EP3898605A2

EP3898605A2 - Materials for electronic devices

Info

Publication number: EP3898605A2
Application number: EP19832612.6A
Authority: EP
Inventors: Elvira Montenegro; Teresa Mujica-Fernaud; Florian MAIER-FLAIG; Frank Voges
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2018-12-20
Filing date: 2019-12-17
Publication date: 2021-10-27
Also published as: JP2022514875A; WO2020127145A3; US20220073447A1; TW202039417A; WO2020127145A2; CN113166088A; KR20210105935A

Abstract

The invention relates to materials for use in electronic devices, to methods for producing said materials, and to electronic devices containing said materials.

Description

Materials for electronic devices

The present application relates to fluorenyl-amine compounds of a certain formula which are each unequally substituted in the 9 and 9 'positions. The connections are suitable for use in electronic devices.

Electronic devices in the sense of this application are understood as so-called organic electronic devices (organic electronic devices), which organic Flalbleitermaterialien as

Functional materials included. In particular, this means OLEDs (organic electroluminescent devices). The term OLEDs is understood to mean electronic devices which have one or more layers containing organic compounds and which emit light when electrical voltage is applied. The structure and the general principle of operation of OLEDs are known to the person skilled in the art.

With electronic devices, in particular OLEDs, there is great interest in improving the performance data. No fully satisfactory solution has yet been found on these points.

A big influence on the performance data of electronic

Devices have emission layers and layers with

hole transporting function. New compounds are still being sought for use in these layers, in particular

hole transporting connections and connections that as

hole-transporting matrix material, in particular for phosphorescent emitters, can serve in an emitting layer. For this purpose, in particular connections are sought that have a high

Glass transition temperature, high stability, and high conductivity for holes. A high stability of the connection is one Prerequisite for achieving a long lifespan for the electronic device.

In the prior art, triarylamine compounds in particular are known as hole transport materials and hole transport matrix materials for electronic devices. The triarylamine compounds known for use in electronic devices also include fluorenylamine compounds, i.e. H. Triarylamine compounds in which at least one aryl group is a fluorenyl group.

However, there is still a need for alternative connections that are suitable for use in electronic devices, in particular for connections that have one or more of the advantageous properties mentioned above. There is still a need for improvement in the performance data achieved when using the connections in electronic devices, in particular in terms of service life,

Operating voltage and efficiency of the devices.

It has been found that certain fluorenyl amine compounds are outstandingly suitable for use in electronic devices, in particular for use in OLEDs, again in particular for use as hole transport materials and for use as hole transporting matrix materials, in particular for

phosphorescent emitters. The connections lead to higher

Service life, high efficiency and low operating voltage

Devices. The compounds also preferably have a high glass transition temperature, high stability and high conductivity for holes. The compounds found correspond to a formula (I) where for the variables that occur:

Z is when the group - [Ar1] _k -N (Ar2) (Ar3) is attached to it is C, and Z is when the group - [Ar1] _k -N (Ar2) (Ar3) is not attached to it , the same or different for each occurrence CR1 or N;

Ar1 is the same or different at each occurrence an aromatic ring system with 6 to 40 aromatic ring atoms which is substituted by radicals R3, or a heteroaromatic ring system with 5 to 40 aromatic ring atoms which is substituted by radicals R3;

Ar2 is an aromatic ring system with 6 to 40 aromatic rings

Ring atoms which are substituted with R4 radicals, or a

heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is substituted by radicals R4;

Ar3 is an aromatic ring system with 6 to 40 aromatic rings

Ring atoms which are substituted with R4 radicals, or a

heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is substituted by radicals R4; Ar4 is phenyl which may be substituted by R2 or naphthyl which may be substituted by R2;

Each occurrence of R1 is selected the same or different from H, D, F, CI, Br, I, C (= 0) R5, CN, Si (R5) ₃ , N (R5) ₂ , P (= 0) (R5 ) ₂ , OR5, S (= 0) R5,

S (= 0) ₂ R5, straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 C atoms, alkenyl or alkynyl groups with 2 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein two or more R1 radicals can be linked together and form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted with radicals R5; and wherein one or more CH ₂ groups in said alkyl,

Alkoxy, alkenyl and alkynyl groups by -R5C = CR5-, -C ^ C-, Si (R5) ₂ , C = 0, C = NR5, -C (= 0) 0-, -C (= 0) NR5 -, NR5, P (= 0) (R5), -O-, -S-, SO or S0 ₂ can be replaced; Each occurrence of R2 is selected identically or differently from D, F, CN, Si (R5) ₃ , N (R5) ₂ , aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted by radicals R5, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms which are substituted with R5 radicals;

Each occurrence of R3 is selected identically or differently from Fl, D, F, CI, Br, I, C (= 0) R5, CN, Si (R5) ₃ , N (R5) ₂ , P (= 0) (R5 ) ₂ , OR5, S (= 0) R5,

S (= 0) ₂ R5, straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 C atoms, alkenyl or alkynyl groups with 2 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; in which two or more radicals R3 can be linked to one another and can form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted with radicals R5; and wherein one or more CF groups in said alkyl,

Alkoxy, alkenyl and alkynyl groups by -R5C = CR5-, -C ^ C-, Si (R5) ₂ , C = 0, C = NR5, -C (= 0) 0-, -C (= 0) NR5 -, NR5, P (= 0) (R5), -0-, -S-, SO or SO2 can be replaced; Each occurrence of R4 is the same or different from H, D, F, CI, Br, I, C (= 0) R5, CN, Si (R5) ₃ , N (R5) ₂ , P (= 0) (R5 ) ₂ , OR5, S (= 0) R5,

S (= 0) ₂ R5, straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 C atoms, alkenyl or alkynyl groups with 2 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein two or more R4 radicals can be linked to one another and form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted with radicals R5; and wherein one or more CF groups in said alkyl, alkoxy, alkenyl and alkynyl groups are represented by -R5C = CR5-, -C ^ C-, Si (R5) ₂ , C = 0, C = NR5, -C (= 0) 0-, -C (= 0) NR5-, NR5, P (= 0) (R5), -O-, -S-, SO or SO2 can be replaced;

Each occurrence of R5 is selected identically or differently from H, D, F, CI, Br, I, C (= 0) R6, CN, Si (R6) ₃ , N (R6) ₂ , P (= 0) (R6 ) ₂ , OR6, S (= 0) R6,

S (= 0) ₂ R6, straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 C atoms, alkenyl or alkynyl groups with 2 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; in which two or more radicals R5 can be linked to one another and form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted with radicals R6; and wherein one or more CF groups in said alkyl,

Alkoxy, alkenyl and alkynyl groups by -R6C = CR6-, -C ^ C-, Si (R6) ₂ , C = 0, C = NR6, -C (= 0) 0-, -C (= 0) NR6 -, NR6, P (= 0) (R6), -0-, -S-, SO or SO ₂ can be replaced; Each occurrence of R6 is selected identically or differently from H, D, F, CI, Br, I, CN, alkyl or alkoxy groups with 1 to 20 C atoms, alkenyl or alkynyl groups with 2 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein said alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems can be substituted with one or more radicals selected from F and CN; k is 0, 1, 2, 3 or 4, where in the case k = 0 the group Ar1 is not present and the groups which bind to Ar1 in formula (I) are directly linked to one another; i is 0, 1, 2, 3, 4 or 5; n is 0, 1, 2, 3 or 4; being the two groups

in formula (I) as a whole, taking their substituents into account, are not the same.

The case i = 1 means that a group R2 is bonded to exactly one position of the benzene ring in question. The case n = 1 means that a group R2 is bonded to exactly one position of the benzene ring in question.

The case i = 2, 3, 4 or 5 means that a group R2 is bonded to 2, 3, 4 or 5 different positions of the benzene ring in question. The case n = 2, 3 or 4 means that on 2, 3 or 4 different ones

Positions of the benzene ring in question are each bound to a group R2.

The case i = 0 or n = 0 means that no R2 radicals are bonded to the benzene ring in question, but only Fl atoms.

The following definitions apply to the chemical groups used in the present application. They apply if no more specific definitions are given.

For the purposes of this invention, an aryl group is either a single aromatic cycle, that is to say benzene, or a condensed one aromatic polycycle, for example naphthalene, phenanthrene or anthracene, understood. For the purposes of the present application, a condensed aromatic polycycle consists of two or more individual aromatic cycles condensed with one another. Condensation between cycles means that the cycles share at least one edge with one another. An aryl group in the sense of this invention contains 6 to 40 aromatic ring atoms, none of which is a hetero atom.

For the purposes of this invention, a heteroaryl group is understood to mean either a single heteroaromatic cycle, for example pyridine, pyrimidine or thiophene, or a condensed heteroaromatic polycycle, for example quinoline or carbazole. A condensed heteroaromatic polycycle in the sense of the present

Registration of two or more individual aromatic or heteroaromatic cycles condensed with one another, at least one of the aromatic and heteroaromatic cycles being a heteroaromatic cycle. Condensation between cycles means that the cycles share at least one edge with one another. A

Heteroaryl group in the sense of this invention contains 5 to 40 aromatic ring atoms, at least one of which represents a hetero atom. The heteroatoms of the heteroaryl group are preferably selected from N, O and S.

Under an aryl or heteroaryl group, each with the above

radicals mentioned can be understood to mean, in particular, groups which are derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, triphenylene,

Fluoranthene, benzanthracene, benzphenanthrene, tetracene, pentacen, benzpyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, acridine, acridine, acridine, acridine 6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, Pyrazole, indazole, imidazole, benzimidazole, Benzimidazolo [1, 2- a] benzimidazole, naphthimidazole, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, oxazole, benzoxazole, naphthoxazole, Anthroxazol, Phenanthroxazol, isoxazole, 1, 2-thiazole, 1, 3- Thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzpyrimidine, quinoxaline, pyrazine, phenazine, 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.

An aromatic ring system in the sense of this invention is a system which does not necessarily only contain aryl groups, but which can additionally contain one or more non-aromatic rings which are condensed with at least one aryl group. Not this one

aromatic rings contain only carbon atoms as

Ring atoms. Examples of groups included in this definition are tetrahydronaphthalene, fluorene and spirobifluorene. The term aromatic ring system also includes systems which consist of two or more aromatic ring systems which are connected to one another via single bonds, for example biphenyl, terphenyl, 7-phenyl-2-fluorenyl, quaterphenyl and 3, 5-diphenyl-1-phenyl. An aromatic ring system in the sense of this invention contains 6 to 40 carbon atoms and no heteroatoms in the ring system. The definition of “aromatic ring system” does not include heteroaryl groups.

A heteroaromatic ring system corresponds to that mentioned above

Definition of an aromatic ring system, with the difference that it must contain at least one heteroatom as a ring atom. As is the case with the aromatic ring system, the heteroaromatic must

Ring system not exclusively aryl groups and heteroaryl groups included, but it cannot additionally include one or more

contain aromatic rings with at least one aryl or

Heteroaryl group are condensed. The non-aromatic rings can contain only carbon atoms as ring atoms, or they can additionally contain one or more heteroatoms, the

Heteroatoms are preferably selected from N, O and S. An example of such a heteroaromatic ring system is benzopyranyl. Furthermore, the term “heteroaromatic ring system” is understood to mean systems which consist of two or more aromatic or heteroaromatic ring systems which are linked to one another via single bonds

are connected, such as 4,6-diphenyl-2-triazinyl. A

Heteroaromatic ring system in the sense of this invention contains 5 to 40 ring atoms which are selected from carbon and heteroatoms, at least one of the ring atoms being a heteroatom. The heteroatoms of the heteroaromatic ring system are preferably selected from N, O and S.

The terms "heteroaromatic ring system" and "aromatic

Ring system ”as defined in the present application

differ from each other in that an aromatic ring system cannot have a hetero atom as a ring atom, whereas a heteroaromatic ring system must have at least one hetero atom as a ring atom. This heteroatom can be used as a ring atom of a non-aromatic heterocyclic ring or as a ring atom of one

aromatic heterocyclic ring are present.

As defined above, each aryl group is included in the term "aromatic ring system" and each heteroaryl group is included in the term "heteroatomatic ring system".

Under an aromatic ring system with 6 to 40 aromatic

Ring atoms or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, in particular groups which are derived from the groups mentioned above under aryl groups and heteroaryl groups and from biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indenofluorene, truxen, isotruxes, spirotruxes, spirotruxes

Indenocarbazole, or combinations of these groups.

In the context of the present invention, a straight-chain alkyl group with 1 to 20 C atoms or a branched or cyclic alkyl group with 3 to 20 C atoms or an alkenyl or alkynyl group with 2 to 40 C atoms, in which also individual H atoms or CH2 groups can be substituted by the groups mentioned above in the definition of the radicals, preferably the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t- Butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neo-pentyl, n-hexyl, cyclohexyl, neo-hexyl, n-heptyl, cycloheptyl, 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 or octynyl understood.

Under an alkoxy or thioalkyl group with 1 to 20 C atoms, in which also individual H atoms or CH2 groups by the above in the

Definition of the groups mentioned radicals can be substituted, preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2nd -Methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n -Butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthioethyl, trifluoroethyl, trifluoro , 2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, Cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio,

Cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio,

Hexinylthio, heptinylthio or octinylthio understood. In the context of the present application, the wording that two or more radicals can form a ring with one another should be understood, inter alia, to mean that the two radicals are linked to one another by a chemical bond. Furthermore, the above-mentioned formulation should also be understood to mean that in the event that one of the two radicals is hydrogen, the second radical is

Formation of a ring at the position to which the hydrogen atom was attached.

The compound of formula (I) is preferably a monoamine. A monoamine is understood to mean one compound, the only one

Triarylamino group contains, and no further triarylamino groups, particularly preferably a compound containing a single amino group, and no further amino groups. z is preferably equal to CR1 when the group - [Ar1] _k -N (Ar2) (Ar3) is not attached to it.

Ar1 is preferably selected from aromatic ring systems with 6 to 20 aromatic ring atoms, which can be substituted with one or more radicals R3, and heteroaromatic ring systems with 5 to 20 aromatic ring atoms, which can be substituted with one or more radicals R3. Particularly preferred groups Ar1 are selected from divalent groups derived from benzene, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene and carbazole, each of which can be substituted by one or more radicals R3. Ar1 is very particularly preferably a divalent group derived from benzene, each with a or more radicals R3 can be substituted. Groups Ar1 can be chosen the same or different for each occurrence.

K is preferably selected from 0 or 1, particularly preferably k is 0.

Preferred groups - (Ar1) _k - for the case k = 1 correspond to the following formulas:

wherein the dashed lines represent the bonds to the rest of the formula (I), and wherein the groups at the unsubstituted positions are each substituted with radicals R3, the radicals R3 in these positions preferably being H.

Groups Ar2 and Ar3 are preferably selected the same or different for each occurrence from monovalent groups derived from benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, fluorene, especially 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, 9-sila-fluorene , in particular 9,9'-dimethyl-9-silafluorene and 9,9'-diphenyl-9-silafluorene, benzofluorene, Spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran,

Dibenzothiophene, benzocarbazole, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine, and triazine, the monovalent groups each being substituted by one or more R4 radicals. Alternatively, the groups Ar2 and Ar3 can be chosen the same or different for each occurrence from combinations of groups derived from benzene, biphenyl, terphenyl,

Quaterphenyl, naphthalene, fluorene, in particular 9,9'-dimethylfluorene and 9,9'-diphenylfluorene, 9-sila-fluorene, in particular 9,9'-dimethyl-9-silafluorene and 9,9'-diphenyl-9-silafluorene, Benzofluorene, spirobifluorene, indenofluorene, indenocarbazole, dibenzofuran, dibenzothiophene, carbazole, benzofuran, benzothiophene, indole, quinoline, pyridine, pyrimidine, pyrazine, pyridazine and triazine, the groups each being substituted by one or more radicals R4.

Particularly preferred groups Ar2 and Ar3 are selected the same or different for each occurrence from phenyl, biphenyl, terphenyl,

Quaterphenyl, naphthyl, fluorenyl, in particular 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl,

Benzofuranyl, benzothiophenyl, benzocondensed dibenzofuranyl, benzocondensed dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, phenyl-substituted-phenyl, carbazolyl

Pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, where the groups mentioned are each substituted by one or more radicals R4. According to a preferred embodiment, exactly one group selected from the groups Ar2 and Ar3 is phenyl which is substituted by radicals R4, which are preferably selected from H, D, F, CN and alkyl groups with 1 to 10 carbon atoms, and are particularly preferably equal to H. Such connections have particularly good hole transport properties.

Particularly preferred groups Ar2 and Ar3 are selected identically or differently from the following formulas:

30th the groups at the positions shown unsubstituted being substituted by radicals R4, where R4 is preferably H in these positions, and wherein the dashed bond is the bond to the amine nitrogen atom.

According to a preferred embodiment, Ar2 and Ar3 in formula (I) are chosen differently.

Ar4 is preferably phenyl, which can be substituted by radicals R2, or 1-naphthyl, which can be substituted by radicals R2, particularly preferably phenyl, which can be substituted by radicals R2. Ar4 is very particularly preferably unsubstituted phenyl or 1-naphthyl, most preferably unsubstituted phenyl.

With each occurrence, R1 is preferably selected identically or differently from H, D, F, CN, Si (R5) 3, N (R5) ₂ , straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or Alkoxy groups with 3 to 20 carbon atoms, aromatic ring systems with 6 to 40

aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein said alkyl and

Alkoxy groups, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted with radicals R5; and wherein in the said alkyl or alkoxy groups one or more CFh groups by -C ^ C-, -R5C = CR5-, Si (R5) ₂ , C = 0, C = NR5, -NR5-, -O-, -S-, -C (= 0) 0- or -C (= 0) NR5- can be replaced. With each occurrence, R1 is particularly preferably selected identically or differently from H, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40

aromatic ring atoms, where the aromatic ring systems and the heteroaromatic ring systems are each substituted with radicals R5. R1 is very particularly preferably equal to H.

According to a preferred embodiment, one or two, preferably one, R1 are selected from aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted with radicals R5 and heteroaromatic ring systems with 5 to 40 aromatic ring atoms which are substituted with radicals R5 and the other radicals R1 are equal to H. Particularly preferred embodiments of aromatic and heteroaromatic ring systems as radicals R1 are in this Case phenyl, biphenyl, terphenyl, fluorenyl, naphthyl, dibenzofuranyl,

Dibenzothiophenyl, and N-phenyl-carbazolyl, which are each substituted with radicals R5, these radicals R5 preferably being F1. The radicals R1, which are selected from aromatic or heteroaromatic ring systems, are preferably bonded in formula (I) in a position selected from positions 5 to 8 on the fluorene in formula (I), particularly preferably in position 5.

R1 is preferably not equal to N (R5) _2. Particularly preferably, radicals R1, including substituents, contain no amino group.

With each occurrence, R2 is preferably selected identically or differently from aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted with radicals R5 and heteroaromatic ring systems with 5 to 40 aromatic ring atoms which are substituted with radicals R5.

R2 is particularly preferably selected from aromatic ring systems having 6 to 40 aromatic ring atoms which are substituted by radicals R5; R2 is very particularly preferably selected from phenyl, fluorenyl, in particular 9,9'-dimethylfluorenyl and 9,9'-diphenylfluorenyl, and naphthyl, where the groups mentioned are each substituted by radicals R5, R5 then preferably being equal to Fl.

R3 is preferably selected the same or different for each occurrence from Fl, D, F, CN, Si (R5) 3, N (R5) ₂ , straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or Alkoxy groups with 3 to 20 carbon atoms, aromatic ring systems with 6 to 40

aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein said alkyl and Alkoxy groups, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted with radicals R5; and wherein in said alkyl or alkoxy groups one or more CF groups are represented by -C ^ C-, -R5C = CR5-, Si (R5) ₂ , C = 0, C = NR5, -NR5-, -0-, -S-, -C (= 0) 0- or -C (= 0) NR5- can be replaced. With each occurrence, R3 is particularly preferably selected identically or differently from H, N (R5) ₂ , straight-chain alkyl groups with 1 to 20 C atoms, branched or cyclic alkyl groups with 3 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms, the alkyl groups, the aromatic ring systems and the

heteroaromatic ring systems are each substituted with radicals R5. R3 is very particularly preferably H. R4 is preferably selected the same or different for each occurrence from H, D, F, CN, Si (R5) 3, N (R5) ₂ , straight-chain alkyl or alkoxy groups with 1 to 20 C- Atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 carbon atoms, aromatic ring systems with 6 to 40

Alkoxy groups, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted with radicals R5; and wherein in said alkyl or alkoxy groups one or more CF groups are represented by -C ^ C-, -R5C = CR5-, Si (R5) ₂ , C = 0, C = NR5, -NR5-, -O-, -S-, -C (= 0) 0- or -C (= 0) NR5- can be replaced. With each occurrence, R4 is particularly preferably selected identically or differently from H, N (R5) ₂ , straight-chain alkyl groups with 1 to 20 C atoms, branched or cyclic alkyl groups with 3 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms, the alkyl groups, the aromatic ring systems and the heteroaromatic ring systems are each substituted with radicals R5. R4 is very particularly preferably equal to H.

R5 is preferably selected the same or different for each occurrence from H, D, F, CN, Si (R6) 3, N (R6) ₂ , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or Alkoxy groups with 3 to 20 carbon atoms, aromatic ring systems with 6 to 40

Alkoxy groups, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted with radicals R6; and wherein in the said alkyl or alkoxy groups one or more CF groups are represented by -C ^ C-, -R6C = CR6-, Si (R6) ₂ , C = 0, C = NR6, -NR6-, -O-, -S-, -C (= 0) 0- or -C (= 0) NR6- can be replaced. With each occurrence, R5 is particularly preferably selected identically or differently from H, straight-chain alkyl groups with 1 to 20 C atoms, branched or cyclic alkyl groups with 3 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 up to 40 aromatic ring atoms, the alkyl groups, the aromatic ring systems and the

heteroaromatic ring systems are each substituted with radicals R6. R5 is very particularly preferably equal to H.

According to a preferred embodiment, i = 0. According to a preferred embodiment, n = 0. I and n are particularly preferably equal to 0.

It is preferred that the group - [Ar1] _k -N (Ar2) (Ar3) in the 1-position, in the 2-position or in the 4-position is bonded to the fluorenyl group in formula (I). It is particularly preferably bound in the 2-position or in the 4-position, very particularly preferably in the 4-position. Preferred embodiments of the formula (I) correspond to the following formulas:

where the symbols and indices that occur are as defined above, and where the bound radical R1 means that all are unsubstituted

shown positions on the benzene ring in question are substituted with residues R1. Is particularly preferred in the above

Formulas i = 0 and n = 0. It is further preferred if R2 is selected from aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted with radicals R5. Again, it is preferred if R1 is H. Again, it is preferred if Ar4 is phenyl or 1-naphthyl, preferably phenyl, each with radicals R2

may be substituted, and are preferably unsubstituted.

Among the above formulas (IA) to (1H), formulas (IA) to (I-D) and (1G) and (1H) are preferred, more preferably formulas (1C), (I-D), (IG) and (lH). Most preferred are formulas (I-C) and (I-D).

Preferred embodiments of the formula (I) correspond to the following formulas where the symbols and indices that occur are as defined above, and where the bound radical R1 means that all are unsubstituted

Formulas n = 0. It is further preferred if R2 is selected from aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted with radicals R5. It is further preferred that R1 is H. It is further preferred if Ar4 is phenyl or 1-naphthyl, is preferably phenyl, which can each be substituted by radicals R2, and are preferably unsubstituted.

Among the above formulas (1-1) to (I-3), formulas (1-1) and (I-2) are preferred.

Preferred embodiments of the formula (I) correspond to the following formulas

where the symbols and indices that occur are as defined above, and where the bonded radical R1 means that all unsubstituted positions on the benzene ring in question are substituted by radicals R1. R1 is preferably equal to F1. It is particularly preferred that Ar1 is selected from divalent groups derived from benzene, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran, dibenzothiophene and carbazole, each of which can be substituted by one or more R3 radicals. It is further preferred that Ar2 and Ar3 are selected the same or different for each occurrence from groups of the formulas (Ar-1) to (Ar-256) as defined above.

Among the above formulas are the formulas (lA-1), (lA-2), (lB-1), (lB-2), (lC-1), (lC-2), (lD-1), (ID-2), (ID-1), (ID-2), (ID-1), (ID-2), (ID-G-1), (ID-2), (ID-FH-1) ) and (lH-2) are particularly preferred.

Preferred embodiments of compounds according to formula (I) are shown below:

The compounds of the formula (I) can be prepared by means of conventional synthetic methods in organic chemistry, for example Buchwald coupling reactions and Suzuki coupling reactions.

A preferred synthetic route for the compounds according to the present application is shown below. The expert can do this

Modify synthesis route within the scope of his general specialist knowledge.

In a first step, a metal organyl is added to a carbonyl derivative which carries a phenyl or naphthyl-substituted phenyl group and a phenyl group. This metal organyl is formed from a biphenyl substituted by two reactive groups, at least one of the reactive groups being bonded to the biphenyl in the ortho position. Following the addition there is cyclization under acidic conditions

carried out. This gives a fluorenyl derivative which contains a phenyl group and a phenyl- or naphthyl-substituted phenyl group on the bridgehead carbon atom and which carries a reactive group on one of its benzene rings. A diarylamino group can be introduced via this reactive group in a Buchwald reaction, or it can be introduced into one

two-step reaction an aromatic or heteroaromatic

Ring system are introduced, to which a diarylamino group is attached. The two step reaction involves a Suzuki reaction in which a aromatic or heteroaromatic ring system bearing a reactive group is introduced at the position of the reactive group, and a Buchwald reaction in which a diarylamino group is introduced at the position of the reactive group on the aromatic or heteroaromatic ring system.

The reactive group is preferably selected from CI, Br and I, particularly preferably it is Br.

The group R is preferably selected the same or different at each occurrence from H, F, heteroaryl groups with 5 to 40 aromatic ring atoms and aryl groups with 6 to 40 aromatic ring atoms. There may be one or more R groups on the benzene rings.

The aryl group Ar4 in the scheme shown above is preferably selected from phenyl, which is preferably unsubstituted.

The application thus relates to a process for the preparation of a compound of the formula (I), characterized in that a

Biphenyl derivative bearing two reactive groups, at least one of which is in the ortho position, is metalated and then added to a carbonyl derivative containing a phenyl or naphthyl substituted phenyl group and a phenyl group attached to the carbonyl group. The process is preferably characterized in that cyclization then takes place under acidic conditions, in which a fluorenyl derivative is obtained which has a phenyl group and a phenyl- or naphthyl-substituted phenyl group on its bridgehead carbon atom, and this with a reactive group is substituted. This fluorenyl derivative is then preferably reacted in a Buchwald reaction with a secondary amine which has two substituents selected from aromatic and heteroaromatic ring systems, a compound of the formula (I) being obtained. According to an alternative, too preferred embodiment, the fluorenyl derivative is reacted in a Suzuki reaction with an aromatic or heteroaromatic ring system which has two reactive groups. According to this

The fluorenyl derivative is then used in one embodiment

Buchwald reaction with a secondary amine, which has two substituents selected from aromatic and heteroaromatic ring systems, whereby a compound of formula (I) is obtained.

The compounds according to the invention described above, in particular compounds which are substituted with reactive leaving groups, such as bromine, iodine, chlorine, boronic acid or boronic acid esters, can be used as monomers to produce corresponding oligomers, dendrimers or polymers. Suitable reactive leaving groups are

for example bromine, iodine, chlorine, boronic acids, boronic esters, amines, alkenyl or alkynyl groups with a terminal C — C double bond or C — C triple bond, oxiranes, oxetanes, groups which undergo a cycloaddition, for example a 1,3-dipolar cycloaddition such as dienes or azides, carboxylic acid derivatives, alcohols and silanes. The invention therefore furthermore relates to oligomers, polymers or dendrimers containing one or more compounds of the formula (I), the bond (s) to the polymer, oligomer or dendrimer

any positions which are substituted in formula (I) by R1, R2, R3 or R4. Depending on the linkage of the compound according to formula (|), the compound is part of a side chain of the oligomer or

Polymers or part of the main chain. For the purposes of this invention, an oligomer is understood to mean a compound which is composed of at least three monomer units. For the purposes of the invention, a polymer is understood to mean a compound which is composed of at least ten monomer units. The polymers according to the invention,

Oligomers or dendrimers can be conjugated, partially conjugated or non-conjugated. The oligomers or polymers according to the invention can be linear, branched, or dendritic. In the linearly linked structures, the units of the formula (I) can be linked directly to one another or they can be linked to one another via a bivalent group, for example via a substituted or unsubstituted alkylene group, via a hetero atom or via a bivalent aromatic or heteroaromatic group. In branched and dendritic structures, for example, three or more units of the formula (I) can be linked via a trivalent or higher-valent group, for example via a trivalent or higher-valent aromatic or heteroaromatic group, to form a branched or dendritic oligomer or polymer.

The same preferences as described above for compounds of the formula (I) apply to the repeat units of the formula (I) in oligomers, dendrimers and polymers.

To produce the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. Suitable and preferred comonomers are selected from fluorenes, spirobifluorenes, paraphenylenes, carbazoles, thiophenes, dihydrophenanthrenes, cis- and trans-lindenofluorenes, ketones,

Phenanthrenes or several of these units. The polymers,

Oligomers and dendrimers usually contain other units, for example emitting (fluorescent or phosphorescent) units, such as. B. vinyl triarylamines or phosphorescent metal complexes, and / or charge transport units, especially those based on triarylamines.

The polymers, oligomers and dendrimers according to the invention have advantageous properties, in particular long life spans

Efficiencies and good color coordinates. The polymers and oligomers according to the invention are generally prepared by polymerizing one or more types of monomer, of which at least one monomer in the polymer leads to repeating units of the formula (I). Suitable polymerization reactions are known to the person skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions which lead to CC or CN linkages are as follows:

(A) SUZUKI polymerization;

(B) YAMAMOTO polymerization;

(C) STILLE polymerization; and

(D) HARTWIG-BUCHWALD polymerization.

How the polymerization can be carried out by these methods and how the polymers can then be separated from the reaction medium and purified is known to the person skilled in the art and is described in detail in the literature.

Formulations of the compounds according to the invention are required for processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes. These formulations can be, for example, solutions, dispersions or emulsions. It may be preferred to use mixtures of two or more solvents for this. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methylbenzoate, mesitylene, tetralin, veratrol, 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, alpha-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethylbenzoate, indane, Methyl benzoate, NMP, p-cymene, phenetol, 1,4-diisopropylbenzene,

Dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether,

Diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether,

Tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene,

Hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis (3,4-dimethylphenyl) ethane or mixtures of these solvents.

The invention therefore also relates to a formulation

in particular containing a solution, dispersion or emulsion

at least one compound of formula (I) or at least one

Polymer, oligomer or dendrimer containing at least one unit of the formula (I) and at least one solvent, preferably an organic solvent. The skilled worker is familiar with how such solutions can be prepared.

The compound of formula (I) is suitable for use in an electronic device, in particular an organic electro luminescent device (OLED). Depending on the substitution, the compound of formula (I) can be used in different functions and layers. Use as a hole-transporting material in a hole-transporting layer and / or as a matrix material in an emitting layer is preferred, particularly preferably in combination with a phosphorescent emitter.

Another object of the invention is therefore the use of a

Compound according to formula (I) in an electronic device. The electronic device is preferably selected from the group consisting of organic integrated circuits (OlCs), organic field-effect transistors (OFETs), organic thin-film transistors

(OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photo- receptors, organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and particularly preferably organic electroluminescent devices (OLEDs).

The invention further relates to an electronic device containing at least one compound of the formula (I). The electronic device is preferably selected from the devices mentioned above.

An organic electroluminescent device containing anode, cathode and at least one emitting layer is particularly preferred, characterized in that the device contains at least one organic layer which contains at least one compound of the formula (I). An organic electroluminescent device is preferred, comprising anode, cathode and at least one emitting layer, characterized in that at least one organic layer in the device, selected from hole-transporting and emitting layers, contains at least one compound of the formula (I).

A hole-transporting layer is understood to mean all layers which are arranged between the anode and the emitting layer, preferably hole injection layer, hole transport layer, and

Electron blocking layer. A hole injection layer is understood to mean a layer that is directly adjacent to the anode. Under one

Hole transport layer is understood to mean a layer that is present between the anode and the emitting layer, but is not directly adjacent to the anode, preferably also not directly adjacent to the emitting layer. An electron blocking layer is understood to mean a layer that is present between the anode and the emitting layer and directly adjoins the emitting layer. An electron blocking layer has prefers an energetically high LUMO and thereby prevents electrons from emerging from the emitting layer.

In addition to the cathode, anode and emitting layer, the electronic device can also contain further layers. These are selected, for example, from one or more hole injection layers,

Hole transport layers, hole blocking layers,

Electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers

(Interlayers), charge generation layers (charge generation layers) and / or organic or inorganic p / n transitions. However, it should be pointed out that each of these layers does not necessarily have to be present and the choice of the layers always depends on the compounds used and in particular also on the fact whether it is a fluorescent or phosphorescent electroluminescent device.

The sequence of the layers of the electronic device is preferably as follows:

-Anode-

-Hole injection layer- -hole transport layer- -optional further hole transport layers- -emitting layer- -optional hole blocking layer- -electron transport layer- -electron injection layer- -Cathode-

It should be pointed out again that not all of the layers mentioned need to be present and / or that additional layers may also be present. The organic electroluminescent device according to the invention can contain several emitting layers. These emission layers particularly preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, so that overall white emission results, ie different emitting layers are present in the emitting layers

Compounds are used that can fluoresce or phosphoresce and that emit blue, green, yellow, orange or red light. Three-layer systems, that is to say systems with three emitting layers, are particularly preferred, one of the three layers being blue, one of the three layers green and one of the three layers

shows orange or red emission. The invention

Connections are preferably present in a hole-transporting layer or in the emitting layer. It should be noted that instead of several color-emitting emitter connections, one was used individually to generate white light

Emitter connection can be suitable, which in a wide

Wavelength range emitted.

It is preferred that the compound of formula (I) as

Hole transport material is used. The emitting layer can be a fluorescent emitting layer or it can be one

be phosphorescent emitting layer. The is preferred

emitting layer a blue fluorescent layer or a green phosphorescent layer.

If the device containing the compound of formula (I) contains a phosphorescent emitting layer, it is preferred that this layer has two or more, preferably exactly two, different ones

Contains matrix materials (mixed matrix system). Preferred

Embodiments of mixed matrix systems are described in more detail below. If the compound of formula (I) as a hole transport material in a hole transport layer, a hole injection layer or

Electron blocking layer used, the compound can be used as

Pure material, i.e. in a proportion of 100% in the hole transport layer, or it can be used in combination with one or more other compounds.

According to a preferred embodiment, one contains

Hole-transporting layer containing the compound of formula (I) additionally one or more further hole-transporting compounds. These further hole-transporting compounds are preferably selected from triarylamine compounds, particularly preferably from mono-triarylamine compounds. They are very particularly preferably selected from the preferred embodiments of hole transport materials specified below. In the described preferred

In one embodiment, the compound of the formula (I) and the one or more further hole-transporting compounds are preferably present in each case in a proportion of at least 10%, particularly preferably in each case in a proportion of at least 20%.

According to a preferred embodiment, one contains

Hole-transporting layer containing the compound of formula (I) additionally one or more p-dopants. According to the present invention, preferred organic p-dopants are organic

Electron acceptor compounds used that can oxidize one or more of the other compounds in the mixture.

Particularly preferred p-dopants are quinodimethane compounds, azaindenofluorendiones, azaphenalenes, azatriphenylenes, I2,

Metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or a metal of the 3rd main group, and transition metal complexes, preferably Complexes of Cu, Co, Ni, Pd and Pt with ligands containing at least one oxygen atom as the binding site. Are also preferred

Transition metal oxides as dopants, preferably oxides of rhenium, molybdenum and tungsten, particularly preferably Re ₂ 07 _, M0O3, WO3 and Re03. Bismuth complexes in which are also preferred

Oxidation stage (III), in particular bismuth (III) complexes with

electron deficient ligands, especially carboxylate ligands.

The p-dopants are preferably largely uniformly distributed in the p-doped layers. This can be achieved, for example, by co-evaporation of the p-dopant and the hole transport material matrix. The p-dopant is preferably present in the p-doped layer in a proportion of 1 to 10%.

The following compounds are particularly preferred as p-dopants:

According to a preferred embodiment, a hole injection layer is present in the device, which is one of the following

Embodiments correspond to: a) it contains a triarylamine and a p-dopant; or b) it contains a single electron deficient material (electron acceptor). According to a preferred embodiment of embodiment a), the triarylamine is a monotriarylamine, in particular one of the preferred triarylamine derivatives mentioned below.

According to a preferred embodiment of embodiment b), the electron-deficient material is a hexaazatriphenylene derivative, as in

US 2007/0092755.

The compound of formula (I) may be contained in a hole injection layer, in a hole transport layer, and / or in an electron blocking layer of the device. If the connection is in a

Hole injection layer or in a hole transport layer, it is preferably p-doped, that is to say it is mixed with a p-dopant, as described above, in the layer.

The compound of the formula (I) is particularly preferred in one

Contain electron blocking layer. In this case, it is preferably not p-doped. In this case, it is furthermore preferred as

Single connection in the layer before, without adding another connection. According to an alternative preferred embodiment, the

Compound of formula (I) used in an emitting layer as matrix material in combination with one or more emitting compounds, preferably phosphorescent emitting compounds. The phosphorescent emitting compounds are preferably selected from red phosphorescent and green

phosphorescent compounds.

The proportion of the matrix material in the emitting layer in this case is between 50.0 and 99.9% by volume, preferably between 80.0 and 99.5% by volume and particularly preferably between 85.0 and 97.0% by volume.

Accordingly, the proportion of the emissive compound is between 0.1 and 50.0% by volume, preferably between 0.5 and 20.0% by volume and particularly preferably between 3.0 and 15.0% by volume.

An emitting layer of an organic electroluminescent device can also contain systems comprising a plurality of matrix materials (mixed-matrix systems) and / or a plurality of emitting compounds. In this case too, the emissive compounds are generally those compounds whose proportion in the system is the smaller and the matrix materials are those compounds whose proportion in the system is the larger. In individual cases, however, the proportion of an individual Matrix material in the system can be smaller than the proportion of a single emitting compound.

It is preferred that the compounds of formula (I) as one

Component of mixed matrix systems, preferred for

phosphorescent emitters can be used. The mixed matrix systems preferably comprise two or three different matrix materials, particularly preferably two different matrix materials. One of the two materials is preferably a material with hole-transporting properties and the other material is a material with electron-transporting properties. It is also preferred if one of the materials is selected from compounds with a large energy difference between HOMO and LUMO (wide band gap materials). . In a mixed matrix system, the compound of the formula (I) preferably represents this

Accordingly, if the compound of the formula (I) is used as the matrix material for a phosphorescent emitter in the emitting layer of an OLED, a second matrix compound is present in the emitting layer which has electron-transporting properties. The two different matrix materials can be combined in one

Ratio of 1:50 to 1: 1, preferably 1:20 to 1: 1, particularly preferably 1:10 to 1: 1 and very particularly preferably 1: 4 to 1: 1.

The desired electron-transporting and hole-transporting properties of the mixed matrix components can, however, also be mainly or completely combined in a single mixed matrix component, the further or the further mixed matrix components fulfilling other functions. The following material classes are preferably used in the above-mentioned layers of the device: Phosphorescent emitters:

The term phosphorescent emitter typically includes compounds in which the light emission by a spin-prohibited

Transition takes place, for example a transition from an excited triplet state or a state with a higher spin quantum number, for example a quintet state.

Particularly suitable as phosphorescent emitters are compounds which, when suitably excited, emit light, preferably in the visible range, and also contain at least one atom of atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. Preferred phosphorescent emitters are compounds which contain copper, molybdenum, tungsten, rhenium,

Ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium are used, in particular compounds containing iridium, platinum or copper.

In the context of the present invention, all luminescent iridium, platinum or copper complexes are used as phosphorescent

Connections viewed.

In general, all phosphorescent complexes, as are used according to the prior art for phosphorescent OLEDs and as are known to the person skilled in the art in the field of organic electroluminescent devices, are suitable for use in the

devices according to the invention. Further examples of suitable phosphorescent emitters are shown in the following table:

30th

Fluorescent emitters:

Preferred fluorescent emitting compounds are selected from the class of arylamines. Under an arylamine or a

aromatic amine in the sense of this invention is understood to mean a compound which contains three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to the nitrogen. At least one of these is preferred aromatic or hetero

aromatic ring systems a condensed ring system, particularly preferably with at least 14 aromatic ring atoms. Preferred examples of this are aromatic anthracenamines, aromatic

Anthracene diamines, aromatic pyrenamines, aromatic pyrendiamines, aromatic chrysenamines or aromatic chrysediamines. An aromatic anthracenamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. An aromatic anthracene diamine is understood to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10 position. Aromatic pyrenamines, pyrendiamines, chrysenamines and chrysenamines are defined analogously, the diarylamino groups being preferably attached to the pyrene in the 1-position or in the 1,6-position. Further preferred emitting compounds are indenofluorenamines or -diamines, benzoindenofluorenamines or -diamines, and dibenzoindenofluoramines or -diamines, and also indenofluorene derivatives with condensed Aryl groups. Pyrene-arylamines are also preferred. Also preferred are benzoindenofluorene amines, benzofluorene amines, extended benzoindenofluorenes, phenoxazines, and fluorene derivatives which are linked to furan units or to thiophene units. Examples of fluorescent emitters are shown in the following table:

30th

Matrix materials for fluorescent emitters:

Preferred matrix materials for fluorescent emitters are selected from the classes of the oligoarylenes (eg 2,2 ', 7,7'-tetraphenyl spirobifluorene), in particular the oligoarylenes containing condensed aromatic groups, the oligoarylenevinylenes, the polypodal metal complexes, the hole-conducting Compounds, the electron-conducting compounds, in particular ketones, phosphine oxides, and sulfoxides; the atropisomers, the boronic acid derivatives or the benzanthracenes.

Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, the oligoarylene vinylenes, the ketones, the phosphine oxides and the sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzphenanthrene and / or pyrene or atropisomers of these compounds. An oligoarylene in the sense of this invention is to be understood as meaning a compound in which at least three aryl or arylene groups are bonded to one another. Preferred matrix materials for fluorescent emitters are shown in the following table:

Matrix materials for phosphorescent emitters:

In addition to the compounds of the formula (I), preferred matrix materials for phosphorescent emitters are aromatic ketones, aromatic ones

Phosphine oxides or aromatic sulfoxides or sulfones, triarylamines, carbazole derivatives, e.g. B. CBP (N, N-biscarbazolylbiphenyl) or carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, aza-carbazole derivatives, bipolar matrix materials, silanes, azaboroles or boronic esters, triazine derivatives, zinc complexes, diazasilol or tetraazasilol derivatives, carbohydrate derivatives, dibenzazole derivatives, dibenzazole derivatives, dibenzazole derivatives, over-derivatives, Derivatives,

Triphenylene derivatives, or lactams.

Electron-transporting materials:

Suitable electron-transporting materials are, for example, those described in Y. Shirota et al. , Chem. Rev. 2007, 107 (4), 953-1010

Compounds or other materials as used in these layers according to the prior art. As materials for the electron transport layer, all materials can be used which are used in the prior art as electron transport materials in the electron transport layer. Aluminum complexes, for example Alq3, are particularly suitable.

Zirconium complexes, for example Zrq4, lithium complexes, for example Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives,

Oxadiazole derivatives, aromatic ketones, lactams, boranes,

Diazaphosphole derivatives and phosphine oxide derivatives. Preferred

Electron-transporting compounds are shown in the following table:

Hole transporting materials:

Further compounds which, in addition to the compounds of the formula (I), are preferably used in hole-transporting layers of the OLEDs according to the invention are indenofluorenamine derivatives, amine derivatives, hexaazatriphenylene derivatives, amine derivatives with condensed aromatics, monobenzoindenofluorenamines, dibenzoindenofluorenamines,

Spirobifluorene amines, fluorene amines, spirodibenzopyran amines,

Dihydroacridine derivatives, spirodibenzofurans and spirodibenzothiophenes, phenanthrene diarylamines, spiro-tribenzotropolones, spirobifluorenes with meta-phenyldiamine groups, spiro-bisacridines, xanthene-diarylamines, and 9,10-dihydroanthracene-spiro-arabino compounds.

Preferred hole transporting compounds are shown in the following table:

30th

Cathode:

Metals with a low work function, metal alloys or multilayer structures are made as the cathode of the electronic device

various metals are preferred, such as alkaline earth metals, alkali metals, main group metals or lanthanoids (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys of an alkali or alkaline earth metal and silver, for example an alloy of, are also suitable

Magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, other metals can also be used which have a relatively high work function, such as, for example, B. Ag or Al, in which case combinations of the metals, such as Ca / Ag, Mg / Ag or Ba / Ag are usually used. It may also be preferred to insert a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor. For example, alkali metal or

Alkaline earth metal fluorides, but also the corresponding oxides or

Carbonates in question (e.g. LiF, L1 ₂ O, BaF ₂ , MgO, NaF, CsF, CS ₂ CO3, etc.). Lithium quinolinate (LiQ) can also be used. The

The layer thickness of this layer is preferably between 0.5 and 5 nm. Anode:

Materials with a high work function are preferred as the anode. The anode preferably has a work function greater than 4.5 eV vs. Vacuum on. On the one hand, metals with a high redox potential are suitable for this, such as Ag, Pt or Au. On the other hand, metal / metal oxide electrodes (eg Al / Ni / NiO _x , Al / PtO _x ) can also be preferred. For some applications, at least one of the electrodes must be transparent or

be partially transparent to either the irradiation of the organic

Materials (organic solar cell) or the coupling of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Also preferred are conductive, doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of several layers, for example an inner layer made of ITO and an outer layer made of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

In a preferred embodiment, the electronic device is characterized in that one or more layers are coated with a sublimation process. The materials are evaporated in vacuum sublimation systems at an initial pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar. However, it is also possible for the initial pressure to be even lower, for example less than 10 ⁷ mbar.

An electronic device is also preferred

characterized that one or more layers with the OVPD

(Organic Vapor Phase Deposition) process or with the help of a

Carrier gas sublimation can be coated. The materials are applied at a pressure between 10 ^-5 mbar and 1 bar. A special case 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 (for example BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

An electronic device is further preferred

characterized in that one or more layers of solution, such as. B. by spin coating, or with any printing method, such as. B. screen printing, flexographic printing, nozzle printing or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or ink-jet printing (ink jet printing). Soluble compounds according to formula (I) are necessary for this. High solubility can be achieved by suitable substitution of the compounds. It is further preferred that one or more layers of solution and one or more layers are applied by a sublimation process to produce an electronic device according to the invention. After application of the layers, depending on the application, the device is structured, contacted and finally sealed in order to exclude damaging effects of water and air.

According to the invention, the electronic devices containing one or more compounds of the formula (I) can be used in displays, as light sources in lighting applications and as light sources in medical and / or cosmetic applications. Examples

A) Synthesis examples Example 1 -1:

N, 9-bis ({[1,1'-biphenyl] -4-yl}) - N- (9,9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-fluoren-4- amine

9 - {[1,1'-biphenyl] -4-yl} -4-bromo-9-phenylfluorene

14.5 g (46.3 mmol) of 2,2'-dibromobiphenyl are dissolved in 150 ml of dried THF in a heated flask. The reaction mixture is cooled to -78 ° C. At this temperature, 20.5 ml of a 2.3 M solution of n-BuLi in hexane (46.3 mmol) are slowly added dropwise. The mixture is stirred at -70 ° C for 1 hour. Then 1 1, 4 g of biphenyl-4-yl-phenyl-methanone (44, 13 mmol) are dissolved in 80 ml of THF and added dropwise at -70 ° C. When the addition is complete, the reaction mixture is allowed to warm up slowly to room temperature, NH4Cl is added and the mixture is then concentrated on a rotary evaporator. The evaporated solution is carefully mixed with 200 ml of acetic acid and then 50 ml of smoking HCl are added. The mixture is heated to 75 ° C. and held there for 6 hours. A white solid precipitates out. The mixture is now allowed to cool to room temperature and the precipitated solid is filtered off and washed with methanol.

The residue is dried in vacuo at 40 ° C. Yield 19.5 g (41 mmol) (90% of th.).

The following connections are made analogously. The

Yields are between 40 and 90%.

10.0 g of N- {1, 1'-biphenyl] -4-yl} -9,9-dimethylfluoren-2-amine (27.7 mmol) and

13.1 g of 9 - {[1, 1'-biphenyl] -4-yl} -4-bromo-9-phenylfluorene (27.7 mol) are dissolved in 300 ml of toluene: the solution is degassed and saturated with N2. Then 340 mg (0.83 mmol) of S-Phos and 250 mg (0.28 mmol) of Pd2 (dba) 3 are added, and 4.6 g of sodium tert-butoxide (41.5 mmol) are then added. The reaction mixture is under for 3 h

Protective atmosphere heated to boiling. The mixture is then partitioned between toluene and water, the organic phase three times

Washed water and dried over Na ₂ S0 ₄ and evaporated. To

Filtration of the crude product over silica gel with toluene is the remaining

Crystallized residue from heptane / toluene. The yield is 16.7 g

(80% of theory). The substance is then sublimed in a high vacuum, the purity is 99.9%.

The following connections are made analogously. The yields are between 65 and 90%.

30th

Example 2-1:

N - {[1 _> 1'-biphenyl] -4-yl} -N- [4- (9 - {[1, 1 '-bi phenyl] -4-yl} -9-phenyl-9H-fluorene-4 -yl) phenyl] -9,9-dimethyl-9H-fluoren-2-amine

Intermediate 111-1: 9 - {[1,1'-biphenyl] -4-yl} -4- (4-chlorophenyl) -9-phenylfluorene

5.90 g (37.7 mmol) of 4-chlorophenylboronic acid and 15 g (37.7 mmol) of intermediate 1-1 are dissolved in 200 ml of THF and 38 ml of a 2M

Potassium carbonate solution (75.5 mmol) suspended. About this suspension 0.87 g (0.76 mmol) of palladium tetrakis (triphenylphosphine) are added, and the reaction mixture is heated under reflux for 12 h. To

After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 100 ml of water and then concentrated to dryness. Filtration of the crude product over silica gel with toluene gives 15.46 g (95%) of intermediate 111-1.

The following connections are made analogously. The yields are between 40 and 90%.

30th

Analogously to Example 1-1, N - {[1,1'-biphenyl] -4-yl} -N- [4- (9 - {[1,1'-biphenyl] -4-yl} -9-phenyl -9H-fluoren-4-yl) phenyl] -9,9-dimethyl-9H-fluoren-2-amine (Compound 2-1) and the following compounds. The yields are between 40 and 85%.

30th

B) Device examples

1) General manufacturing process for the OLEDs and characterization of the OLEDs

Glass plates coated with structured ITO (indium tin oxide) with a thickness of 50 nm form the substrates to which the OLEDs are applied. The OLEDs basically have the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electrons

blocking layer (EBL) / emission layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of the OLEDs can be found in the following tables. The materials required to manufacture the OLEDs are shown in the following table.

All materials are thermally evaporated in a vacuum chamber. The emission layer consists of at least one matrix material (host material, host material) and an emitting dopant (dopant, emitter) that passes through the matrix material or the matrix materials

Cover vaporization is added in a certain volume fraction. An indication like H: SEB (95%: 5%) means that the material H is present in the layer in a volume fraction of 95% and SEB in a proportion of 5%.

The electron transport layer and the

Hole injection layer made of a mixture of two materials. The

Structures of the materials used in the OLEDs are shown in Table 3. The OLEDs are characterized by default. For this purpose, the electroluminescence spectra, the external quantum efficiency (EQE, measured in%) as a function of the luminance, calculated from current-voltage-luminance characteristics under the assumption of a Lambertian radiation characteristic, and the service life are determined. The specification EQE @ 10mA / cm ² denotes the external quantum efficiency that is achieved at 10mA / cm ² . The specification U @ 10 mA / cm ² denotes the

Operating voltage at 10 mA / cm ² . The service life LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion during operation with a constant current density. Specifying LT80 means that the specified service life corresponds to the time after which the luminance reaches 80% of its initial value has sunk. The specification @ 60 or 40 mA / cm ² means that the relevant service life is measured at 60 or 40 mA / cm ² .

2) Use of the compounds according to the invention in the HIL / HTL and EBL of blue fluorescent and green phosphorescent devices

OLEDs with the following structure are manufactured:

OLEDs E1 and E14 show the use of the compounds HTM-4 and HTM-7 according to the application in the HIL (p-doped) and HTL of a blue fluorescent OLED.

OLEDs E2 to E7 show the use of the compounds HTM-1 to HTM-6 in the EBL of blue fluorescent OLEDs.

OLEDs E8 to E13 show the use of the compounds HTM-1 to HTM-6 in the EBL of green phosphorescent OLEDs.

The OLEDs show the following values for operating voltage, EQE and service life:

The OLEDs have a good service life, high efficiency and low operating voltage. This result is obtained in all three OLED structures used and for all the connections according to the application used above.

3) Comparison test with compounds HTM-4 and Ref-1

The HTM-4 connection according to the application is connected to the

Reference compound Ref-1 compared. The connections differ only in the substituents on the bridgehead carbon

Fluorens and are otherwise identical: there is one with HTM-4

asymmetric substitution before, with a phenyl group and a meta-biphenyl group as a substituent. At Ref-1 lies symmetrical

Substitution in the position mentioned before, with two phenyl groups.

An OLED stack as in part 2) is used, in which the compounds in the EBL are in a blue fluorescent stack. Ref-1 shows a voltage at 10mA / cm ² of 3.7 V and EQE at 10mA / cm ² of 8.5%. In the equivalent structure E5, HTM-4 shows a better EQE of 8.9% with a similar voltage (3.8 V).

This shows the advantage of using one

asymmetric substitution at the bridgehead carbon atom results, in particular a substitution with biphenyl and phenyl at this atom, compared to a symmetrical substitution with two phenyl groups.

4) Comparison test with compounds HTM-7 and Ref-2

The HTM-7 connection according to the application is connected to the

Reference compound Ref-2 compared. The compounds differ only in the substituents on the bridgehead carbon atom of fluorene: Ref-2 has alkyl substitution on the phenyl group on the above

Bridgehead carbon atom, while HTM-7 has no alkyl substitution. An OLED structure as in part 2) is used, in which the compounds in the HIL and HTL are present in a blue fluorescent stack. The reference connection Ref-2 shows a voltage at 10mA / cm ² of 4.2 V. The service life LT80, measured at 60mA / cm ² , is 150h. HTM-7, on the other hand, shows a significantly better LT80 of 310h with comparable voltage (4.3 V). This shows the improvement that is due to the omission of

Alkyl groups on the substituents on the bridgehead carbon atom. This improvement is not limited to the structures shown, but occurs generally.

Claims

Expectations

1. Compound according to formula (I)

Formula (I), where the following applies to the variables that occur:

Ar2 is an aromatic ring system with 6 to 40 aromatic rings

Ring atoms which are substituted with R4 radicals, or a

Ar3 is an aromatic ring system with 6 to 40 aromatic rings

Ring atoms which are substituted with R4 radicals, or a heteroaromatic ring system with 5 to 40 aromatic ring atoms, which is substituted by radicals R4;

Ar4 is phenyl which may be substituted by R2 or naphthyl which may be substituted by R2;

S (= 0) ₂ R5, straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 C-

Atoms, alkenyl or alkynyl groups with 2 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein two or more R1 radicals can be linked together and form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted with radicals R5; and wherein one or more CH ₂ groups in said alkyl, alkoxy, alkenyl and alkynyl groups are represented by -R5C = CR5-, -C ^ C-, Si (R5) ₂ , C = 0, C = NR5, - C (= 0) 0-, -C (= 0) NR5-, NR5, P (= 0) (R5), -O-, -S-, SO or

S0 ₂ can be replaced;

Each occurrence of R2 is selected identically or differently from D, F, CN, Si (R5) ₃ , N (R5) ₂ , aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted by radicals R5, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms which are substituted with R5 radicals;

S (= 0) ₂ R5, straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 C- Atoms, alkenyl or alkynyl groups with 2 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein two or more radicals R3 can be linked to one another and form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted with radicals R5; and wherein one or more CF groups in said alkyl, alkoxy, alkenyl and alkynyl groups are represented by -R5C = CR5-, -C ^ C-, Si (R5) ₂ , C = 0, C = NR5, -C (= 0) 0-, -C (= 0) NR5-, NR5, P (= 0) (R5), -O-, -S-, SO or

SO2 can be replaced;

Each occurrence of R4 is the same or different from H, D, F, CI, Br, I, C (= 0) R5, CN, Si (R5) ₃ , N (R5) ₂ , P (= 0) (R5 ) ₂ , OR5, S (= 0) R5,

S (= 0) ₂ R6, straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 to 20 C- Atoms, alkenyl or alkynyl groups with 2 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; where two or more radicals R5 can be linked to one another and form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted with radicals R6; and wherein one or more CF groups in said alkyl, alkoxy, alkenyl and alkynyl groups are represented by -R6C = CR6-, -C ^ C-, Si (R6) ₂ , C = 0, C = NR6, -C (= 0) 0-, -C (= 0) NR6-, NR6, P (= 0) (R6), -O-, -S-, SO or

SO ₂ can be replaced;

Each occurrence of R6 is selected identically or differently from H, D, F, CI, Br, I, CN, alkyl or alkoxy groups with 1 to 20 C atoms, alkenyl or alkynyl groups with 2 to 20 C atoms, aromatic ring systems with 6 to 40 aromatic ring atoms and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein said alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems can be substituted with one or more radicals selected from F and CN; k is 0, 1, 2, 3 or 4, where in the case k = 0 the group Ar1 is not present and the groups which bind to Ar1 in formula (I) are directly linked to one another; i is 0, 1, 2, 3, 4 or 5; n is 0, 1, 2, 3 or 4; being the two groups

2. A compound according to claim 1, characterized in that it is a monoamine.

3. A compound according to claim 1 or 2, characterized in that Z, when the group - [Ar1] _k -N (Ar2) (Ar3) is not bound to it, is equal to CR1.

4. A compound according to one or more of claims 1 to 3, characterized in that k is 0.

5. A compound according to one or more of claims 1 to 3, characterized in that the group - (Ar1) _k - for the case k = 1 corresponds to one of the following formulas wherein the dashed lines represent the bonds to the rest of the formula (I), and wherein the groups at the unsubstituted positions are each substituted with radicals R3, the radicals R3 in these positions preferably being H.

6. Compound according to one or more of claims 1 to 5, characterized in that Ar2 and Ar3 are chosen the same or different for each occurrence from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, in particular 9,9'-dimethylfluorenyl and 9 , 9'-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl,

Benzofuranyl, benzothiophenyl, benzocondensed dibenzofuranyl, benzocondensed dibenzothiophenyl, naphthyl-substituted phenyl,

Fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl,

Dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted

Phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl,

Pyrimidyl-substituted phenyl, and triazinyl-substituted phenyl, where the groups mentioned are each substituted by one or more radicals R4.

7. Compound according to one or more of claims 1 to 6, characterized in that exactly one group selected from the groups Ar2 and Ar3 is phenyl which is substituted by radicals R4, which are preferably selected from H, D, F, CN and alkyl groups with 1 to 10 C atoms, and are particularly preferably H.

8. A compound according to one or more of claims 1 to 7, characterized in that Ar2 and Ar3 are selected identically or differently from the following formulas:

the groups at the positions shown unsubstituted being substituted by radicals R4, where R4 is preferably H in these positions, and wherein the dashed bond is the bond to the amine nitrogen atom.

9. A compound according to one or more of claims 1 to 8, characterized in that Ar4 is phenyl which can be substituted with radicals R2.

10. A compound according to one or more of claims 1 to 9, characterized in that

R1 is selected the same or different for each occurrence from H, aromatic ring systems with 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms, the aromatic ring systems and the heteroaromatic

Ring systems are each substituted with radicals R5; and

R2 is selected from aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted with radicals R5; and

Each occurrence of R3 is chosen identically or differently from H, N (R5) ₂ , straight-chain alkyl groups with 1 to 20 C atoms, branched or cyclic alkyl groups with 3 to 20 C atoms aromatic

Ring systems with 6 to 40 aromatic ring atoms, and

heteroaromatic ring systems with 5 to 40 aromatic ring atoms, the alkyl groups, the aromatic ring systems and the

heteroaromatic ring systems are each substituted with radicals R5; and

Each occurrence of R4 is selected identically or differently from H, N (R5) ₂ , straight-chain alkyl groups with 1 to 20 C atoms, branched or cyclic alkyl groups with 3 to 20 carbon atoms aromatic

Ring systems with 6 to 40 aromatic ring atoms, and

heteroaromatic ring systems are each substituted with radicals R5; and

R5 is chosen the same or different for each occurrence from H, straight-chain alkyl groups with 1 to 20 C atoms, branched or cyclic alkyl groups with 3 to 20 C atoms, aromatic

Ring systems with 6 to 40 aromatic ring atoms, and

heteroaromatic ring systems are each substituted with radicals R6.

11. A compound according to one or more of claims 1 to 10, characterized in that one or two R1 radicals are selected from aromatic ring systems with 6 to 40 aromatic ring atoms, which are substituted with R5 radicals, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms which are substituted by radicals R5 and the other radicals R1 are H.

12. A compound according to one or more of claims 1 to 11, characterized in that i and n are equal to 0.

13. A compound according to one or more of claims 1 to 12, characterized in that the group - [Ar1] _k -N (Ar2) (Ar3) in the 2-position or in the 4-position is bonded to the fluorenyl group in formula (I) is.

14. A compound according to one or more of claims 1 to 13, characterized in that it corresponds to one of the following formulas

wherein the symbols and indices occurring are as defined in one or more of claims 1 to 13, and wherein the bonded radical R1 means that all unsubstituted positions on the benzene ring in question are substituted by radicals R1.

15. A method for producing a compound according to one or more of claims 1 to 14, characterized in that a biphenyl derivative which carries two reactive groups, of which at least one is in the ortho position, is metalated, and is then added to a carbonyl derivative containing a phenyl or naphthyl substituted phenyl group and a phenyl group attached to the carbonyl group.

16. oligomer, polymer or dendrimer containing one or more compounds according to one or more of claims 1 to 14, wherein the bond (s) to the polymer, oligomer or dendrimer to any, in formula (I) with R1, R2, R3 or R4 substituted positions can be localized.

17. Formulation containing at least one compound according to one or more of claims 1 to 14 or at least one polymer, oligomer or dendrimer according to claim 16, and at least one solvent.

18. Electronic device containing at least one compound according to one or more of claims 1 to 14, or at least one polymer, oligomer or dendrimer according to claim 16.

19. Electronic device according to claim 18, characterized in that it is an organic electroluminescent device and contains anode, cathode and at least one emitting layer, and that the connection in a hole-transporting layer or in one

emitting layer of the device is included.

20. Organic electroluminescent device according to claim 19, characterized in that the compound is contained in a hole-transporting layer, which is a hole transport layer or

Is electron blocking layer.

21. Use of a connection according to one or more of the

Claims 1 to 14 in an electronic device.