 6 carbon atoms or a cyclic alkyl group with 3 to 6 carbon atoms, the alkyl group in each case with a or more radicals R ¹ can be substituted, or an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, which in each case can be substituted ^{by one or more radicals R 1;} two radicals R ^{e can} also form a ring system with one another. ^{R e} is particularly preferably selected identically or differently on each occurrence from the group consisting of a straight-chain alkyl group with 1, 2, 3 or 4 carbon atoms or a branched or cyclic alkyl group with 3 to 6 carbon atoms, the alkyl group in each case may be substituted with one or more radicals R ¹ , but is preferably unsubstituted, or an aromatic ring system with 6 to 12 aromatic ring atoms, in particular with 6 aromatic ring atoms, each of which can be substituted by one or more, preferably non-aromatic radicals R ¹ , but is preferably unsubstituted; two radicals R ^e here can form a ring system with one another. ^{R e} is very particularly preferably selected identically or differently on each occurrence from the group consisting of a straight-chain alkyl group with 1, 2, 3 or 4 carbon atoms, or a branched alkyl group with 3 to 6 carbon atoms. ^{R e} very particularly preferably represents a methyl group or a phenyl group, where two phenyl groups can together form a ring system, a methyl group being preferred over a phenyl group.

Preferred aromatic or heteroaromatic ring systems Substituents R, R ^a , R ^b , R ^c , R ^d , R ^e or Ar or Ar 'are selected from phenyl, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, fluorene, which 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, in particular 1- or 2- linked naphthalene, indole, benzofuran, benzothiophene, carbazole, which via the 1-, 2-, 3- or 4-position, dibenzofuran, 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 can, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or Triphenylene, which can each be substituted by one or more radicals R, R ¹ or R ^2. The structures Ar-1 to Ar-75 listed above are particularly preferred, structures of the formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), ( Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), (Ar-75), preferred and structures of the formulas (Ar-1), (Ar-2 ), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16) are particularly preferred. With regard to the structures Ar-1 to Ar-75, it should be noted that these are represented with a substituent R ¹ . In the case of the ring systems Ar, these substituents R ^{1 are to be} replaced by R and in the case of R ^e , these substituents R ^{1 are to be} replaced by R ² . Further suitable groups R, R ^a , R ^b , R ^c , R ^d are groups of the formula -Ar ⁴ -N (Ar ² ) (Ar ³ ), where Ar ² , Ar ³ and Ar ^{4 are} identically or differently on each occurrence are an aromatic or heteroaromatic ring system with 5 to 24 aromatic ring atoms, which can in each case be substituted ^{by one or more radicals R 1.} The total number of aromatic ring atoms of Ar ² , Ar ³ and Ar ^{4 is} a maximum of 60 and preferably a maximum of 40.

Ar ⁴ and Ar ² can be linked to one another and / or Ar ² and Ar ^{3 to} one another by a group selected from C (R ¹ ) 2, NR ¹ , O or S. The linkage of Ar ⁴ and Ar ² with one another or of Ar ² and Ar ³ with one another is preferably carried out in each case ortho to the position of the linkage with the nitrogen atom. In a further embodiment of the invention, none of the groups Ar ² , Ar ³ or Ar ⁴ are connected to one another.

^{Ar 4} is preferably an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, preferably with 6 to 12 aromatic ring atoms, which can each be substituted with one or more radicals R ¹ . ^{Ar 4} is particularly preferably selected from the group consisting of ortho-, meta- or para-phenylene or ortho-, meta- or para-biphenyl, which can each be ^{substituted by one or more radicals R 1} , but are preferably unsubstituted. ^{Ar 4} is very particularly preferably an unsubstituted phenylene group.

^{Ar 2} and Ar ³ are preferably, identically or differently on each occurrence, an aromatic or heteroaromatic ring system with 6 to 24 aromatic ring atoms, which can in each case be substituted ^{by one or more radicals R 1.} Particularly preferred groups Ar ² and Ar ³ , identically or differently on each occurrence, are selected from the group consisting of benzene, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta -, para- or branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene, 1-, 2-,

3- or 4-carbazole, 1-, 2-, 3- or 4-dibenzofuran, 1-, 2-, 3- or 4-dibenzothiophene, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2 -,

4- or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene or tri- phenylene, each of which can be substituted by one or more radicals R ^1. ^{Ar 2} and Ar ^3, identically or differently on each occurrence, are very particularly preferably selected from the group consisting of benzene, biphenyl, in particular ortho-, meta- or para-biphenyl, terphenyl, in particular ortho-, meta-, para or branched Ter - phenyl, quaterphenyl, especially ortho-, meta-, para- or ver branched quaterphenyl, fluorene, especially 1-, 2-, 3- or 4-fluorene, or spirobifluorene, especially 1-, 2-, 3- or 4- Spirobifluoren.

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

In a further preferred embodiment of the invention, R ^2, identically or differently on each occurrence, is H, an alkyl group with 1 to 4 carbon atoms or an aryl group with 6 to 10 carbon atoms which is substituted by an alkyl group with 1 to 4 carbon atoms can be, but is preferably unsubstituted.

In compounds according to the invention which are processed by vacuum evaporation, the alkyl groups preferably have not more than five carbon atoms, particularly preferably not more than 4 carbon atoms, entirely particularly preferably not more than 1 carbon atom. For compounds that are processed from solution, compounds are also suitable which are substituted with alkyl groups, in particular branched alkyl groups, with up to 10 carbon atoms or which are substituted with oligoarylene groups, for example ortho-, meta-, para- or branched terphenyl or quaterphenyl groups.

Furthermore, it can be provided that the compound has exactly two or exactly three structures according to formula (I), (IIIa) to (IIId), (purple) to (IIIv), (IV-1) to (IV-36), (V -1) to (V-22) and / or (VI-1) to (VI-22).

In a preferred embodiment, the compounds are selected from compounds according to the formula (D-1) or (D-2). where the group L ^{1 represents} a connecting group, preferably a bond or an aromatic or heteroaromatic ring system with 5 to 40, preferably 5 to 30 aromatic ring atoms, which is through one or more radicals R ¹ can be substituted, and the other symbols and indices used have the meanings given above, in particular for formula (I).

In a further preferred embodiment of the invention, L ^{1 represents} a bond or an aromatic or heteroaromatic ring system with 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system with 6 to 12 carbon atoms, which can be substituted ^{by one or more radicals R 1} , but is preferably unsubstituted, where R ^{1 can have} the meaning given above, in particular for formula (I). ^{L 1 is} particularly preferably an aromatic ring system with 6 to 10 aromatic ring atoms or a heteroaromatic ring system with 6 to 13 heteroaromatic ring atoms, which ^{can be substituted by one or more radicals R 2} , but is preferably unsubstituted, where R ^{2 is} the above , in particular for formula (I) can have the meaning mentioned.

^{Furthermore, the symbol L 1} set out in formula (D2), among other things, preferably stands identically or differently on each occurrence for a bond or an aryl or fleteroaryl radical having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, particularly preferably 6 to 10 ring atoms, so that an aromatic or heteroaromatic group of an aromatic or heteroaromatic ring system is bonded directly, ie via an atom of the aromatic or heteroaromatic group, to the respective atom of the further group.

Furthermore, it can be provided that the group L ¹ set out in formula (D2) comprises an aromatic ring system with at most two condensed aromatic and / or heteroaromatic 6-membered rings, preferably no condensed aromatic or heteroaromatic ring system. Accordingly, naphthyl structures are preferred over anthracene structures. Furthermore, fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structures are preferred over naphthyl structures. Structures which have no condensation, such as, for example, phenyl, biphenyl, terphenyl and / or quaterphenyl structures, are particularly preferred.

Examples of suitable aromatic or heteroaromatic ring systems L ¹ are selected from the group consisting of ortho-, meta- or para-phenylene, ortho-, meta- or para-biphenylene, terphenylene, especially branched terphenylene, quaterphenylene, especially branched quaterphenylene, fluorenylene, Spirobifluorenylene, dibenzofuranylene, dibenzothienylene and carbazolylene, each of which ^{can be substituted by one or more radicals R 1} , but are preferably unsubstituted.

The above-mentioned preferred embodiments can be combined with one another as desired within the restrictions 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;



30th

35



Preferred embodiments of compounds according to the invention are described in more detail in the examples, it being possible for these compounds to be used alone or in combination with others for all of the uses according to the invention. Provided that the conditions mentioned in claim 1 are met, the preferred embodiments mentioned above can be combined with one another as desired. In a particularly preferred embodiment of the invention, the above-mentioned preferred embodiments apply simultaneously.

The compounds according to the invention can in principle be prepared by various methods. However, the methods described below have proven to be particularly suitable.

The present invention therefore further provides a process for the preparation of the compounds according to the invention, in which a basic structure with at least one of the groups W ¹ , W ² , W ³ , W ⁴ or a precursor of one of the groups W ¹ , W ² , W ³ , W ^{4 is} synthesized and the group Z is introduced by means of a metalation reaction, a nucleophilic aromatic substitution reaction or a coupling reaction.

Suitable compounds comprising a basic structure with a group W ¹ , W ² , W ³ , W ⁴ can in many cases be obtained commercially, the starting compounds set out in the examples being obtainable by known processes, so reference is made to them.

These compounds can be reacted with further compounds by known coupling reactions, the necessary conditions for this being known to the person skilled in the art and detailed information in the examples helping the person skilled in the art to carry out these reactions.

Particularly suitable and preferred coupling reactions, all of which lead to C-C linkages and / or CN linkages, are those according to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA and HIYAMA. These reactions are well known, the examples providing further guidance to those skilled in the art. The basics of the manufacturing processes outlined above are in

Principle known from the literature for similar compounds and can easily be used by the person skilled in the art for the preparation of the compounds according to the invention

Connections can be adjusted. More information can be found at the

Examples are taken.

By these methods, optionally followed by purification, e.g. B. recrystallization or sublimation, the compounds according to the invention can be obtained in high purity, preferably more than 99% (determined by means of ¹ H-NMR and / or HPLC).

The compounds according to the invention can also be mixed with a polymer. It is also possible to incorporate these compounds covalently into a polymer. This is possible in particular with compounds which are substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic acid esters, or with reactive, polymerizable groups such as olefins or oxetanes. These can be used as monomers for producing corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization takes place preferably via the halogen functionality or the boronic acid functionality or via the polymerizable group. It is also possible to crosslink the polymers via such groups. The compounds and polymers according to the invention can be used as a crosslinked or uncrosslinked layer.

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

To produce the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. Preference is given to copolymers in which the units of the formula (I) or the preferred embodiments set out above and below are present in an amount of 0.01 to 99.9 mol%, preferably 5 to 90 mol%, particularly preferably 20 to 80 mol%. Suitable and preferred comonomers which form the polymer backbone are selected from fluorene (e.g. according to EP 842208 or WO 2000/022026), spirobifluoren (e.g. according to EP 707020, EP 894107 or WO 2006/061181), para phenylenes (e.g. according to WO 92/18552), carbazoles (e.g. according to WO 2004/070772 or WO 2004/113468), thiophenes (e.g. according to EP 1028136), dihydrophenanthrenes (e.g. according to WO 2005/014689), cis- and trans-indenofluorenes (e.g. according to WO 2004/041901 or WO 2004/113412), ketones (e.g. according to WO 2005/040302), phenanthrenes (e.g. according to WO 2005 / 104264 or WO 2007/017066) or several of these units. The polymers, oligomers and dendrimers can also contain further units, for example hole transport units, in particular those based on triarylamines, and / or electron transport units.

Furthermore, compounds according to the invention which are distinguished by a high glass transition temperature are of particular interest. In this context, compounds according to the invention are particularly preferred, comprising structures according to the formula (I) or the preferred embodiments set out above and below which have a glass transition temperature of at least 70 ° C., particularly preferably of at least 110 ° C., very particularly preferably of at least 125 ° C and particularly preferably at least 150 ° C, determined according to DIN 51005 (version 2005-08). For the processing of 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 can be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 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, ethylbenzoate, 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, diethylene glycol monobutyl ether, tripropylene glycol monobutyl ether, tripropyleneglycol, 1-benzene, 1-propylene glycol, 1-octylene glycol, 1-propylene glycol, 1-benzenedimethyl ether, 1-hexylene glycol, bis-1-propylene glycol, 1-octylene glycol, 1-benzo-propylene glycol, 1-octylbenzene-2-benzene-1-benzene, bis-1-propylene glycol, 2-pentylene 3,4-dimethylph enyl) ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexylhexanoate or mixtures of these solvents.

The present invention therefore also provides a formulation or a composition containing at least one compound according to the invention and at least one further compound. The further compound can be, for example, a solvent, in particular one of the above-mentioned solvents or a mixture of these solvents. If the further compound comprises a solvent, this mixture is referred to herein as a formulation. The further compound can, however, also be at least one further organic or inorganic compound which is also used in the electronic device, for example an emitter and / or a matrix material, these compounds being different from the differentiate compounds according to the invention. Suitable emitters and matrix materials are listed below in connection with the organic electroluminescent device. The further compound can also be polymeric.

The present invention therefore again further provides a composition containing a compound according to the invention and at least one further organically functional material. Functional materials are generally the organic or inorganic materials that are inserted between the anode and cathode. The organically functional material is preferably selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that show TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocking materials, hole blocking materials, wide band Gap materials and n-dopants.

Another object of the present invention is the use of a compound according to the invention in an electronic device, in particular in an organic electroluminescent device, preferably as an emitter, particularly preferably as a green, red or blue emitter. In this connection, compounds according to the invention preferably show fluorescent properties and thus preferably provide fluorescent emitters. Furthermore, compounds according to the invention can be used as host materials, electron transport materials and / or hole conductor materials. In particular, compounds according to the invention in which the group Z stands for N can advantageously be used as hole conductor material.

Yet another subject matter of the present invention is an electronic device containing at least one compound according to the invention. An electronic device in the sense of the present invention is a device which contains at least one layer which contains at least one organic compound. The component can in this case also contain inorganic materials or also layers which are composed entirely of inorganic materials.

The electronic device is preferably selected from the group consisting of Particularly preferably electronic device is selected from the group consisting of organic electroluminescent devices (OLEDs, sOLED, PLEDs, LECs, etc.), preferably organic light-emitting diodes (OLEDs), organic light-emitting diodes based on small molecules (sOLEDs), organic light-emitting diodes based on polymers (PLEDs), light-emitting electrochemical cells (LECs), organic laser diodes (O lasers), "organic plasmon emitting devices" (DM Koller et al., Nature Photonics 2008, 1-4); organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quench devices (O-FQDs) and organic electrical sensors, preferably organic electroluminescent devices (OLEDs, sOLED, PLEDs, LECs, etc.), particularly preferably organic light-emitting diodes (OLEDs), organic light-emitting diodes based on small molecules (sOLEDs), organic light-emitting diodes based on polymers (PLEDs), especially phosphorescent OLEDs.

The organic electroluminescent device contains a cathode, anode and at least one emitting layer. In addition to these layers, it can also 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 and / or charge generation layers. Interlayers, which for example have an exciton-blocking function, can also be introduced between two emitting layers. It should be noted, however, that it is not necessary for each of these layers to be present. The organic electrical luminescent device contain an emitting layer, or it can contain a plurality of emitting layers. If several emission 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, the three layers showing blue, green and orange or red emission. The organic electroluminescent device according to the invention can also be a tandem electroluminescent device, in particular for white-emitting OLEDs.

The compound according to the invention can be used in different layers, depending on the precise structure. Preference is given to an organic electroluminescent device containing a compound of the formula (I) or the preferred embodiments set out above in an emitting layer as an emitter, preferably a red, green or blue emitter.

If the compound according to the invention is used as an emitter in an emitting layer, a suitable matrix material which is known as such is preferably used.

A preferred mixture of the compound according to the invention and a matrix material contains between 99 and 1% by volume, preferably between 98 and 10% by volume, particularly preferably between 97 and 60% by volume, in particular between 95 and 80% by volume of matrix material based on the total mixture of emitter and matrix material. Correspondingly, the mixture contains between 1 and 99% by volume, preferably between 2 and 90% by volume, particularly preferably between 3 and 40% by volume, in particular between 5 and 20% by volume of the emitter based on the total mixture made of emitter and matrix material.

Suitable matrix materials which can be used in combination with the compounds according to the invention are aromatic Ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, e.g. B. according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives, e.g. B. CBP (N, N-biscarbazolylbiphenyl) or those in 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. B. according to WO 2010/136109, WO 2011/000455, WO 2013/041176 or WO 2013/056776, azacarbazole derivatives, e.g. B. according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar matrix materials, e.g. B. according to WO 2007/137725, silanes, e.g. B. according to WO 2005/111172, aza borole or boronic ester, z. B. according to WO 2006/117052, triazine derivatives, e.g. B. according to WO 2007/063754, WO 2008/056746, WO 2010/015306, WO 2011/057706, WO 2011/060859 or WO 2011/060877, zinc complexes, e.g. B. according to EP 652273 or WO 2009/062578, diazasilol or tetraazasilol derivatives, z. B. according to WO 2010/054729, diazaphosphole derivatives, e.g. B. 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. B. according to WO 2012/048781, dibenzofuran derivatives, e.g. B. according to WO 2015/169412, WO 2016/015810, WO 2016/023608, WO 2017/148564 or WO 2017/148565 or biscarbazole, e.g. B. according to JP 3139321 B2.

Furthermore, a connection can be used as a co-host which does not participate or does not participate to a significant extent in the charge transport, as described, for example, in WO 2010/108579. In particular, in combination with the compound according to the invention as a co-matrix material, compounds are suitable which have a large band gap and themselves do not, or at least not to a significant extent, participate in the charge transport of the emitting layer. Such materials are preferably pure hydrocarbons. Examples of such materials can be found, for example, in WO 2009/124627 or in WO 2010/006680.

In a preferred embodiment, a compound according to the invention which is used as an emitter is preferably used in combination with one or more phosphorescent materials (triplet emitter) and / or a compound which is a TADF host material (thermally activated delayed fluorescence). A hyperfluorescence and / or hyperphosphorescence system is preferably formed here.

WO 2015/091716 A1 and WO 2016/193243 A1 disclose OLEDs which contain both a phosphorescent compound and a fluorescent emitter in the emission layer, the energy being transferred from the phosphorescent compound to the fluorescent emitter (hyperphosphorescence). In this context, the phosphorescent compound behaves like a host material. As the person skilled in the art knows, host materials have higher singlet and triplet energies compared to the emitter, so that the energy of the host material is also transferred to the emitter as optimally as possible. The systems disclosed in the prior art have precisely such an energy relation.

Phosphorescence in the context of this invention is understood to mean the luminescence from an excited state with a higher spin multiplicity, that is to say a spin state> 1, in particular from an excited triplet state. For the purposes of this application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum and copper complexes, are to be regarded as phosphorescent compounds.

Particularly suitable phosphorescent compounds (= triplet emitters) are compounds which, with suitable excitation, emit light, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80 , especially a metal with this atomic number. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium are preferably used as phosphorescent emitters, in particular compounds containing iridium or platinum. 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 2018/001990, WO 2018/019687, WO 2018/019688, WO 2018/041769,

WO 2018/054798, WO 2018/069196, WO 2018/069197, WO 2018/069273, WO 2018/178001, WO 2018/177981, WO 2019/020538,

WO 2019/115423, WO 2019/158453 and WO 2019/179909 can be found. In general, all phosphorescent complexes as used according to the prior art for phosphorescent electroluminescent devices and as they are known to the person skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art can use further phosphorescent complexes without any inventive step.

A compound according to the invention can preferably be used in combination with a TADF floss material and / or a TADF emitter, as set out above.

The process known as thermally activated delayed fluorescence (TADF = “thermally activated delayed fluorescence”) is described, for example, by B. H. Uoyama et al. , Nature 2012, Vol. 492, 234. To enable this process, there is a comparatively small singlet-triplet distance AE (Si - Ti) in the emitter of, for example, less than about

2000 cm ¹ required. In order to open the spin-forbidden transition Ti - »Si, a further connection can be provided in the matrix in addition to the emitter, which has a strong spin-orbit coupling, so that the spatial proximity and the possible interaction between the An inter-system crossing is made possible for molecules, or the spin-orbit coupling is generated via a metal atom contained in the emitter.

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

Furthermore, an organic electroluminescent device is preferred, is an organic electroluminescent device containing a compound according to formula (I) or the preferred embodiments set out above in a hole-conducting layer as hole conductor material. In this connection, compounds in which Z is N are particularly preferred.

In the further layers of the organic electroluminescent device according to the invention, all materials can be used as they are usually used according to the prior 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 according to formula (I) or the preferred embodiments set out above, without inventive intervention.

An organic electroluminescent device is also preferred, characterized in that one or more layers are coated with 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.} It is also possible that the initial pressure is even lower, for example less than 10 ⁷ mbar.

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

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

Formulations for applying a compound according to formula (I) or their or their preferred embodiments set out above are new. The present invention therefore also relates to formulations containing at least one solvent and a compound according to formula (I) or their preferred embodiments set out above.

Hybrid methods are also possible in which, for example, one or more layers are applied from solution and one or more additional layers are vapor-deposited.

These methods are generally known to the person skilled in the art and can be applied by him to organic electroluminescent devices containing the compounds according to the invention without any inventive step. The compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished from the prior art in particular by an improved service life. The other electronic properties of the electroluminescent devices, such as efficiency or operating voltage, remain at least as good. In a further variant, the compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished from the prior art in particular by an improved efficiency and / or operating voltage and a longer service life.

The electronic devices according to the invention, in particular organic electroluminescent devices, are distinguished by one or more of the following surprising advantages over the prior art:

1. Electronic devices, in particular organic electroluminescent devices containing compounds according to formula (I) or the preferred embodiments set out above and below as emitters have very narrow emission bands with low FWHM values (full width half maximum) and lead to particularly pure color emission , recognizable by the small CIE y values. It is particularly surprising here that both blue emitters with low FWHM values and emitters with low FWHM values are provided which emit in the green, yellow or red range of the color spectrum.

2. Electronic devices, in particular organic electroluminescent devices containing compounds according to formula (I) or the preferred embodiments set out above and below, in particular as emitters and / or as hole conductor material, have a very good service life. In this case, these connections cause, in particular, a low roll-off, that is to say a small drop in the power efficiency of the device at high luminance levels. 3. Electronic devices, especially organic ones

Electroluminescent devices containing compounds according to

Formula (I) or the preferred ones set out above and below

Embodiments as an emitter and / or as a hole conductor material have excellent efficiency. Here, compounds according to the invention according to formula (I) or the preferred embodiments set out above and below bring about a low operating voltage when used in electronic devices.

4. The compounds according to the invention according to formula (I) or the preferred ones set out above and below

Embodiments show a very high stability and

Lifespan.

5. With compounds of the formula (I) or the preferred embodiments set out above and below, the formation of optical devices in electronic devices, in particular organic electroluminescent devices

Loss channels are avoided. As a result, these devices are characterized by a high PL and thus high EL efficiency of emitters and excellent energy transfer from the matrices to dopants.

6. Compounds according to formula (I) or the preferred embodiments set out above and below exhibit excellent glass film formation.

7. Compounds according to formula (I) or the preferred embodiments set out above and below form very good films from solutions and show excellent solubility.

These advantages mentioned above are not accompanied by an inordinately large deterioration in other electronic properties. It should be noted that variations of the embodiments described in the present invention fall within the scope of this invention. Each feature disclosed in the present invention can, unless this is explicitly excluded, be replaced by alternative features that serve the same, an equivalent or a similar purpose. Thus, unless otherwise stated, each feature disclosed in the present invention is to be regarded as an example of a generic series or an equivalent or similar feature.

All features of the present invention can be combined with one another in any way, unless certain features and / or steps are mutually exclusive. This is particularly true of preferred features of the present invention. Likewise, features of non-essential combinations can be used separately (and not in combination).

It should also be pointed out that many of the features, and in particular those of the preferred embodiments of the present invention, are in themselves inventive and not merely to be regarded as part of the embodiments of the present invention. Independent protection may be sought for these features in addition to or as an alternative to any presently claimed invention.

The teaching on technical action disclosed with the present invention can be abstracted and combined with other examples.

The invention is illustrated in more detail by the following examples, without wishing to restrict it thereby. The person skilled in the art can use the descriptions to carry out the invention in the entire disclosed range and, without inventive intervention, produce further compounds according to the invention 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 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. In the case of compounds that can have several enantiomeric, diastereomeric or tautomeric forms, one form is shown as a representative.

Synthesis of synthons S: Example S1:

A mixture of 13.0 g (110 mmol) benzimidazole [51-17-2], 11.3 g (50 mmol) 1-bromo-2,3-dichlorobenzene [56691-77-4], 27.6 g (130 mmol) tripotassium phosphate, anhydrous [7778-53-2], 240 mg (0.5 mmol) tetramethyl-di-tBuXPhos [857356-94-6], 124 mg (0.5 mmol) palladium (II) acetate [3375-31-3], 50 g glass spheres ( 3 mm diameter) and 250 ml of toluene are stirred at 80 ° C. for 3 h and then at 110 ° C. for 6 h. After cooling, the reaction mixture is mixed with 500 ml of ethyl acetate and 500 ml of water, the org. Phase is separated, once with 500 ml of water and twice with 300 ml of sat. Washed brine and dried over magnesium sulfate. It is filtered through a bed of silica gel pre-slurried with ethyl acetate, the filtrate is concentrated to dryness, the residue is boiled with 50 ml of ethanol, the solid is filtered off, washed twice with 20 ml of ethanol, dried in vacuo and recrystallized from o-xylene. Yield: 14.7 g (42 mmol) 85%; Purity: approx. 95% according to ¹ H-NMR.



 Example dopant D1 Step 1: lithiation of S1

15.5 g (50 mmol) S1 and 200 ml tert-butylbenzene are placed in a heated four-necked flask with a magnetic stirrer bar, dropping funnel, water separator, reflux condenser and argon blanket and cooled to -40 ° C. 64.7 ml (110 mmol) of tert-BuLi, 1.7 M in n-pentane are added dropwise to the mixture over a period of 10 minutes. The reaction mixture is allowed to warm to room temperature and stirred for 3 h at 60 ° C., the n-pentane being distilled off via the water separator.

Step 2: transmetalation and cyclization

The reaction mixture is cooled again to -40 ° C. 5.7 ml (60 mmol) of boron tribromide are added dropwise over a period of about 10 minutes. After the addition is complete, the reaction mixture is stirred at RT for 1 h. The reaction mixture is then cooled to 0 ° C. and 21.0 ml (120 mmol) of di- / propylethylamine are added dropwise over a period of about 30 minutes. The reaction mixture is then stirred at 130 ° C. for 5 h. After cooling, it is diluted with 500 ml of toluene, hydrolyzed by adding 300 ml of aqueous 10% strength by weight potassium acetate solution, and the org. Phase off and concentrate this to dryness in a vacuum. ^{The oily residue is absorbed onto ISOLUTE ®} using DCM and poured over hot with an n-pentane-DCM mixture (5: 1) Filtered silica gel bed. The filtrate is concentrated to dryness. The residue is flash chromatographed, silica gel, n-heptane / ethyl acetate, gradient, automatic column machine Torrent from A. Semrau. Further purification is carried out by repeated industrial extraction crystallization with DCM / acetonitrile mixtures and subsequent fractional sublimation or tempering in a flea vacuum. Yields: 5.5 g (17 mmol) 34%; Purity: approx. 99.9% according to ¹ H-NMR

The following connections can be represented in the same way:

Example Dotand D18P:

Representation from D18 by flash vacuum pyrolysis, carrier gas argon, vacuum approx. 10 ² torr, temperature pyrolysis zone 600 ° C, contact 5% PdO on aluminum oxide. Yield 22%.

1) Vacuum processed devices:

OLEDs according to the invention and OLEDs according to the prior art are produced by 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) that are 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) and within 30 min for improved processing with 20 nm PEDOT: PSS coated (poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate), obtained as CLEVIOS ™ P VP AI 4083 from Heraeus Precious Metals GmbH Germany, spun on from an aqueous solution) and then baked at 180 ° C. for 10 minutes. These coated glass flakes form the substrates to which the OLEDs are applied.

The OLEDs basically have the following layer structure: substrate / hole injection layer 1 (HIL1) consisting of Ref-HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm / hole transport layer 1 (HTL1) made of: 150 nm HTM1 for UV & Blue OLEDs; 50 nm for Green & Yellow OLEDs; 110 mn for red OLEDs / hole transport layer 2 (HTL2) made of: 10 nm for blue OLEDs; 20 nm for Green & Yellow OLEDs; 10 mn for red OLEDs / emission layer (EML): 25 nm for blue OLEDs; 40 nm for Green & Yellow OLEDs; 35 nm for red OLEDs / hole blocking layer (HBL) 10 nm / electron transport layer (ETL) 30 nm / electron injection layer (EIL) made of 1 nm ETM2 / and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer.

First, vacuum-processed OLEDs are described. For this purpose, all materials are thermally vapor deposited in a vacuum chamber. The emission layer always consists of at least one matrix material (host material, host material) and an emitting dopant (dopant, emitter), which is added to the matrix material or the matrix materials by co-evaporation in a certain volume proportion. A specification such as SMB1: D1 (95: 5%) means that the material SEB1 is present in the layer in a volume fraction of 95% and D1 in a proportion of 5%. Similarly, the electron transport layer can also consist of a mixture of two materials. The exact structure of the OLEDs is shown in Table 1. The materials used to produce the OLEDs are shown in Table 3.

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 calculated as a function of the luminance, calculated from current-voltage-luminance characteristics ( IUL characteristics) assuming a Lambertian radiation characteristic. the Electroluminescence spectra are determined at a luminance of 1000 cd / m ² and from this the emission color and the EL-FWHM values (ELectroluminescence - Full Width Half Maximum - width of the EL emission spectra at half the peak height in eV, for better comparability over the entire spectral range) taken.

Use of compounds according to the invention as materials in OLEDs:

The compounds according to the invention can be used, inter alia, as hole transport material and dopant in the emission layer in OLEDs. Compounds D-Ref.1 according to Table 3 are used as a comparison according to the prior art. The results of the OLEDs are summarized in Table 2.

Table 1: Structure of the OLEDs

Table 2: Results of the vacuum-processed OLEDs

Compared to the reference, the compounds according to the invention sometimes show narrower or comparatively narrow electroluminescence spectra, recognizable by the lower or equally large EL-FWHM values (ELectroluminescence - full width half maximum - width of the EL emission spectra in eV at half the peak height) . Narrower electroluminescence spectra lead to significantly improved color purity (lower CIE y values). In addition, the EQE values (external quantum efficiencies) of the examples according to the invention are significantly greater and the operating voltages lower compared to the reference, which leads to significantly improved power efficiencies of the device and thus to lower power consumption.

Claims

1. A compound comprising at least one structure of the formula (I),

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

Z is on each occurrence, identically or differently, N or B;

W ¹ , W ² , W ³ , W ⁴ stand on each occurrence, identically or differently, for N or CR, where at least one W ¹ , W ² , W ³ , W ⁴ per ring stands for N;

X ¹ stands on each occurrence, identically or differently, for N, CR ^a or CAr with the proviso that not more than two of the groups X ¹ , X ² in a cycle stand for N;

X ² stands on each occurrence, identically or differently, for N, CR ^b or CAr with the proviso that not more than two of the groups X ¹ , X ² in a cycle stand for N;

X ³ stands on each occurrence, identically or differently, for N, CR ^C or CAr with the proviso that not more than two of the groups X ³ , X ⁴ in a cycle stand for N; X ⁴ stands on each occurrence, identically or differently, for N, CR ^d ,

CAr or C, if a ring system is formed by a bond with a group X ⁴ , with the proviso that not more than two of the groups X ³ , X ⁴ in a cycle represent N;

Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which can be substituted by one or more radicals R, here the group Ar can form a ring system with at least one group Ar, R or another group;

R, R ^a , R ^b , R ^c , R ^d is on each occurrence, identically or differently, H, D, OH, F, CI, Br, I, CN, N0 ₂ , N (Ar ') ₂ , N (R ¹ ) ₂ , C (= 0) Ar ', C (= 0) R ¹ , C (= 0) OAr', C (= 0) 0R ¹ , C (= 0) N (Ar ') ₂ , C (= 0) N (R ¹ ) ₂ , C (Ar ') ₃ ,

C (R ¹ ) ₃ , Si (Ar ') ₃ , Si (R ¹ ) ₃ , B (Ar') ₂ , B (R ¹ ) ₂ , P (= 0) (Ar ') ₂ , P (= 0 ) (R ¹ ) ₂ , P (Ar ') ₂ , P (R ¹ ) ₂ , S (= 0) Ar', S (= 0) R ¹ , S (= 0) ₂ Ar ', S (= 0 ) ₂ R ¹ ,

OS0 ₂ Ar ', OS0 ₂ R ¹ , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or an alkenyl or alkynyl group with 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group can each be ^{substituted with one or more radicals R 1} , one or more nonadjacent CH ₂ groups being substituted by C. = NR ¹ , -C (= 0) 0-, - SO or S0 ₂ can be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which ^{can be substituted by one or more radicals R 1} , or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, the can be substituted by one or more radicals R ^1; two radicals R, R ^a , R ^b , R ^c , R ^{d can} also form a ring system with one another or with a further group;

Ar 'is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system with 5 to 60 aromatic rings Ring atoms, which can be substituted with one or more radicals R ¹ , two radicals Ar ', which bond to the same C atom, Si atom, N atom, P atom or B atom, also by a single bond or a bridge selected from B (R ¹ ), C (R ¹ ) ₂ , Si (R ¹ ) ₂ , C = 0, C = NR ¹ , C = C (R ¹ ) ₂ ,

0, S, S = 0, S0 ₂ , N (R ¹ ), P (R ¹ ) and P (= 0) R ¹ , be bridged to one another;

R ¹ is on each occurrence, identically or differently, H, D, F, CI, Br, I, CN, N0 ₂ , N (Ar ”) ₂ , N (R ² ) ₂ , C (= 0) Ar”, C ( = 0) R ² , C (= 0) 0Ar ”, C (= 0) 0R ² , P (= 0) (Ar”) ₂ , P (Ar ”) ₂ , B (Ar”) ₂ , B (R ² ) ₂ , C (Ar ”) ₃ , C (R ² ) ₃ , Si (Ar”) ₃ , Si (R ² ) ₃ , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms or an alkenyl group with 2 to 40 carbon atoms, each of which ^{can be substituted by one or more radicals R 2} , where one or more non-adjacent CH ₂ - Groups through -R ² C = CR ² -, -CsC-, Si (R ² ) ₂ , C = 0, C = S, C = Se,

C = NR ² , -C (= 0) 0-, -C (= 0) NR ² -, NR ² , P (= 0) (R ² ), -O-, -S-, SO or S0 ₂ replaced can be and where one or more H atoms can be replaced by D, F, CI, Br, I, CN or N0 ₂ , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each by one or more radicals R ² , or an aryloxy or fleteroaryloxy group with 5 to 60 aromatic ring atoms, which ^{can be substituted by one or more radicals R 2} , or an aralkyl or fleteroaralkyl group with 5 to 60 aromatic ring atoms, which can be substituted with one or more radicals R ² may be substituted, or a combination of these systems; two or more radicals R ¹ here can form a ring system with one another, while one or more radicals R ¹ can form a ring system with another part of the compound;

Ar ”is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which with one or more radicals R ² can be substituted, two radicals Ar ”, which bond to the same C atom, Si atom, N atom, P atom or B atom, also by a single bond or a bridge, selected from B (R ² ) , C (R ² ) ₂ , Si (R ² ) ₂ , C = 0, C = NR ² , C = C (R ² ) ₂ ,

0, S, S = 0, S0 ₂ , N (R ² ), P (R ² ) and P (= 0) R ² , be bridged to one another;

R ² is selected identically or differently on each occurrence from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical with 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms in which one or more H atoms can be replaced by D, F, CI, Br, I or CN and which can be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, two or more substituents R ^{2 here} forming a ring system form.

2. A compound according to claim 1, comprising at least one structure of the formula (lla), (Mb), (llc) and / or (lld), Formula (lld) where Z, X ¹ , X ² , X ³ , X ⁴ , R, R ^a , R ^b , R ^c and R ^{d have} the meanings given in claim 1 and the following applies to the other symbols and indices:

Y ¹ is on each occurrence, identically or differently, a bond, N (Ar '), N (R ¹ ), B (Ar'), B (R ¹ ), P (= 0) (Ar '), P (= 0 ) (R ¹ ), C (= 0), C (Ar ') ₂ , C (R ¹ ) ₂ , Si (Ar') ₂ , Si (R ¹ ) ₂ , 0, S, Se, S = 0, S0 ₂ , C (= 0) N (Ar '), C (= 0) N (R ¹ ), P (Ar') or P (R ¹ ), - (O) CC (O) -, - N ( Ar ') - C (0) -, - (R ¹ ) ₂ CC (R ¹ ) ₂ -, - (R ¹ ) C = C (R ¹ ) -, an aryl or heteroaryl group with 5 to 40 aromatic ring atoms, where the aryl or heteroaryl group bonds to the other parts of the structure via two adjacent and interconnected carbon atoms and ^{can be substituted by one or more radicals R 1} , the symbols R ¹ and Ar 'having the meaning set out in claim 1; j is 0, 1 or 2; p is 0 or 1, where p = 0 means that the group Y ^{1 is} not present; k is 0 or 1, where k = 0 if p = 1.

3. A compound of claim 1 or 2, comprising at least one structure of the formula (lilac) to (lllv),

Formula (purple)

Formula (llld) 9

Formula (I Mg) Formula (lllp) where Z, R, R ^a , R ^b , R ^c and R ^{d have} the meanings given in claim 1, the symbol Y ¹ and the indices k and j in Claim 2 have the meanings mentioned and the other symbols have the following meanings:

Y ² , Y ³ , is on each occurrence, identically or differently, a bond N (Ar '), N (R ¹ ), B (Ar'), B (R ¹ ), P (= 0) (Ar '), P (= 0) (R ¹ ), C (= 0),

C (Ar ') ₂ , C (R ¹ ) ₂ , Si (Ar') ₂ , Si (R ¹ ) ₂ , 0, S, Se, S = 0, S0 ₂ ,

C (= 0) N (Ar '), C (= 0) N (R ¹ ), P (Ar') or P (R ¹ ), where the symbols R ¹ and Ar 'have the meaning given in claim 1; and m is 0, 1, 2, 3, or 4.

4. A compound according to one or more of claims 1 to 3, characterized in that at least two radicals R, R ^a , R ^b , R ^c , R ^d with the further groups to which the two radicals R, R ^a , R ^b , R ^c , R ^d bond, form a condensed ring, the two radicals R, R ^a , R ^b , R ^c , R ^d forming at least one structure of the formulas (RA-1) to (RA-12)

Formula RA-1 Formula RA-2 Formula RA-3 Formula RA-10 Formula RA-11 Formula RA-12 where R ^{1 has} the meaning set out above, the dashed bonds represent the attachment points via which the two radicals R, R ^a , R ^b , R ^c , R ^d bond, and the other symbols have the following meanings:

Y ⁴ is on each occurrence, identically or differently, C (R ¹ ) 2, (R ¹ ) ₂ CC (R ¹ ) ₂ , (R ¹ ) C = C (R ¹ ), NR ¹ , NAr ', 0 or S;

R ^e is on each occurrence, identically or differently, F, a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or an alkenyl or alkynyl group with 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy - Or thioalkoxy group with 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group can each be ^{substituted by one or more radicals R 2} , one or more non-adjacent CH ₂ groups being substituted by or S0 ₂ can be replaced, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which ^{can be substituted by one or more radicals R 2} , or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms which can be substituted ^{by one or more radicals R 2;} two radicals R ^{e can} also form a ring system with one another or one radical R ^e with one radical R ¹ or with another group; s is 0, 1, 2, 3, 4, 5 or 6; t is 0, 1, 2, 3, 4, 5, 6, 7 or 8; v is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.

5. A compound according to one or more of claims 1 to 11, that at least two radicals R, R ^a , R ^b , R ^c , R ^d with the further groups to which the two radicals R, R ^a , R ^b , R ^c , R ^d bond, form a condensed ring, whereby the two radicals R, R ^a , R ^b , R ^c , R ^{d form} structures of the formulas (RA-1a) to (RA-4f),

Formula RA-3a Formula RA-3b Formula RA-4d Formula RA-4e

Formula RA-4f where the dashed bonds represent the attachment points via which the two radicals R, R ^a , R ^b , R ^c , R ^d bond, the index m is 0, 1, 2, 3 or 4 and the symbols R ¹ , R ² , R ^e and the indices s and t have the meaning given above, in particular in claims 1 and 4.

6. A compound according to one or more of claims 1 to 5, that at least two radicals R, R ^a , R ^b , R ^c , R ^d with the further groups to which the two radicals R, R ^a , R ^b , R ^c , R ^d bond, form a condensed ring, where the two radicals R, R ^a , R ^b , R ^c , R ^{d form} the structures of the formula (RB),

Formula RB where R ^{1 has} the meaning given in claim 1, the dashed bonds the attachment points to the atoms of the

Groups to which the two radicals R, R ^a , R ^b , R ^c , R ^d bond represent, the index m is 0, 1, 2, 3 or 4 and Y ^{5 is} C (R ¹ ) ₂ , NR ¹ 'NAr', BR ¹ , BAr ', 0, or S.

7. A compound according to one or more of claims 1 to 6, comprising at least one structure of the formulas (IV-1) to (IV-36), wherein the compounds have at least one condensed ring,

Formula (IV-7) Formula (IV-8) Formula (IV-15) Formula (IV-16) Formula (IV-23) Formula (IV-24) Formula (IV-31) Formula (IV-32) Formula (IV-35) Formula (IV-36) where Z, R, R ^a , R ^c and R ^{d have} the meanings given in Claim 1, the symbol Y ¹ and the indices k and j have the meanings given in Claim 2 , the symbols Y ² and Y ^{3 have} the meanings given in claim 3, the symbol o stands for the attachment points and the index m is 0, 1, 2, 3 or 4.

8. A compound according to one or more of claims 1 to 7, comprising at least one structure of the formulas (V-1) to (V-22), the compounds having at least one condensed ring Formula (V-9) Formula (V-10) where Z, R, R ^a , R ^c and R ^{d have} the meanings mentioned in claim 1, the symbol Y ¹ and the indices k and j have the meanings mentioned in claim 2, the symbols Y ² and Y ^{3 have} those in claim 3 Have the meanings mentioned, the symbol o stands for the attachment points and the index m is 0, 1, 2, 3 or 4.

9. Compound according to one or more of claims 4 to 8, wherein the compounds have at least two condensed rings, wherein at least one condensed ring comprises structures of the formulas (RA-1) to (RA-12) and another ring comprises structures of the formulas ( RA-1) to (RA-12) or (RB), comprising at least one structure of the formulas (VI-1) to (VI-22) where Z, R, R ^a , R ^c and R ^{d have} the meanings given in claim 1, the symbol Y ¹ and the indices k and j have the meanings given in claim 2, the symbols Y ² and Y ^{3 have} the meanings in

Claim 3 have the meanings mentioned and the symbol o stands for the connection points.

10. A compound according to at least one of the preceding claims, characterized in that the compound has exactly two or exactly three structures according to formula (I), (lla) to (lld), (purple) to (Mir), (IV-1) to (IV-36), (V-1) to (V-22) and / or (VI-1) to (VI-22).

11. A compound according to claim 10, selected from compounds of

Formula (D-1) or (D-2),

Formula (D-1) where the group L ^{1 represents} a connecting group, and the other symbols and indices used have the meanings given in claim 1.

12. Oligomer, polymer or dendrimer containing one or more compounds according to one of claims 1 to 9, wherein instead of one

Hydrogen atom or a substituent one or more bonds of the compounds to the polymer, oligomer or dendrimer are present.

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

14. Composition containing at least one compound according to one or more of claims 1 to 11 or an oligomer, polymer or dendrimer according to claim 12 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters which show TADF, Host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocking materials, and hole blocking materials.

15. The method for producing a compound according to one or more of claims 1 to 11, characterized in that a basic structure with at least one of the groups W ¹ , W ² , W ³ , W ⁴ or a precursor of one of the groups W ¹ , W ² , W ³ , W ^{4 is} synthesized and the group Z is introduced by means of a metalation reaction, a nucleophilic aromatic substitution reaction or a coupling reaction.

16. Use of a compound according to one or more of claims 1 to 11 or an oligomer, polymer or dendrimer according to

Claim 12 in an electronic device.

17. Electronic device containing at least one compound according to one or more of claims 1 to 11 or an oligomer,

Polymer or dendrimer according to claim 12.