EP3589624A1 - Materials for organic electronic devices - Google Patents

Abstract

The present invention relates to triarylamine compounds of general formula (I). The present invention further relates to methods for producing said compounds, oligomers, polymers or dendrimers and to formulations containing said compounds, to the use of the compounds in electronic devices, and to electronic devices containing the compounds.

Description

 MATERIALS FOR ORGANIC ELECTRONIC DEVICES

The present application relates to triarylamine compounds according to a formula (I) defined below. These compounds are suitable for

 Use in electronic devices. Furthermore, the concerns

 present application Process for the preparation of said

 Compounds, and electronic devices containing the

 mentioned compounds.

For the purposes of this application, electronic devices are understood as meaning so-called organic electronic devices (organic electronic devices) which use organic semiconductor materials

 Functional materials included. In particular, these include OLEDs

 (Organic electroluminescent devices) understood. Under the

 Designation OLEDs are understood as electronic devices,

 which have one or more layers containing organic compounds and emit light when electrical voltage is applied.

 The structure and general operating principle of OLEDs are the

 Specialist known.

In electronic devices, in particular OLEDs, there is great

 Interest in improving performance, in particular

 Lifetime, efficiency and operating voltage. In these points could not be found a completely satisfactory solution.

Furthermore, materials with a high refractive index are sought, in particular for use in hole-transporting layers of

 OLEDs, especially for use in electron blocking layers of OLEDs.

A big impact on the performance of electronic

 Devices have emission layers and layers

 Hole transporting function. For use in these layers

 continue to seek new connections, in particular

 hole transporting compounds and compounds known as

Matrix material, in particular for phosphorescent emitters, in one can serve emitting layer. Furthermore, compounds are sought that combine hole and electron transporting properties in one compound. Such compounds are referred to as bipolar compounds. Preferred are the hole-transporting properties in one part of the compound, and the electron-transporting properties are in another part of the

Connection isolated.

Various triarylamine compounds are known in the art as hole transport materials for electronic devices.

Also known is the use of certain triarylamine compounds as matrix materials in emitting layers.

However, there remains a need for alternative compounds suitable for use in electronic devices. There is also a need for improvement in performance data for use in electronic devices, particularly in terms of life and efficiency, and refractive index.

It has now been found that certain triarylamine compounds are outstandingly suitable for use in electronic devices, in particular for use in OLEDs, again especially for use as hole transport materials and for use as matrix materials for phosphorescent emitters. The materials preferably satisfy the above-mentioned desirable properties in terms of life, efficiency and refractive index.

The subject of the present application is thus compounds according to a formula (I)

where, for the variables that occur, is the same or different for each occurrence selected from CR ¹ and N, where Z ¹ is C when a group Ar ¹ or T is attached thereto;

Ar ¹ is the same or different at each occurrence

Heteroaryl group having 5 to 30 aromatic ring atoms which may be substituted by one or more R ² radicals; is a single bond, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted with one or more R ² radicals, or a heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more R ² radicals;

Ar ² corresponds to a formula (A), (B) or (C)

Z ² is the same or different CR ³ or N at each occurrence, where Z ² is C when a group L ^{2 is} attached thereto; L2 is a single bond, or an aromatic ring system having 6 to 30 aromatic ring atoms, with one or more groups R may be substituted ³ or a heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted with one or more radicals R ³ ; is selected from C (R ³ ) ₂ , NR ³ , O, and S; is selected from CR ³ and N; corresponds to a formula (A), a formula (B) or a formula (C), or is an aromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R ⁴ , or a heteroaromatic ring system having 5 to 30 aromatic ring atoms which may be substituted by one or more radicals R ⁴ ; is selected from C (R ¹ ) ₂ , NR ¹ , O, and S; R ² , R ³ , R ⁴ are each the same or different selected from H, D, F, C (= O) R ⁵ , CN, Si (R ⁵ ) ₃ , N (R ⁵ ) ₂ , P (= O) (R ⁵ ) ₂ , OR ⁵ , S (= O) R ⁵ , S (= O) ₂ R ⁵ , 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 having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more radicals R ¹ or R ² or R ³ or R ^{4 may} be linked together and form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems may each be substituted with one or more R ⁵ radicals; and wherein one or more CH ₂ groups in said alkyl, alkoxy, alkenyl and

Alkynyl groups by -R ⁵ C = CR ⁵ -, -C ^ C-, Si (R ⁵ ) ₂ , C = O,

C = NR ⁵ , -C (= O) O-, -C (= O) NR ⁵ -, NR ⁵ , P (= O) (R ⁵ ), -O-, -S-, SO or SO ₂ could be; is identical or different on each occurrence from H, D, F, C (OO) R ⁶ , CN, Si (R ⁶ ) ₃ , N (R ⁶ ) ₂ , P (OO) (R ⁶ ) ₂ , OR ⁶ , S (= O) R ⁶ , S (= O) ₂ R ⁶ , straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20

C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more R ^{5 may} be linked together and form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems may each be substituted with one or more R ⁶ radicals; and wherein one or more Ch groups in said alkyl, alkoxy, alkenyl and alkynyl groups are represented by -R ⁶ C = CR ⁶ -, -C ^ C-, Si (R ⁶ ) ₂ , C = O, C = NR ⁶ , -C (= O) O-, -C (= O) NR ⁶ -, NR ⁶ , P (= O) (R ⁶ ), -O-

, -S-, SO or SO2 may be replaced;

R ⁶ is the same or different at each occurrence selected from H, D, F, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic Ring atoms and heteroaromatic

Ring systems with 5 to 40 aromatic ring atoms; wherein two or more R ^{6 may} be linked together and form a ring; and wherein said alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted with F or CN; n is equal to 0 or 1, where the group T is absent when n is 0; i is 0, 1, 2, 3, 4, or 5, wherein the group -L ¹ -Ar ¹ indexed with i is absent when i is 0; k is 0, 1, 2, 3, or 4, where the k-indexed group -L ¹ -Ar ¹ is absent when k is 0; where the sum of k and i is at least equal to 1, and excluding: An aryl group in the context of this invention contains 6 to 40 aromatic ring atoms, none of which represents a heteroatom. An aryl group within the meaning of this invention either becomes a simpler one

aromatic cycle, ie benzene, or a fused aromatic polycycle, for example naphthalene, phenanthrene or anthracene, understood. A condensed aromatic polycycle consists in the context of the present application of two or more with each other

condensed simple aromatic cycles. By condensation between cycles it is to be understood that the cycles share at least one edge with each other.

A heteroaryl group in the context of this invention contains from 5 to 40 aromatic ring atoms, at least one of which represents a heteroatom. The heteroatoms of the heteroaryl group are preferably selected from N, O and S. A heteroaryl group in the context of this invention is understood to mean either a simple heteroaromatic cycle, for example pyridine, pyrimidine or thiophene, or a fused heteroaromatic polycycle, for example quinoline or carbazole. For the purposes of the present application, a condensed heteroaromatic polycycle consists of two or more simple heteroaromatic rings condensed together. By condensation between cycles it is to be understood that the cycles share at least one edge with each other.

An aryl or heteroaryl group which may be substituted in each case by the abovementioned radicals and which may be linked via any position on the aromatic or heteroaromatic compounds is understood in particular to mean groups which are derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, Dihydropyrenes, chrysene, perylene, triphenylene, fluoranthene, benzanthracene, benzphenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, Isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzene imidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazine imidazole, quinoxal in imidazole, oxazole, benzoxazole, naphthoxazole,

Anthroxazole, phenanthroxazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyhdazine, benzopyhdazine, pyrimidine, benzpyrimidine, quinoxaline, pyrazine, phenazine, naphthylhdine, azacarbazole, benzocarboline, phenanthroline, 1, 2, 3-thazole, 1, 2,4-thazole, 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-thazine, 1, 2,4-thazine, 1, 2,3-thazine, 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 contains 6 to 40 C atoms in the ring system and does not comprise any heteroatoms as aromatic ring atoms. An aromatic ring system in the sense of this invention therefore contains no heteroaryl groups. Under an aromatic

Ring system in the context of this invention is to be understood as a system which does not necessarily contain only aryl groups, but in which several aryl groups by a single bond or by a non-aromatic moiety, such as one or more optionally substituted C, Si, N, O - or S-atoms, can be connected. In this case, the non-aromatic unit preferably comprises less than 10% of the atoms other than H, based on the total number of H atoms

different atoms of the system. For example, too

Systems such as 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ethers and stilbene are understood as aromatic ring systems in the context of this invention, and also systems in which two or more aryl groups, for example by a linear or cyclic alkyl, Alkenyl or alkynyl group or linked by a silyl group. Furthermore, systems in which two or more aryl groups over

Single bonds are linked together, as aromatic

Ringsystems understood in the context of this invention, such as systems such as biphenyl and terphenyl.

A heteroaromatic ring system in the context of this invention contains 5 to 40 aromatic ring atoms, of which at least one

Represents heteroatom. The heteroatoms of the heteroaromatic Ring systems are preferably selected from N, O and / or S. A heteroaromatic ring system corresponds to the abovementioned definition of an aromatic ring system, but has at least one heteroatom as one of the aromatic ring atoms. It differs from an aromatic ring system as defined by the

present application, which according to this definition no

Heteroatom may contain as aromatic ring atom.

Under an aromatic ring system with 6 to 40 aromatic

Ring atoms or a heteroaromatic ring system having 5 to 40 aromatic ring atoms, are understood in particular groups which are derived from the groups mentioned above under aryl groups and heteroaryl groups and of biphenyl, terphenyl, quaterphenyl,

Fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene,

Tetrahydropyrene, indenofluorene, truxene, isotruxene, spirotruxene,

Spiroisotruxene, indenocarbazole, or combinations of these groups.

In the context of the present invention, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, in which also individual H atoms or CH 2 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 having 1 to 20 carbon atoms, in which also single H atoms or CH 2 groups by the above in the

Definition of the groups mentioned may be substituted, are preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2 Methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, Cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 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-ethylhexylthio, T fluoromethylthio, pentafluoroethylthio, 2,2,2-thfluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio , Heptenylthio, cycloheptenylthio, octenylthio,

Cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio,

Hexinylthio, heptynylthio or octynylthio understood. In the context of the present application, it should be understood, inter alia, that the two radicals are linked to one another by a chemical bond. Furthermore, it should also be understood by the above formulation that in the event that one of the two radicals is hydrogen, the second radical forms a ring to the position to which the hydrogen atom

was bound binds.

When T is selected from O and S, L ¹ preferably contains none

Carbazole unit, and Ar ¹ , including its substituents, preferably contains no carbazole unit. This means that L ¹ and Ar ¹ also have no groups derived from carbazole by condensation of rings, such as benzocarbazole.

When T is selected from O and S, L ¹ is preferably selected

Single bond and aromatic ring system having 6 to 30 aromatic ring atoms which may be substituted with one or more R ² , and Ar ¹ is selected from a group of the formula shown below (Ar ¹ -A).

Preferably, Z ¹ is CR ¹ wherein Z ¹ is C when a group Ar ¹ or T is attached thereto.

Preferably, Ar ^{1 is the} same or different at each occurrence

Heteroaryl group having 6 to 20 aromatic ring atoms, which with a or a plurality of R ² may be substituted. More preferably, Ar ^{1 is the} same or different selected from groups of the following formulas at each occurrence

where the occurring variables are defined as follows:

V is identical or different at each occurrence N or CR ² , wherein in formula (Ar ¹ -A) and (Ar ¹ -D) at least one group V per formula is equal to N;

W is the same or different at each occurrence N or CR ² ; U is O, S, or NR ² ; wherein at least one group R ² per formula is replaced by the bond to the group L ¹ .

Among the abovementioned groups of the formulas (Ar ¹ -A) to (Ar ¹ -D), preference is given to groups of the formulas (Ar ¹ -A).

Ar ¹ is more preferably identically or differently selected on each occurrence from pyridine, pyrimidine, pyridazine, pyrazine, triazine, dibenzofuran, dibenzothiophene, carbazole, benzimidazole, benzoxazole, and benzothiazole, very particularly preferably selected from pyridine, pyrimidine, triazine, Dibenzothiophene, dibenzofuran and carbazole, even more preferably selected from pyridine, pyrimidine, triazine, dibenzothiophene and

Dibenzofuran, most preferably selected from pyridine, pyrimidine and triazine, wherein said groups each may be substituted with one or more R ² radicals.

Examples of Preferred Substructures of Formula (I)

where the dashed bond denotes the bond to the rest of the formula (I), are shown below:

 Particularly preferred among the above-mentioned groups are the following: Formula (IA-1), Formula (IA-2), Formula (IA-3), Formula (IA-19), Formula (IA-20), Formula (IA) 21), Formula (IA-22), Formula (IA-78), Formula (IA-79), Formula (IA-80), Formula (IA-105), Formula (IA-106), Formula (IA-107 ), Formula (IA-108), Formula (IA-123), Formula (IA-126), Formula (IA-132), Formula (IA-133), Formula (IA-134), Formula (IA-135) ,

Preferably, L ^{1 is} a single bond or a divalent group selected from phenylene, biphenylene, terphenylene, naphthylene, dibenzofuran, dibenzothiophene, carbazole, and fluorene, where the divalent group may be substituted with one or more R ² groups. More preferably, L ^{1 is} a single bond. Preferably, the embodiment is that L ^{1 is} a single bond, for all the preferred embodiments of the formula (I) given below.

Ar ² preferably corresponds to the formula (A) or (C), particularly preferably of the formula (A). Preferred embodiments of the formula (C) correspond to the following formulas:

wherein Z ² is CR ³ , and wherein L ^{2 is} defined as above.

Preferred groups Ar ² according to the formulas (A), (B) and (C) are shown below:

Particularly preferred among the above-mentioned groups are the following: Ar ² -2, Ar ² -6, Ar ² -17, Ar ² -25, Ar ² -45, Ar ² -65, Ar ² -74, Ar ² -105 , Ar ² - 165, Ar ² -173.

Preferably, Z ² is CR ³ wherein Z ² is C when a group L ^{2 is} attached thereto.

Preferably, L ^{2 is} selected from single bond and aromatic

Ring system having 6 to 20 aromatic ring atoms, which may be substituted by one or more R ³ radicals. Divalent groups selected from phenylene, biphenylene, terphenyls, naphthylene, dibenzofuran, dibenzothiophene, carbazole, and fluorene are particularly preferred as aromatic ring systems for L ² , where the divalent groups may each be substituted by one or more radicals R ³ . Even more preferably, L ^{2 is} a single bond or a phenylene group, which may be with one or more may be substituted by several radicals R ³ . As the phenylene group, preferred is a 1,4-phenylene group which may be substituted with one or more R ³ groups. Most preferably, L ^{2 is} a single bond

Preferred divalent groups L ² are shown below:

(L ² -37) where the dotted bonds denote the bonds of the divalent group to the rest of the compound, and where the groups at the unsubstituted positions can each be substituted with a radical R ³ , but preferably at these positions

unsubstituted.

Preferably Y is N. Ar ³ preferably does not correspond to one of the formulas (A), (B) and (C).

Ar ³ is preferably an aromatic ring system having 6 to 20 aromatic ring atoms, which may be substituted by one or more R ⁴ radicals. Ar ³ is particularly preferably selected from phenyl, biphenyl,

Terphenyl, fluorenyl, naphthyl, spirobifluorenyl, pyridyl, pyrimidyl, triazinyl, dibenzofuranyl, benzo-fused dibenzofuranyl,

Dibenzothiophenyl, benzo-fused dibenzothiophenyl, carbazolyl, and benzo-fused carbazolyl, and combinations of two, three or four of these groups, all of which groups may be substituted with one or more R ⁴ each.

Preferred embodiments of Ar ³ are shown below:

Preferred among the above-mentioned groups are the following groups: Ar ³ -1, Ar ³ -2, Ar ³ -3, Ar ³ -4, Ar ³ -74, Ar ³ -85, Ar ³ -1 10, Ar ³ - 132, Ar ³ - 165, Ar ³ -235. Preferably, R ¹ , R ² , R ³ and R ⁴ in each occurrence are the same or different selected from H, D, F, CN, Si (R ⁵ ) 3, N (R ⁵ ) 2, straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 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; wherein said alkyl and alkoxy groups, those mentioned

aromatic ring systems and said heteroaromatic

Ring systems each with one or more radicals R ⁵ may be substituted; and wherein in said alkyl or alkoxy groups one or more CH ₂ groups are represented by -C 1 -C-, -R ⁵ C = CR ⁵ -, Si (R ⁵ ) ₂ , C = O, C = NR ⁵ , - NR ⁵ -, -O-, -S-, -C (= O) O- or -C (= O) NR ⁵ - may be replaced.

More preferably, R ¹ is H, with the exception of groups R ¹ attached to a group T equal to C (R ¹ ) ₂ or NR ¹ . In this case, R ^{1 is} preferably selected from alkyl groups having 1 to 20 C atoms and aromatic ring systems having 5 to 40 aromatic ring atoms, wherein said alkyl groups and said aromatic ring systems may each be substituted by one or more R ⁵ radicals.

More preferably, R ² is H.

Most preferably, R ³ is H, with the exception of groups R ³ attached to a group X which is C (R ³ ) ₂ or NR ³ . In this case, R ^{3 is} preferably selected from alkyl groups having 1 to 20 C atoms and aromatic ring systems having 5 to 40 aromatic ring atoms, wherein said alkyl groups and said aromatic ring systems may each be substituted by one or more R ⁵ radicals.

More preferably, R ⁴ is H. Preferably, R ^{5 is the} same or different on each occurrence selected from H, D, F, CN, Si (R ⁶ ) ₃ , N (R ⁶ ) 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 having 5 to 40 aromatic ring atoms; wherein said alkyl and

Alkoxy groups, said aromatic ring systems and said heteroaromatic ring systems may each be substituted with one or more R ⁶ radicals; and wherein, in the above-mentioned alkyl or alkoxy groups, one or more CH groups are replaced by -C = C-, - R ⁶ C = CR ⁶ -, Si (R ⁶⁾ _2, C = O, C = NR ^6, -NR ⁶ -, -O-, -S-, -C (= 0) 0- or - C (= O) NR ⁶ - may be replaced. More preferably, R ⁵ is H. Preferably, n is 0.

I is preferably 0 or 1.

Preferably, k is 0 or 1.

Preferably, the sum of i and k is equal to 1

Preferably, T is selected from C (R ¹ ) 2 and NR ¹ .

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

wherein the occurring variables are defined as above, and wherein T ^{1 is} selected from O, S or NR ¹ .

Preferably, in formulas (1-1) to (I-3), Z ¹ is CR ¹ , wherein Z ¹ is C when a group -L ¹ -Ar ^{1 is} attached thereto. Furthermore, in formulas (1-1) to (I-3), the sum of i and k is preferably equal to 1.

According to a particularly preferred embodiment, the formulas (1-1) to (I-3) correspond to the following formulas:

-55-

wherein the occurring variables are defined as above, and wherein T ^{1 is} selected from O, S or NR ¹ and wherein at least one group V per formula is equal to N.

Preferably, in formulas (1-1 -1), (1-2-1) and (1-3-1) Z ¹ is CR ^1, wherein Z ¹ is C, when a bound with k or i indexed group thereto is. Furthermore, in formulas (1-1-1), (1-2-1) and (1-3-1), the sum of i and k is preferably equal to 1. It is further preferred that one, two or three groups V per formula are equal to N. Particularly preferred is the group

 each selected from pyridyl, pyrimidyl and triazinyl.

According to a particularly preferred embodiment, the formulas (1-1-1), (1-2-1) and (1-3-1) correspond to the following formulas:

wherein the occurring variables are defined as above, and wherein T ^{1 is} selected from O, S or NR ¹ , and wherein at least one group V per formula is N, and further wherein:

Ar ^2-1 is selected from formulas (A-1) and (B-1)

Formula (B-1) wherein Z ² and L ^{2 are} as defined above, and wherein X ^{1 is} selected from NR ³ , O, and S;

Ar ^{2 "2} is selected from formulas (A-2), (B-2) and (C)

Formula (A-2)

wherein L ² and Z ^{2 are} as defined above.

Particularly preferably, Ar ^2-1 in the abovementioned formulas corresponds to the formula (A-1). Ar ^2-2 in the abovementioned formulas particularly preferably corresponds to the formula (A-2) or (C), particularly preferably of the formula (A-2).

Preferably, in the above formulas, Z ¹ is CR ¹ where Z ¹ is C when a group indicated by k or i is attached thereto. Furthermore, in the abovementioned formulas, the sum of i and k is preferably equal to 1. It is further preferred that one, two or three groups V per formula are equal to N. Particularly preferred is the group

 each selected from pyridyl, pyrimidyl and triazinyl.

According to a particularly preferred embodiment, formulas (1-1) to (I-3) correspond to the following formulas:

wherein the occurring variables are defined as above, and wherein T ^{1 is} selected from O, S or NR ¹ , and where V is the same or different at each instance of CR ² and N, where V is C when a group L ^{1 is} attached thereto, and wherein U is O, S or NR ² , where U is N when a group L ^{1 is} attached thereto.

Preferably, in formulas (1-1-2), (1-2-2) and (1-3-2), Z ¹ is CR ¹ , wherein Z ¹ is C when a group indexed by k or i is attached thereto is. Furthermore, in formulas (1-1-2), (I-2-2) and (I-3-2), the sum of i and k is preferably equal to 1. Particularly preferred is the group

each selected from dibenzofuran, dibenzothiophene and carbazole, wherein carbazole may be attached via the nitrogen atom or via a binding site on one of the six-membered rings. Very particular preference is given to dibenzofuran and dibenzothiophene.

According to a particularly preferred embodiment, the formulas (1-1-2), (I-2-2) and (I-3-2) correspond to the following formulas:

30

wherein the occurring variables are defined as above, and wherein T ^{1 is} selected from O, S or NR ¹ , and where V is the same or different at each instance of CR ² and N, where V is C when a group L ¹ is attached to it, and wherein U is O, S or NR ² , where U is N when a group L ^{1 is} attached thereto, and further wherein: is selected from formulas (A-1) and (B-1)

Formula (B-1) wherein Z ² and L ^{2 are} as defined above, and wherein X ^{1 is} selected from NR ³ , O, and S;

Ar ^2-2 is selected from formulas (A-2), (B-2) and (C)

Formula (C) wherein L ² and Z ^{2 are} as defined above.

Particularly preferably, Ar ^2-1 in the abovementioned formulas corresponds to the formula (A-1). More preferably Ar ^2-2 in the abovementioned formulas corresponds to the formula (A-2) or (C), very particularly preferably below the formula (A-2).

Preferably, in the above formulas, Z ¹ is CR ¹ where Z ¹ is C when a group indicated by k or i is attached thereto. Further preferably, the sum of iuk is equal to 1 for the abovementioned formulas. Particularly preferred is the group

each selected from dibenzofuran, dibenzothiophene and carbazole, wherein carbazole may be bonded via the nitrogen atom or via a binding site on one of the six-membered rings. Very particular preference is given to dibenzofuran and dibenzothiophene.

For the above formulas, it is preferred that L ^{2 is} selected from single bond and aromatic ring system having from 10 to 30 aromatic ring atoms substituted with one or more R ³ radicals can. In this case, L ² is particularly preferably a single bond. This applies in particular to the formulas (1-1 -2-1) and (1-1 -2-2).

Further, it is preferable for the above-mentioned formulas that Ar ² corresponds to a formula (A-1), (A-2), (B-1) or (B-2), particularly preferably a formula (A-1) or (A-2), most preferably a formula (A-1). This applies in particular to the formulas (1-1 -2-1) and (1-1 -2-2).

Further, it is preferable for the above formulas that Ar ³ corresponds to a formula (A-1), (A-2), (B-1) or (B-2), or that Ab is selected from aromatic ring systems having 6 to 18 aromatic ring atoms, each of which may be substituted by one or more radicals R ⁴ and heteroaromatic ring systems having from 5 to 30 aromatic

Ring atoms, each of which may be substituted by one or more R ⁴ radicals. This applies in particular to the formulas (1-1 -2-1) and (1-1 -2-2). Preferred compounds of the formula (I) are listed below. In these compounds, the unit of formula (IA) corresponds to one of the preferred ones listed in the table below

Embodiments, the group Ar ² corresponds to one of the in the

The preferred arrays listed below are listed in the table below and the group Ar ³ corresponds to one of the preferred embodiments listed in the table below:

The above groups carry no further substituents, except those explicitly shown.

The following compounds are preferred embodiments of the compounds of formula (I):

The compounds of formula (I) can be prepared according to conventional methods of organic synthetic chemistry known to those skilled in the art. In the preparation of the compounds in particular transition metal-catalyzed coupling reactions, such as Buchwald coupling reactions and Suzuki coupling reactions, and halogenation reactions are used.

The invention thus provides a process for preparing a compound of formula (I) as defined above, characterized in that a diarylamine which is a secondary amine is reacted with a halogen-substituted aromatic or heteroaromatic ring system to form a triarylamine compound which is a tertiary amine. The reaction is preferably carried out by a Buchwald coupling reaction.

The halogen-substituted aromatic or heteroaromatic

Ring system preferably corresponds to a formula (lX)

 wherein the occurring variables are as defined above, and wherein Q is a halogen atom or a triflate or tosylate group, and is preferably Cl, Br or I, more preferably Cl or Br.

The diarylamine preferably corresponds to a formula (I-Y)

 where the occurring variables are as defined above.

The compounds of the formula (I) described above, in particular compounds which are substituted by reactive leaving groups, such as bromine, iodine, chlorine, boronic acid or boronic acid esters, can be used as monomers for producing 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 terminal C-C double bond or C-C triple bond, oxiranes, oxetanes, groups which undergo cycloaddition, for example, a 1, 3-dipolar cycloaddition, as received

for example, dienes or azides, carboxylic acid derivatives, alcohols and silanes. Another object of the invention are therefore oligomers, polymers or dendrimers containing one or more compounds according to

Formula (I), wherein the bond (s) to the polymer, oligomer or dendrimer can be located at any, in formula (I) with R ¹ , R ² , R ³ or R ⁴ substituted positions. Depending on the linkage of the compound of the formula (I), the compound is part of a side chain of the oligomer or polymer or constituent of the main chain. An oligomer in the context of this invention is understood as meaning a compound which is composed of at least three monomer units. A polymer in the context of the invention is understood as meaning a compound which is composed of at least ten monomer units. The polymers, oligomers or dendrimers according to the invention may be conjugated, partially conjugated or non-conjugated. The oligomers or polymers of the invention may 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 divalent group, for example via a substituted or unsubstituted alkylene group, via a heteroatom or via a divalent aromatic or heteroaromatic group. In branched and dendritic structures, for example, three or more units of formula (I) may be linked via a trivalent or higher valent group, for example via a trivalent or higher valent aromatic or heteroaromatic group, to a branched or dendritic oligomer or polymer.

For the repeat units according to formula (I) in oligomers, dendrimers and polymers the same preferences apply as above for

Compounds according to formula (I) described.

To prepare the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with further monomers. Suitable and preferred comonomers are selected from fluorenes (eg according to EP 842208 or WO 2000/22026), Spirobifluorenes (eg according to EP 707020, EP 894107 or WO

2006/061 181), paraphenylenes (for example according to WO 1992/18552), carbazoles (for example according to WO 2004/070772 or WO 2004/1 13468), thiophenes (for example according to EP 1028136), dihydrophenanthrenes (eg according to WO

2005/014689 or WO 2007/006383), cis-and trans-indenofluorenes (for example according to WO 2004/041901 or WO 2004/1 13412), ketones (for example according to WO 2005/040302), phenanthrenes (eg B. according to WO 2005/104264 or WO 2007/017066) or even more of these units. The polymers, oligomers and dendrimers usually also contain further units, for example emitting (fluorescent or phosphorescent) units, such as. Vinyltriarylamines (for example according to WO 2007/068325) or phosphorescent metal complexes (for example according to WO 2006/003000), and / or charge transport units, especially those based on triarylamines.

The polymers and oligomers according to the invention are generally prepared by polymerization of one or more types of monomer, of which at least one monomer in the polymer leads to repeat units of the formula (I). Suitable polymerization reactions are known in the art and described in the literature. Particularly suitable and preferred polymerization reactions which lead to C-C and C-N linkages, respectively, are the Suzuki polymerisation

Yamamoto polymerisation; the silent polymerization; and the Hartwig-Buchwald polymerization.

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 may be, for example, solutions, dispersions or emulsions. It may be preferable to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene,

Methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl THF, THP, chlorobenzene, dioxane, phenoxytoluene, 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, α-terpineol, benzothiazole, butyl benzoate, cumene,

Cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether,

Triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether,

Triethylene glycol dimethyl ether, diethylene glycol monobutyl ether,

Tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene,

Octylbenzene, 1, 1 -Bis (3,4-dimethylphenyl) ethane or mixtures of these solvents.

The invention therefore further provides a formulation, in particular a solution, dispersion or emulsion containing at least one compound of the formula (I) and at least one solvent, preferably an organic solvent. How such solutions can be prepared is known to the person skilled in the art and described, for example, in WO 2002/072714, WO 2003/019694 and the literature cited therein.

The compounds according to the invention are suitable for use in electronic devices, in particular in organic electroluminescent devices (OLEDs). Depending on the substitution, the compounds are used in different functions and layers.

Another object of the invention is therefore the use of

A compound according to formula (I) in an electronic device. In this case, the electronic device is preferably selected from the group consisting of organic integrated circuits (OICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic light emitting transistors (OLETs),

organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field quench devices

(OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and more preferably organic electroluminescent devices (OLEDs).

Another object of the invention, as stated above, an electronic device containing at least one compound of formula (I). In this case, the electronic device is preferably selected from the abovementioned devices.

Particularly preferably, it is an organic electroluminescent device (OLED), comprising anode, cathode and at least one emitting layer, characterized in that at least one organic layer containing an emitting layer, a

hole-transporting layer or another layer, at least one compound according to formula (I) contains.

In addition to the cathode, anode and the emitting layer, the organic electroluminescent device may contain further layers. These are, for example, selected from in each case 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 (IDMC 2003, Taiwan, Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and / or organic or inorganic p / n transitions. The sequence of the layers of the organic electroluminescent device containing the compound of the formula (I) is preferably the following:

Anode hole injection layer hole transport layer-optionally further hole transport layer (s) -electively electron-blocking layer-emitting layer-optionally hole-blocking layer-electron transport layer-electron injection layer cathode. There may be additional layers in the OLED. The organic electroluminescent device according to the invention may contain a plurality of emitting layers. In this case, 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, in the emitting layers

uses different emissive compounds that can fluoresce or phosphoresce and emit blue, green, yellow, orange or red light. Particular preference is given to three-layer systems, that is to say systems having three emitting layers, the three layers exhibiting blue, green and orange or red emission (for the basic structure see, for example, WO 2005/01 1013). The

Compounds according to the invention are preferably in one

Hole transport layer, hole injection layer, electron blocking layer, emitting layer, hole blocking layer and / or

electron transporting layer present, particularly preferably in an emitting layer as a matrix material, in a hole blocking layer and / or in an electron transport layer.

It is preferred according to the invention if the compound according to formula (I) is used in an electronic device containing one or more phosphorescent emitting compounds. In this case, the compound in different layers, preferably in a hole transport layer, an electron blocking layer, a

Hole injection layer, an emitting layer, a

Lochblockierschicht, and / or an electron transport layer may be included. It is particularly preferred in an emitting layer in FIG

Combined with a phosphorescent emitting compound.

The term phosphorescent emissive compounds typically includes compounds in which the light emission occurs through a spin-forbidden transition, for example a transition from an excited triplet state or a state with a higher spin quantum number, for example a quintet state. Suitable phosphorescent emissive compounds (= triplet emitters) are in particular compounds which emit light, preferably in the visible range, when suitably excited, and also contain at least one atom of atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80 , As phosphorescent emissive compounds, compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium are preferably used, in particular compounds containing iridium, platinum or copper. For the purposes of the present invention, all luminescent iridium, platinum or copper complexes are used as

considered phosphorescent emitting compounds.

Examples of the above-described emitting compounds can be found in the applications WO 00/70655, WO 01/41512, WO 02/02714,

WO 02/15645, EP 1 191613, EP 1 191612, EP 1 191614, WO 05/033244, WO 05/019373 and US 2005/0258742. In general, all phosphorescent complexes which are used according to the prior art for phosphorescent OLEDs and as are known to the person skilled in the art of organic electroluminescent devices are suitable. Also, the skilled person without inventive step further phosphorescent complexes in

Use combination with the compounds of formula (I) in organic electroluminescent devices. Other examples are listed in the following table:

30 - 100 -

- 101 -

- 102-

- 103-

- 104 -

30

30 - 107 -

In a preferred embodiment of the invention, the compounds of the formula (I) are used as a hole-transporting material. The compounds are then preferably present in a hole-transporting layer. Preferred embodiments of hole transporting Layers are hole transport layers, electron blocking layers and hole injection layers.

A hole transport layer according to the present application is a hole transporting layer located between the anode and the emissive layer. In particular, it is one

hole transporting layer which is not a hole injection layer and an electron blocking layer.

Hole injection layers and electron blocking layers are understood in the context of the present application as special embodiments of hole-transporting layers. In the case of a plurality of hole-transporting layers between the anode and the emitting layer, a hole injection layer is a hole-transporting layer which adjoins directly to the anode or only through a single hole

Coating the anode is separated from her. A

Electron blocking layer is the one in the case of a plurality of hole transporting layers between the anode and the emitting layer

hole-transporting layer, which adjoins the emitting layer directly on the anode side. The OLED according to the invention preferably contains two, three or four hole-transporting layers between anode and emitting layer, of which preferably at least one contains a compound according to formula (I), more preferably exactly one or two contain a compound according to formula (I).

If the compound according to formula (I) as hole transport material in a hole transport layer, a hole injection layer or a

Used electron blocking layer, so the compound as

Pure material, ie in a proportion of 100%, be used in the hole transport layer, or it can be used in combination with one or more other compounds. According to a preferred embodiment, the organic layer comprising the compound of the formula (I) then additionally contains one or more p-dopants. As p-dopants according to the present invention preferably those organic electron acceptor compounds are used which can oxidize one or more of the other compounds of the mixture. Particularly preferred embodiments of p-dopants are those described in WO 201 1/073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US 8057712, WO

2009/003455, WO 2010/094378, WO 201 1/120709, US 2010/0096600, WO 2012/095143 and DE 102012209523 disclosed compounds.

Particularly preferred as p-dopants are quinodimethane compounds, azaindenofluorendiones, azaphenalens, 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 a binding site. Preference is still given

Transition metal oxides as dopants, preferably oxides of rhenium, molybdenum and tungsten, particularly preferably Re2O ₇ , M0O3, WO3 and ReO ₃ .

The p-dopants are preferably present 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.

Particularly preferred p-dopants are the following compounds:

In a further preferred embodiment of the invention, the compound according to formula (I) is used as hole transport material in combination with a hexaazatriphenylene derivative as described in US 2007/0092755 in an OLED. This is particularly preferred

Hexaazatriphenylenderivat thereby used in a separate layer. In a preferred embodiment of the present invention, the compound of formula (I) is employed in an emissive layer as matrix material in combination with one or more emissive compounds, preferably phosphorescent emissive 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 emitting 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 may also contain systems comprising a plurality of matrix materials (mixed-matrix systems) and / or a plurality of emitting compounds. Also in this case, the emissive compounds are generally those compounds whose proportion in the system is smaller and the matrix materials are those compounds whose proportion in the system is larger. In individual cases, however, the proportion of a single matrix material in the system may be smaller than the proportion of a single emitting compound.

It is preferred that the compounds according to formula (I) be used as a

Component of mixed-matrix systems, preferred for

phosphorescent emitters are used. The mixed-matrix systems preferably comprise two or three different ones

Matrix materials, more preferably two different ones

Matrix materials. In this case, one of the two materials preferably constitutes a material with hole-transporting properties and the other material a material with electron-transporting properties. The compound of formula (I) preferably represents the matrix material with hole-transporting properties. Accordingly, if the compound of formula (I ) as a matrix material for a phosphorescent emitter is used in the emitting layer of an OLED, a second matrix compound in the emitting layer present, which has electron-transporting properties. The two different matrix materials can be in one

Ratio of 1: 50 to 1: 1, preferably 1: 20 to 1: 1, more preferably 1:10 to 1: 1 and most preferably 1: 4 to 1: 1.

More detailed information on mixed-matrix systems are contained inter alia in the application WO 2010/108579, the corresponding technical teaching is included in this context with. However, the desired electron-transporting and hole-transporting properties of the mixed-matrix components may also be mainly or completely combined in a single mixed-matrix component, with the further or the further mixed-matrix components fulfilling other functions. The mixed-matrix systems may comprise one or more emitting compounds, preferably one or more

phosphorescent emitting compounds. In general, mixed-matrix systems are preferred in phosphorescent organic

Electroluminescent devices used.

Particularly suitable matrix materials which can be used in combination with the compounds according to the invention as matrix components of a mixed-matrix system are selected from the below-mentioned preferred matrix materials for phosphorescent emitting compounds, including in particular those which have electron-transporting properties.

The following are preferred embodiments for the

various functional materials of the electronic device listed. Preferred fluorescent emitting compounds are selected from the class of arylamines. Under an arylamine or a

aromatic amine in the context of this invention is a compound understood that contains three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to the nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a fused ring system, more preferably at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic

Anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysendiamines. By an aromatic anthracene amine is meant a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. An aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously thereto, the diarylamino groups being attached to the pyrene preferably in the 1-position or in the 1,6-position. Further preferred emitting compounds are indenofluorenamines or -diamines, for example according to WO 2006/108497 or WO 2006/122630, benzoindenofluoreneamines or -diamines, for example according to

WO 2008/006449, and dibenzoindenofluoreneamines or diamines, for example according to WO 2007/140847, and the indenofluorene derivatives with condensed aryl groups disclosed in WO 2010/012328.

Also preferred are those in WO 2012/048780 and in

WO 2013/185871 disclosed pyrene-arylamines. Also preferred are the benzoindenofluorene amines disclosed in WO 2014/037077, the benzofluorene amines disclosed in WO 2014/106522, which are incorporated herein by reference

WO 2014/1 1 1269 and WO 2017/036574

Benzoindenofluorenes, the phenoxazines disclosed in WO 2017/028940 and WO 2017/028941 and those disclosed in WO 2016/150544

Fluorene derivatives linked to furan units or to thiophene units.

As matrix materials, preferably for fluorescent emitting

Compounds, materials of different substance classes come into question. Preferred matrix materials are selected from the classes of oligoarylenes (for example 2,2 ', 7,7'-tetraphenylspirobifluorene according to EP 676461 or dinaphthylanthracene), in particular the oligoarylenes containing condensed aromatic groups, the oligoarylenevinylenes (eg DPVBi or spiro-DPVBi according to EP 676461), the polypodal metal complexes (eg according to WO 2004/081017), the hole-conducting compounds (e.g. B. according to WO 2004/05891 1), the electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (eg

WO 2005/084081 and WO 2005/084082), the atropisomers (for example according to WO 2006/048268), the boronic acid derivatives (for example according to WO

2006/1 17052) or the benzanthracenes (for example according to WO 2008/145239). Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, the oligoarylenevinylenes, the ketones, the phosphine oxides and the sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzphenanthrene and / or pyrene or atropisomers of these compounds. In the context of this invention, an oligoarylene is to be understood as meaning a compound in which at least three aryl or arylene groups are bonded to one another. Preference is furthermore given to those in WO 2006/097208,

WO 2006/131 192, WO 2007/065550, WO 2007/110129, WO 2007/065678, WO 2008/145239, WO 2009/100925, WO 201 1/054442, and EP 1553154 disclosed anthracene derivatives described in EP 1749809, EP 1905754 and

US 2012/0187826 disclosed pyrene compounds which are disclosed in US Pat

WO 2015/158409 disclosed benzanthracenyl-anthracene compounds, the indeno-benzofurans disclosed in WO 2017/025165, and the phenanthryl-anthracenes disclosed in WO 2017/036573. Preferred matrix materials for phosphorescent emitting

 Compounds in addition to the compounds of formula (I) are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for. B. according to WO 2004/013080, WO 2004/093207, WO

2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives, z. B. CBP (Ν, Ν-biscarbazolylbiphenyl) or in WO 2005/039246, US

2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851 disclosed carbazole derivatives, indolocarbazole derivatives, z. B. according to WO 2007/063754 or WO 2008/056746, indenocarbazole derivatives, for. B. according to WO 2010/136109, WO 201 1/000455 or WO 2013/041 176, Azabarbazolderivate, z. B. according to EP 1617710, EP 161771 1, EP 1731584, JP 2005/347160, bipolar matrix materials, for. B. according to

 WO 2007/137725, Silanes, z. B. according to WO 2005/1 1 1 172, azaborole or boronic esters, z. B. according to WO 2006/1 17052, triazine derivatives, for. B. according to WO 2010/015306, WO 2007/063754 or WO 2008/056746, zinc complexes, for. B. according to EP 652273 or WO 2009/062578, diazasilol or tetraazasilol derivatives, z. B. according to WO 2010/054729, diazaphosphole derivatives, z. B. according to WO 2010/054730, bridged carbazole derivatives, z. B. according to US 2009/0136779, WO 2010/050778, WO

 201 1/042107, WO 201 1/088877 or WO 2012/143080,

 Triphenylene derivatives, eg. B. according to WO 2012/048781, or lactams, z. B. according to WO 201 1/1 16865 or WO 201 1/137951.

Suitable charge transport materials, as used in the hole injection or hole transport layer or in the electron blocking layer or in the

 Electron transport layer of the inventive electronic

 In addition to the compounds of the formula (I), the compounds which can be used are, for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107 (4), 953-1010 or other materials as described in the prior art Technique can be used in these layers.

Preferred materials with hole-transporting properties, which are used, for example, in hole injection layers, hole transport layers,

 Electron blocking layers and / or emitting layers of OLEDs can be used, are shown in the following table:

 The OLED according to the invention preferably comprises two or more different hole-transporting layers. The compound of formula (I) may be in one or more or all

 hole transporting layers are used. According to a preferred embodiment, the compound of the formula (I) is used in exactly one or exactly two hole-transporting layers, and in the other hole-transporting layers present other compounds are used, preferably aromatic ones

 Amin connections. Further compounds which are preferably used in addition to the compounds of the formula (I) in hole-transporting layers of the OLEDs according to the invention are, in particular, indenofluorenamine derivatives (for example according to WO 06/122630 or US Pat

 WO 06/100896), the amine derivatives disclosed in EP 1661888,

Hexaazatriphenylene derivatives (for example according to WO 01/049806), amine derivatives with condensed aromatics (for example, according to US 5,061,569), which are described in US Pat

WO 95/09147 disclosed amine derivatives, monobenzoindenofluoreneamines (for example according to WO 08/006449), dibenzoindenofluoreneamines (for example according to WO 07/140847), spirobifluorene amines (for example according to WO 2012/034627 or WO 2013 / 120577), fluorene amines (for example according to WO 2014/015937, WO 2014/015938, WO 2014/015935 and WO 2015/082056), spiro-dibenzopyran amines (for example according to WO 2013/083216), Dihydroacridine derivatives (eg according to WO 2012/150001), spirodibenzofurans and

Spirodibenzothiophenes, e.g. according to WO 2015/022051 and

WO 2016/102048 and WO 2016/131521, phenanthrene-diarylamines, e.g. according to WO 2015/131976, spiro-tribenzotropolone, e.g. according to

 WO 2016/087017, spirobifluorenes with meta-phenyldiamine groups, e.g. according to WO 2016/078738, spiro-bisacridines, eg. according to WO 2015/15841 1, xanthene-diarylamines, e.g. according to WO 2014/072017, and 9,10-dihydroanthracene spiro compounds with diarylamino groups according to WO 2015/086108.

As materials for the electron transport layer, it is possible to use all materials as used in the prior art as electron transport materials in the electron transport layer. In particular, aluminum complexes are, for example, Alq3, zirconium, for example Zrq _4, 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,

Diazaphospholderivate and Phosphinoxidderivate. Further suitable materials are derivatives of the abovementioned compounds, as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300.

Preferred as the cathode of the electronic device are low workfunction metals, metal alloys or multilayer structures of various metals, such as alkaline earth metals, alkali metals, main group metals or lanthanides (eg Ca, Ba, Mg, Al, In, Mg, Yb, Sm, Etc.). Furthermore, alloys of an alkali or alkaline earth metal and silver, for example an alloy of Magnesium and silver. In multilayer structures, it is also possible, in addition to the metals mentioned, to use further metals which have a relatively high work function, such as, for example, As Ag or Al, which then usually combinations of metals, such as Ca / Ag, Mg / Ag or Ba / Ag are used. It may also be preferred to introduce between a metallic cathode and the organic semiconductor a thin intermediate layer of a material with a high dielectric constant. For this example, come alkali metal or

Alkaline earth metal fluorides, but also the corresponding oxides or

Carbonates in question (eg LiF, Li ₂ O, BaF ₂ , MgO, NaF, CsF, Cs ₂ CO ₃ , etc.). Furthermore, lithium quinolinate (LiQ) can be used for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 nm.

As the anode, high workfunction materials are preferred. Preferably, the anode has a work function greater than 4.5 eV. Vacuum up. On the one hand, metals with a high redox potential, such as Ag, Pt or Au, are suitable for this purpose. It may on the other hand electrodes (z. B. AI / Ni / NiO, AI / PtO _x) may be preferred, metal / metal oxide. For some applications, at least one of the electrodes must be transparent or

be partially transparent to either the irradiation of the organic

Material (organic solar cell) or the extraction of light (OLED, O-LASER) to allow. Preferred anode materials here are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is furthermore given to conductive, doped organic materials, in particular conductive doped polymers. Furthermore, the anode can also consist of several layers, for example of an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide,

Molybdenum oxide or vanadium oxide.

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

In a preferred embodiment, the electronic device is characterized in that one or more layers with a Sublimation method to be coated. The materials in vacuum sublimation systems become smaller at an initial pressure

10 ^-5 mbar, preferably less than 10 ^-6 mbar evaporated. However, it is also possible that the initial pressure is even lower, for example less than 10 ^-7 mbar.

Also preferred is an electronic device, thereby

characterized in that one or more layers with the OVPD

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

Carrier gas sublimation are coated. 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 thus structured (for example, BMS Arnold et al., Appl. Phys. Lett., 2008, 92, 053301). Further preferred is an electronic device, characterized

characterized in that one or more layers of solution, such. B. by spin coating, or with any printing process, such. As 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), are produced. For this purpose, soluble compounds according to formula (I) are necessary. High solubility can be achieved by suitable substitution of the compounds.

It is further preferred that, to produce an electronic device according to the invention, one or more layers of solution and one or more layers are applied by a sublimation method.

According to the invention, the electronic devices containing one or more compounds of the formula (I) in displays, as

Light sources used in lighting applications and as light sources in medical and / or cosmetic applications (eg light therapy). Examples

A) Synthesis examples

Synthesis of the compound (9,9-dimethyl-9H-fluoren-2-yl) - (9,9-spirobifluoren-2-yl) - (3'-pyridin-3-ylbiphenyl-2-yl) -annin ( 1 -1) and the compounds (1 -2) to (1 -15)

Synthesis of Intermediate 1-1: 3- (2'-Bromo-biphenyl-3-yl) -pyridine

10.0 g (81.4 mmol) of pyridine-3-boronic acid (CAS No .: 1692-25-7), 29.2 g (81.4 mmol) of 2-bromo-3'-iodo-biphenyl (CAS No .: 1776936-09-4) and 93 ml of an aqueous 2 M Na 2 CO 3 solution (186 mmol) are suspended in 75 ml of ethanol and 120 ml of toluene. To this suspension are added 0.94 g (0.82 mmol) of tetrakis (thphenyl) phosphine-palladium (0). The reaction mixture is refluxed for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 150 ml of water and then concentrated to dryness. After filtration of the crude product over silica gel with

Heptane / acetic acid ester gives 19 g (79%) of 3- (2'-bromo-biphenyl-3-yl) -pyridine. Analogously, the following compounds are prepared:

Synthesis of (9,9-dimethyl-9H-fluoren-2-yl) - (9,9-spirobifluoren-2-yl) - (3'-pyridin-3-ylbiphenyl-2-yl) -amine (1 -1) and the compounds (1 -2) to (1-15)

25.3 g (9,9-dimethyl-9H-fluoren-2-yl) - (9,9-spirobifluoren-2-yl-amine

(48.4 mmol) and 20 g of 3- (2'-bromo-biphenyl-3-yl) -pyridine (48.4 mmol) are dissolved in 300 ml of toluene. The solution is degassed and saturated with N 2. It is then treated with 1.95 ml (2.17 mmol) of a 1 M tri-tert-butylphosphine solution and 0.217 g (0.97 mmol) of palladium (II) acetate. Subsequently, 1 1, 2 g of sodium pentoxide (96.7 mmol) was added. The reaction mixture is heated to boiling for 4 h under a protective atmosphere. The mixture is then partitioned between toluene and water, the organic phase washed three times with water, dried over Na ₂ SO ₄ and concentrated by rotary evaporation. After filtration of the crude product over silica gel with toluene, the remaining residue from

 Recrystallized heptane / toluene The residue 22.9 g (70% of theory) is finally sublimed under high vacuum.

Analogously, the following compounds are prepared:

B) Device examples

OLEDs containing compounds of formula (I) are prepared according to methods well known in the art.

Subsequently, the OLEDs are put into operation, and the

Properties of the OLEDs are investigated.

The following general method is used in the production of the OLEDs: The substrates used are glass plates coated with structured ITO (indium tin oxide) in a layer thickness of 50 nm. The ITO layer forms the anode. Then the following layers are applied in the given order: Hole injection layer (HIL), optionally hole transport layer (HTL), electron blocking layer (EBL), emitting layer (EML), optionally hole blocking layer (HBL), electron transport layer (ETL),

Electron injection layer (EIL) and cathode. The materials used in the layers are as shown in the below

 Tables shown. The cathode is formed by an aluminum layer having a thickness of 100 nm.

The materials are each applied by thermal deposition from the gas phase. As shown below, the layers may consist of a single material, or of a mixture of two or three different materials. If they consist of a mixture, they are produced by co-evaporation of the materials contained. If an indication H1: SEB (3%) is made as shown below, this means that H1 is contained in a volume fraction of 97% and SEB in a volume fraction of 3% in the film.

All produced OLEDs are put into operation. It is noted that the produced OLEDs are functional, i. Emit light of the expected color.

Finally, the produced OLEDs are examined for their properties. The operating voltage U, the external

Quantum efficiency EQE, and the lifespan LT80 determined. For the values U, EQE and LT80, the luminance is in cd / m ² respectively

Current density in mA / cm ² , at which the corresponding values are determined. LT80 represents the time that elapses until the value for the respective OLED has fallen from 100% to 80%, in each case based on the specified luminance or current density. The corresponding calculation uses an acceleration factor of 1 .8.

1 . Experimental Design: Blue fluorescent OLEDs are prepared having the structure given in the table below. The invention

Compounds 1 -21, 1 -22, 1 -5 and 1 -8 are used in the EBL.

 The following results are obtained:

This shows that OLEDs containing compounds of the invention show good performance in the EBL.

2. Experimental arrangement:

Blue fluorescent OLEDs having the structure shown in the table below are prepared. The compounds 1 -1, 1 -2, 1 -3, 1 -4, 1 -7, 1 -10, 1 -12 and 1 -13 according to the invention are used in the HTL and doped with F4TCNQ in the HIL.

The following results are obtained

This shows that OLEDs containing inventive compounds in the HIL and the HTL show good performance data.

In tests E9-1, E9-2 and E9-3, satisfactory results for life and EQE are obtained.

3. Experimental arrangement:

Blue fluorescent OLEDs having the structure shown in the table below are prepared. The compound 1 -6 according to the invention is used in the EBL.

The following results are obtained:

This shows how the 1. Experimental arrangement that show OLEDs containing compounds of the invention in the EBL good performance data.

4. Experimental arrangement:

There are green phosphorescent OLEDs with in the

 prepared in the table below. The

 Compounds 1 -1 1, 1 -14 and 1 -15 according to the invention are used in the EML as matrix material.

The following results are obtained:

This shows that OLEDs containing compounds according to the invention exhibit good performance data as matrix materials for triplet emitters. 5. Experimental arrangement:

There are green phosphorescent OLEDs with in the

 prepared in the table below. The compounds 1 -9 according to the invention are described in the EML as

 Matrix material and used in the EBL.

The following results are obtained:

This shows that OLEDs containing compounds according to the invention exhibit good performance data as matrix materials for triplet emitters and as electron blocking materials.

Claims

claims 1 . Compound according to formula (I) where the following applies for the occurring variables: Z ¹ is the same or different at each instance of CR ¹ and N, where Z ¹ is C when a group Ar ¹ or T is attached thereto; Ar ¹ is the same or different at each occurrence Heteroaryl group having 5 to 30 aromatic ring atoms which may be substituted by one or more R ² radicals; L ¹ is a single bond, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted with one or more R ² radicals, or a heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more R ² radicals can; Ar ² corresponds to a formula (A), (B) or (C)  Formula (C) Z ² is the same or different CR ³ or N at each occurrence, where Z ² is C when a group L ^{2 is} attached thereto; L ² is a single bond, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted with one or more R ³ radicals, or a heteroaromatic ring system with 5 to 30 aromatic ring atoms, which may be substituted by one or more R ³ radicals; X is selected from C (R ³ ) ₂ , NR ³ , O, and S; Y is selected from CR ³ and N; Ar ³ corresponds to a formula (A), a formula (B) or a formula (C), or is an aromatic ring system having 6 to 30 aromatic ring atoms, which may be substituted by one or more radicals R ⁴ , or a heteroaromatic ring system with 5 to 30 aromatic ring atoms which may be substituted by one or more R ⁴ radicals; T is selected from C (R ¹ ) ₂ , NR ¹ , O, and S; R ¹ , R ² , R ³ , R ⁴ are each the same or different selected from H, D, F, C (= O) R ⁵ , CN, Si (R ⁵ ) ₃ , N (R ⁵ ) ₂ , P (= O) (R ⁵ ) ₂ , OR ⁵ , S (= O) R ⁵ , S (= O) ₂ R ⁵ , straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or Alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more radicals R ¹ or R ² or R ³ or R ^{4 may} be linked together and form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems may each be substituted with one or more R ⁵ radicals; and wherein one or more CH ₂ groups in said alkyl, alkoxy, alkenyl and Alkynyl groups by -R ⁵ C = CR ⁵ -, -C ^ C-, Si (R ⁵ ) ₂ , C = O, C = NR ⁵ , -C (= O) O-, -C (= O) NR ⁵ -, NR ⁵ , P (= O) (R ⁵ ), -O-, -S-, SO or SO ₂ could be; is the same or different on each occurrence selected from H, D, FC (= O) R ⁶ , CN, Si (R ⁶ ) ₃ , N (R ⁶ ) ₂ , P (= O) (R ⁶ ) ₂ , OR ⁶ , S (= O) R ⁶ , S (= O) ₂ R ⁶ , straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein two or more R ^{5 may} be linked together and form a ring; wherein said alkyl, alkoxy, alkenyl and alkynyl groups and said aromatic ring systems and heteroaromatic ring systems may each be substituted with one or more R ⁶ radicals; and wherein one or more Ch groups in said alkyl, alkoxy, alkenyl and alkynyl groups are represented by -R ⁶ C = CR ⁶ -, -C ^ C-, Si (R ⁶ ) ₂ , C = O, C = NR ⁶ , -C (= O) O-, -C (= O) NR ⁶ -, NR ⁶ , P (= O) (R ⁶ ), -O-, -S-, SO or SO 2 may be replaced; R ⁶ is the same or different at each occurrence selected from H, D, F, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic Ring atoms and heteroaromatic ring systems with 5 to 40 aromatic ring atoms; wherein two or more R ^{6 may} be linked together and form a ring; and wherein said alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted with F or CN; n is equal to 0 or 1, where the group T is absent when n is 0; i is 0, 1, 2, 3, 4, or 5, wherein the group -L ¹ -Ar ¹ indexed with i is absent when i is 0; k is 0, 1, 2, 3, or 4, where the k-indexed group -L ¹ -Ar ¹ is absent when k is 0; where the sum of k and i is at least equal to 1, and being ausgenonnnnen A compound according to claim 1, characterized in that Z ¹ is CR ¹ , wherein Z ¹ is C when a group Ar ¹ or T is attached thereto. 3. A compound according to claim 1 or 2, characterized in that Ar ^{1 is the} same or different selected on each occurrence of groups of the following formulas where the occurring variables are defined as follows: V is identical or different at each occurrence N or CR ² , wherein in formula (Ar ¹ -A) and (Ar ¹ -D) at least one group V per formula is equal to N; W is the same or different at each occurrence N or CR ² ; U is O, S, or NR ² ; wherein at least one group R ² per formula (Ar ¹ -A) to (Ar ¹ -D) is replaced by the bond to the group L ¹ . 4. A compound according to one or more of claims 1 to 3, characterized in that Ar ^{1 is the} same or different selected on each occurrence of pyridine, pyrimidine, pyridazine, pyrazine, triazine, Dibenzofuran, dibenzothiophene, carbazole, benzimidazole, benzoxazole, and benzothiazole, wherein said groups may each be substituted by one or more R ² radicals. 5. A compound according to one or more of claims 1 to 4, characterized in that L ^{1 is} a single bond. 6. A compound according to one or more of claims 1 to 5, characterized in that Ar ² corresponds to the formula (A) as defined in claim 1. 7. A compound according to one or more of claims 1 to 6, characterized in that Z ² is CR ³ , wherein Z ² is C when a group L ² is bound thereto. 8. A compound according to one or more of claims 1 to 7, characterized in that L ^{2 is} a single bond. 9. A compound according to one or more of claims 1 to 8, characterized in that Y is equal to N. 10. A compound according to one or more of claims 1 to 9, characterized in that Ar ³ does not correspond to one of the formulas (A), (B) and (C). 1 1. A compound according to one or more of claims 1 to 9, characterized in that Ar ^{3 is} selected from phenyl, biphenyl, terphenyl, fluorenyl, naphthyl, spirobifluorenyl, pyridyl, pyrimidyl, triazinyl, Dibenzofuranyl, benzo-fused dibenzofuranyl, dibenzothiophenyl, benzo-fused dibenzothiophenyl, carbazolyl, and benzo-fused carbazolyl, and combinations of two, three or four of these groups, which groups may each be substituted with one or more R ⁴ groups. 12. The compound according to one or more of claims 1 to 1 1, characterized in that groups R ¹ , which are not bound to a group T, which is equal to C (R ¹ ) 2 or NR ¹ , equal to H. 13. A compound according to one or more of claims 1 to 12, characterized in that groups R ³ which are not bound to a group X which is C (R ³ ) 2 or NR ³ , equal to H. 14. A compound according to one or more of claims 1 to 13, characterized in that n is equal to 0. 15. A compound according to one or more of claims 1 to 14, characterized in that the sum of i and k is equal to 1. 16. A compound according to one or more of claims 1 to 15, characterized in that the compound of formula (I) corresponds to one of the following formulas: wherein the occurring variables are defined as in one or more of claims 1 to 15, and wherein T ^{1 is} selected from O, S or NR ¹ . 17. A process for preparing a compound according to one or more of claims 1 to 16, characterized in that a diarylamine, which is a secondary amine, is reacted with a halogen-substituted aromatic or heteroaromatic ring system to form a triarylamine compound which is a tertiary Amine is. 18. oligomer, polymer or dendrimer comprising one or more compounds according to one or more of claims 1 to 16, wherein the bond (s) to the polymer, oligomer or dendrimer to any, in formula (I) with R ¹ , R ² , R ³ or R ⁴ substituted positions can be located. 19. Formulation containing at least one compound according to one or more of claims 1 to 18 and at least one Solvent. 20. An electronic device comprising at least one compound according to one or more of claims 1 to 16. 21. Electronic device according to claim 20, characterized in that it is an organic electroluminescent device comprising anode, cathode and at least one emitting layer, wherein at least one organic layer of the device, which may be an emitting layer or a hole transporting layer containing at least one compound , 22. Use of a compound according to one or more of Claims 1 to 16 in an electronic device.