EP3887478A1

EP3887478A1 - Compounds for electronic devices

Info

Publication number: EP3887478A1
Application number: EP19809475.7A
Authority: EP
Inventors: Amir Parham; Jonas Kroeber; Jens ENGELHART; Anja JATSCH; Christian EICKHOFF; Christian Ehrenreich; Jens Kaiser
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2018-11-30
Filing date: 2019-11-28
Publication date: 2021-10-06
Also published as: KR20210097741A; CN113166639A; US20220013730A1; WO2020109434A1

Abstract

The present invention relates to compounds of formula (I), to processes for producing the compounds, and to electronic devices containing at least one compound of formula (I).

Description

Connections for electronic devices

The present application relates to compounds containing a cyclic lactam group. The connections are suitable for use in electronic devices.

Electronic devices in the sense of this application are understood as organic electronic devices, which are organic semiconductor materials

Functional materials included. In particular, it includes OLEDs

(organic electroluminescent devices) understood. 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, in particular

Lifetime, efficiency, operating voltage and color purity. In these

No fully satisfactory solution has yet been found. There is also a need for new, alternative connections for use in electronic devices, particularly in OLEDs. A big influence on the performance data of electronic

Devices have emissive layers, in particular

phosphorescent emitting layers, again in particular red phosphorescent emitting layers. New compounds are still being sought for use in these layers, in particular compounds which can serve as matrix material, in particular for red or green phosphorescent emitters, in an emitting layer. For this purpose, in particular connections are sought that have a high Glass transition temperature TG and have a high oxidation and temperature stability and which result in a high efficiency of the devices when used in OLEDs. A large number of heteroaromatic are in the prior art

Compounds known for use as matrix material for phosphorescent emitting layers, for example carbazole derivatives and quinazoline derivatives. 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, efficiency and color purity of the devices.

It has been found that certain compounds which contain a cyclic lactam group are eminently suitable for use in electronic devices, in particular for use in OLEDs, again particularly for use as matrix materials for

phosphorescent emitters, especially red or green

phosphorescent emitters. The connections lead to higher

Lifetime, high efficiency, low operating voltage and high color purity of the devices. Furthermore, the

Compounds have a high glass transition temperature TG and a high oxidation and temperature stability.

The compounds correspond to a formula (I) Formula (I) where the following applies to the variables that occur:

Each occurrence of G is selected identically or differently from a group of the formula (G-1)

Formula (G-1) which is attached via the dashed bond, wherein in formula (G-1) W is the same or different at each occurrence CR ² or N; or one or more units from two adjacent groups W are selected the same or different from units of the formulas (W-1) to (W-2) for each occurrence

Formula (W-1) Formula (W-2) wherein the dashed bonds are the bonds to the rest of the formula (G-1); where U is chosen the same or different for each occurrence from O, S, NR ³ and C (R ³ ) ₂ ; and wherein in formulas (W-1) to (W-2) V is the same or different CR ² or N at each occurrence; or one or more units from two adjacent groups V are selected the same or different for each occurrence from units of the formulas (V-1) to (V-2)

Formula (V-1) Formula (V-2) wherein the dashed bonds are the bonds to the rest of formulas (W-1) to (W-2); where Z is the same or different N or CR ² on each occurrence;

X is, if no G or T is attached to it, the same or different N or CR ¹ on each occurrence; and X when C or T is attached to it is C;

T is a single bond that connects the relevant groups X;

Each occurrence of R ¹ is the same or different from H, D, F, CI, Br, I, C (= 0) R ⁴ , CN, Si (R ⁴ ) ₃ , N (R ⁴ ) ₂ , P (= 0) (R ⁴ ) ₂ , OR ⁴ , S (= 0) R ⁴ , S (= 0) ₂ R ⁴ , 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 R ¹ 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 R ⁴ ; and wherein one or more CFh groups in said alkyl, alkoxy, alkenyl and alkynyl groups are represented by -R ⁴ C = CR ⁴ -, -C ^ C-, Si (R ⁴ ) 2, C = 0, C = NR ⁴ , -C (= 0) 0-, -C (= 0) NR ⁴ -, NR ⁴ , P (= 0) (R ⁴ ), -O-, -S-, SO or SO2 can be replaced;

Each occurrence of R ² is the same or different from H, D, F, CI, Br, I, C (= 0) R ⁴ , CN, Si (R ⁴ ) ₃ , N (R ⁴ ) ₂ , P (= 0) (R ⁴ ) ₂ , OR ⁴ , S (= 0) R ⁴ , S (= 0) ₂ R ⁴ , straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 up 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 R ² 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 R ⁴ ; and wherein one or more CFh groups in said alkyl, alkoxy, alkenyl and alkynyl groups are represented by -R ⁴ C = CR ⁴ -, -C ^ C-, Si (R ⁴ ) 2, C = 0, C = NR ⁴ , -C (= 0) 0-, -C (= 0) NR ⁴ -, NR ⁴ , P (= 0) (R ⁴ ), -O-, -S-, SO or SO2 can be replaced; Each occurrence of R ³ is the same or different from H, D, F, CI, Br, I, CN, Si (R ⁴ ) ₃ , N (R ⁴ ) 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; where two or more radicals R ^{3 may} be linked to one another and form a ring; wherein said alkyl groups and said aromatic ring systems and heteroaromatic

Ring systems are each substituted with radicals R ⁴ ;

Each occurrence of R ⁴ is the same or different from H, D, F, CI, Br, I, C (= 0) R ⁵ , CN, Si (R ⁵ ) ₃ , N (R ⁵ ) ₂ , P (= 0) (R ⁵ ) ₂ , OR ⁵ , S (= 0) R ⁵ , S (= 0) ₂ R ⁵ , straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 up 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 R ⁴ 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 R ⁵ ; and wherein one or more CH ₂ groups in said alkyl, alkoxy, alkenyl and alkynyl groups are represented by -R ⁵ C = CR ⁵ -, -C ^ C-, Si (R ⁵ ) ₂ , C = 0, C = NR ⁵ , -C (= 0) 0-, -C (= 0) NR ⁵ -, NR ⁵ , P (= 0) (R ⁵ ), -O-, -S-, SO or S0 ₂ can;

Each occurrence of R ⁵ 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 two or more radicals R ⁵ can be linked to one another and form a ring; and wherein said alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems with one or more radicals selected from F and CN can be substituted; k is 0 or 1, where if k is 0, T is absent and the relevant groups X are not linked; Each occurrence of m, n, o is the same or different from 0 and 1, with at least one of the indices m, n and o being equal to 1; wherein in at least one of the rings to which a group G is bound, at least one group X is N.

A circle drawn in a ring means that the ring in question has aromaticity, preferably from three delocalized double bonds.

The following definitions apply to the chemical groups used in the present application. They apply if no more specific definitions are given. An aryl group in the sense of this invention is understood to mean either a single aromatic cycle, that is to say benzene, or a condensed aromatic polycycle, for example naphthalene, phenanthrene or anthracene. 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 either a single heteroaromatic cycle, for example pyridine, pyrimidine or thiophene, or a condensed heteroaromatic polycycle, for example quinoline or carbazole, understood. A condensed heteroaromatic polycycle exists 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, pentacene, benzpyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, acridine, acridine, acridine 6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, benzimidazolo [1,2-ajbenzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole,

Pyrazinimidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzpyrimidine, quinoxaline, azachazidine, pyrazin 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 only contain aryl groups and heteroaryl groups, but one or more can not

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 "heteroaromatic 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 are understood in particular to be 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, truxene, indenofluorene , Isotruxes, spirotruxes, spiroisotruxes,

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-T rifluoroethyl, 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 CFh 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 is to 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 under Formation of a ring at the position to which the hydrogen atom was attached.

One, two, three or four groups X in formula (I) are preferably N, particularly preferably two or three, very particularly preferably two.

In one of the three rings in formula (I) which contain groups X, two groups X are preferably N. In a ring to which a group G binds, exactly one or two, particularly preferably two, groups X are N. In a ring to which a group G binds, one or two groups X which are adjacent for binding to G are preferably equal to N. Particularly preferred in the ring to which a group G binds are two groups X adjacent to the bond at G, and both are equal to N.

K is preferably 0.

The sum of the indices m, n and o is preferably 1, so that exactly one group G is present in formula (I). At least one of the indices m and n is particularly preferably 1, very particularly preferably one of the indices m and n is 1 and the other of the indices m and n is 0. Furthermore, it is preferred that index o is 0. It is preferred that in a ring in formula (I) to which a group G binds no radical R ¹ is Fl or D and at least one group X is N, in particular two groups X are N. In a ring in formula (I) to which a group G binds, all radicals R ¹ selected from F, CN, Si (R ⁴ ) 3, straight-chain alkyl groups having 1 to 20 are preferred

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, said alkyl groups, said aromatic ring systems and said

heteroaromatic ring systems are each substituted with radicals R ⁴ , and at least one group X is equal to N, in particular two groups X are equal to N. Particular preference is given to all radicals R ¹ in a ring in formula (I) to which a group G binds chosen from aromatic

Ring systems with 6 to 40 aromatic ring atoms, which are substituted by one or more radicals R ⁴ , and heteroaromatic

Ring systems with 5 to 40 aromatic ring atoms which are substituted with one or more radicals R ⁴ and at least one group X is N, in particular two groups X are N. It is furthermore preferred that this preferred embodiment is preferred in combination with that Embodiment occurs in which in a ring to which a group G binds one or two groups X, which are adjacent for binding to G, are equal to N; in particular two groups X, which are adjacent for binding to G, are equal to N.

With each occurrence, R ¹ is preferably selected identically or differently from H, D, F, CN, Si (R ⁴ ) 3, 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; wherein said alkyl groups, said aromatic

Ring systems and the heteroaromatic ring systems mentioned are each substituted with radicals R ⁴ ; and wherein in the alkyl groups mentioned one or more CFh groups by -C ^ C-, -R ⁴ C = CR ⁴ -, Si (R ⁴ ) 2, C = 0, C = NR ⁴ , -NR ⁴ -, - O-, -S-, -C (= 0) 0- or -C (= 0) NR ⁴ - can be replaced. With each occurrence, R ¹ is particularly preferably selected identically or differently from H, aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted with radicals R ⁴ , and heteroaromatic ring systems with 5 to 40 aromatic ring atoms which are substituted with radicals R ⁴ . R ¹ is preferably in a ring to which a group G binds, selected from F, CN, Si (R ⁴ ) 3, 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, said alkyl groups, said aromatic ring systems and said

heteroaromatic ring systems are each substituted with radicals R ⁴ . R ¹ in a ring to which a group G binds is particularly preferred, selected from aromatic ring systems with 6 to 40 aromatic ring atoms and heteroaromatic ring systems with 5 to 40

aromatic ring atoms, which are each substituted with radicals R ⁴ .

Each occurrence of R ² is preferably selected identically or differently from H, D, F, CN, Si (R ⁴ ) 3, 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; wherein said alkyl groups, said aromatic

Ring systems and the heteroaromatic ring systems mentioned are each substituted with radicals R ⁴ ; and wherein in the alkyl groups mentioned one or more CFh groups by -C ^ C-, -R ⁴ C = CR ⁴ -, Si (R ⁴ ) 2, C = 0, C = NR ⁴ , -NR ⁴ -, - O-, -S-, -C (= 0) 0- or -C (= 0) NR ⁴ - can be replaced. With each occurrence, R ² is particularly preferably selected identically or differently from H, aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted with radicals R ⁴ , and heteroaromatic ring systems with 5 to 40 aromatic ring atoms which are substituted with radicals R ⁴ . R ² is very particularly preferably equal to H.

With each occurrence, R ³ is 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 hetero- aromatic ring systems with 5 to 40 aromatic ring atoms; where two R ³ radicals can be linked to one another and form a ring; said alkyl groups and said

aromatic ring systems and heteroaromatic ring systems are each substituted with radicals R ⁴ . With each occurrence, R ³ is very particularly preferably selected identically or differently from 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; where two R ³ radicals can be linked to one another and form a ring; wherein said alkyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted with radicals R ⁴ . In the case of linking two radicals R ³ which form a ring, it is preferred that these two radicals are components of a group U which is equal to C (R ³ ) 2, so that a spiro system is formed. In this case, the two radicals R ³ are preferably selected from aromatic ring systems with 6 to 40 aromatic ring atoms and heteroaromatic ones

Ring systems with 5 to 40 aromatic ring atoms, each with

R ⁴ radicals are substituted, particularly preferably from phenyl groups, each of which is substituted by R ⁴ radicals, so that a spirobifluorene unit is formed. Each occurrence of R ⁴ is preferably selected identically or differently from H, D, F, CN, Si (R ⁵ ) 3, 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; wherein said alkyl groups, said aromatic

Ring systems and the heteroaromatic ring systems mentioned are each substituted with radicals R ⁵ ; and being in said alkyl groups one or more CFh groups by -C ^ C-, -R ⁵ C = CR ⁵ -, Si (R ⁵ ) 2, C = 0, C = NR ⁵ , -NR ⁵ -, -O-, -S- , -C (= 0) 0- or -C (= 0) NR ⁵ - can be replaced. With each occurrence, R ⁴ is particularly preferably selected identically or differently from H, aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted with radicals R ⁵ , and heteroaromatic ring systems with 5 to 40 aromatic ring atoms which are substituted with radicals R ⁵ . R ⁴ is very particularly preferably equal to H.

Preferred in formula (G-1) is a unit consisting of two adjacent groups W selected from units of formulas (W-1) and (W-2), preferably (W-2), and the remaining groups W are in each Occurrence of the same or different N or CR ² , preferably CR ² .

According to an alternative, likewise preferred embodiment, all groups W in formula (G-1) are selected identically or differently from N and CR ² , preferably CR ² . In this case, it is preferred that one or more of the radicals R ² are carbazole, preferably C-bonded carbazole, which is in each case substituted by radicals R ⁴ , or contain a carbazole unit which is each substituted by radicals R ⁴ . C-bonded carbazole is understood to mean carbazole which is bonded via one of its C atoms.

According to an alternative, likewise preferred embodiment, in formula (G-1) two units each consisting of two adjacent groups W are selected from units of the formulas (W-1) to (W-2), and the remaining groups W are present each time the same or different N or CR ² , preferably CR ² . According to this embodiment, it is particularly preferred that of the two units each consisting of two

neighboring groups W correspond to a unit of the formula (W-1), V being preferably CR ² , and the other unit corresponding to the formula (W-2), V preferably being CR ² . A unit consisting of two is preferred in formula (W-1)

neighboring groups V selected from units of the formulas (V-1) and (V-2), and the remaining groups V are the same or different N or CR ² , preferably CR ^2, each time they occur.

According to an alternative, likewise preferred embodiment, all groups V in formula (W-1) are selected identically or differently from N and CR ² , preferably CR ² . A unit consisting of two is preferred in formula (W-2)

neighboring groups V selected from units of the formulas (V-1) and (V-2), and the remaining groups V are the same or different N or CR ² , preferably CR ^2, each time they occur. According to an alternative, likewise preferred embodiment, all groups V in formula (W-2) are selected identically or differently from N and CR ² , preferably CR ² .

Z is preferably CR ² .

Preferred groups of formula (G-1) correspond to one of the following

25th

30th

- wherein in formula (G-1-1) W is defined as above, and preferably W

is equal to CR ² or N, particularly preferably equal to CR ² ; and wherein the unsubstituted positions in formula (G-1 -1) are substituted with radicals R ⁴ ; - wherein in formula (G-1-2) a unit W ¹ -W ^{1 is} selected from the formula below, the dashed lines being the bonds of the unit to the rest of the formula (G-1 -2), and wherein remaining groups W ^{1 are selected} identically or differently from CR ² and N, and are preferably equal to CR ² ; and wherein W is defined as above, and is preferably equal to CR ² or N, particularly preferably equal to CR ² ; and wherein U is defined as above, and is preferably selected from O, NR ³ and C (R ³ ) 2, particularly preferably from NR ³ ; and wherein V is defined as above, and is preferably N or CR ² , particularly preferably CR ² ;

- wherein in formula (G-1-3) a unit W ¹ -W ^{1 is} selected from the middle formula, the dashed lines being the bonds of the unit to the rest of the formula (G-1 -3), and wherein the remaining groups W ^{1 are selected} identically or differently from CR ² and N, and are preferably equal to CR ² ; and wherein W is defined as above, and preferably W is CR ² or N, particularly preferably CR ² ; and wherein in formula (G-1 -3) a unit VV is selected from the formula below, the dashed lines being the bonds of the unit to the rest of formula (G-1-3), and wherein the remaining groups V are the same or are selected differently from CR ² and N, and are preferably equal to CR ² ; and wherein U is defined as above, and is preferably selected from O, NR ³ and C (R ³ ) 2; and wherein Z is defined as above and is preferably CR ² ;

- wherein in formula (G-1-4) a unit W ¹ -W ^{1 is} selected from the middle formula, the dashed lines being the bonds of the unit to the rest of the formula (G-1 -4), and wherein remaining groups W ^{1 are selected} identically or differently from CR ² and N, and are preferably equal to CR ² ; and wherein a unit W ² -W ^{2 is} selected from the formula below, the dashed lines being the bonds of the unit to the rest of the formula (G-1-4), and wherein the rest Groups W ^{2 are selected} identically or differently from CR ² and N, and are preferably equal to CR ² ; and wherein V is defined as above, and preferably V is selected identically or differently from CR ² and N, and preferably is equal to CR ² ; and wherein U is defined as above, and is preferably selected from O, NR ³ and C (R ³ ) 2; wherein in formula (G-1 -5) W is defined as above, and preferably W is CR ² or N, particularly preferably CR ² ; and wherein U is defined as above, and is preferably selected from S; and wherein V is defined as above, and is preferably N or CR ² , particularly preferably CR ² ; wherein in formula (G-1 -6) a unit W ¹ -W ^{1 is} selected from the middle formula, the dashed lines being the bonds of the unit to the rest of the formula (G-1 -6), and wherein the rest Groups W ^{1 are selected} identically or differently from CR ² and N, and are preferably equal to CR ² ; and wherein W is defined as above, and preferably W is CR ² or N, particularly preferably CR ² ; and wherein in formula (G-1-6) a unit VV is selected from the formula below, the dashed lines being the bonds of the unit to the rest of formula (G-1-6), and wherein the remaining groups V are the same or are selected differently from CR ² and N, and are preferably equal to CR ² ; and wherein U is defined as above, and is preferably selected from C (R ³ ) 2; and wherein Z is defined as above and is preferably CR ² ; wherein in formula (G-1 -7) a unit W ¹ -W ^{1 is} selected from the middle formula, the dashed lines being the bonds of the unit to the rest of the formula (G-1 -7), and wherein the rest Groups W ^{1 are selected} identically or differently from CR ² and N, and are preferably equal to CR ² ; and wherein in formula (G-1-7) a unit W ² -W ^{2 is} selected from the formula below, the dashed lines being the bonds of the unit to the rest of formula (G-1-7), and wherein the remaining groups W ^{2 are selected} identically or differently from CR ² and N, and are preferably equal to CR ² ; and wherein U is as defined above, and is preferably equal to C (R ³ ) 2; and wherein V is as defined above, and is preferably the same or different CR ² or N on each occurrence, particularly preferably CR ² .

Preferred formulas (G-1 -1) to (G-1 -7) are formulas (G-1 -1) to (G-1 -5), particularly preferred formula (G-1 -1) . The formula (G-1 -1) preferably corresponds to the following formula (G-1 -1 -1)

wherein the unsubstituted positions are substituted with radicals R ⁴ , and where W is selected from N and CR ² and is preferably equal to CR ² .

The formula (G-1 -2) preferably corresponds to one of the following formulas:

Formula (G-1 -2-1) where W, U and V are as defined above, and wherein preferably W is the same or different at each occurrence CR ² or N and is particularly preferably CR ² ; and wherein U is preferably C (R ³ ) 2, and wherein V is preferably the same or different CR ² or N with each occurrence and is particularly preferably equal to CR ² .

The formula (G-1-3) preferably corresponds to the following formula:

Formula (G-1 -3-1), where W, U, V and Z are as defined above, and wherein preferably W is the same or different at each occurrence CR ² or N and is particularly preferably CR ² ; and wherein U is preferably C (R ³ ) 2, and wherein V is preferably the same or different CR ² or N at each occurrence and is particularly preferably equal to CR ² ; and where Z is preferably equal to CR ² . The formula (G-1-4) preferably corresponds to the following formula:

wherein U and V are as defined above, and wherein V is preferably the same or different at each occurrence CR ² or N and is particularly preferably equal to CR ² ; and where U is preferably C (R ³ ) 2.

The formula (G-1-5) preferably corresponds to the following formula: Formula (G-1 -5-1) where U is defined as above and is preferably equal to S.

A preferred embodiment of the formula (G-1-6) corresponds to the following formula:

Formula (G-1 -6-1),

where U is defined as above and is preferably C (R ³ ) 2.

A preferred embodiment of the formula (G-1-7) corresponds to the following formula:

Formula (G-1 -7-1),

where U is defined as above and is preferably C (R ³ ) 2.

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

where the symbols appearing are defined as above, and in the ring to which the group G is attached at least one X is N. G is particularly preferably selected from the preferred embodiments mentioned above. It is further preferred that in the ring to which the group G is bonded two groups X are equal to N. Furthermore, it is preferred that in the event that two groups X are present adjacent to the bond to group G, at least one of them, more preferably both of them, are equal to N. Furthermore, it is preferred that in the case that there is only one group X adjacent to the bond to group G, this group X is equal to N.

Preferred embodiments of the formulas (1-1) and (I-2) correspond to the following formulas, in which the group G is selected from formulas (G-1 -1) to (G-1-7):

Preferred embodiments of the formulas (1-1) and (I-2) correspond to the following formulas where the symbols appearing are defined as above, and wherein R ^{1 1 is} defined as R ¹ above. G is preferably selected from the preferred embodiments mentioned above. R ^1_1 is preferably selected from F, CN, Si (R ⁴ ) 3, 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, wherein said alkyl groups, said aromatic

Ring systems and the heteroaromatic ring systems mentioned are each substituted with radicals R ⁴ . R ^{1 1} is particularly preferably selected from aromatic ring systems with 6 to 40 aromatic ring atoms and heteroaromatic ring systems with 5 to 40 aromatic ring atoms, each of which is substituted by radicals R ⁴ . According to a preferred embodiment, one of the groups X in the formulas above is N. According to an alternative preferred embodiment, all groups X in the formulas above are CR ¹ .

Preferred embodiments of the formulas (1-1 -A), (1-1 -B), (I-2-A) and (I-2-B) correspond to the following formulas, in which the group G is selected from formulas ( G-1-1 -1) to (G-1-7-1):

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

30th

According to a preferred method for producing the

Compounds according to the invention are first prepared the cyclic lactam backbone, and this is then in further

Reaction steps for the compound of the invention further implemented. According to a first preferred process for the preparation of the lactam backbone (Scheme 1 a), starting from an aromatic which has an ester group and a halogen atom in the vicinal position and a further aromatic which has an amino group and a boronic acid group in the vicinal position, is carried out by Suzuki clutch and ring closure for

Lactam is the cyclic lactam backbone. One of the two aromatics has an alkyl thioether group, preferably a methyl thioether group, which is bonded to the ring of the aromatic. The halogen atom is preferably selected from CI, Br and I, particularly preferably CI.

Scheme 1 a

Hai = halogen, preferably CI, Br, I.

N in the ring: the ring can have one or more nitrogen atoms as ring members.

According to a second preferred method (Scheme 1 b)

starting from an aromatic which has a carboxylic acid group and a boronic acid group in the vicinal position, and a further aromatic which has an amino group and a halogen atom in the vicinal position, by Suzuki coupling and ring closure to form the lactam cyclic lactam backbone. One of the two aromatics has an alkyl thioether group, preferably a methyl thioether group, which is bonded to the ring of the aromatic. The halogen atom is preferably selected from CI, Br and I, particularly preferably CI.

Scheme 1 b

Hai = halogen, preferably CI, Br, I.

N in the ring: the ring can have one or more nitrogen atoms as ring members.

The compound obtained in Scheme 1 a and 1 b is then reacted further by Ullmann coupling to the NH of the lactam. Then in a further reaction the alkylthioether group is replaced by a chlorine atom. The corresponding type of reaction is described in Ham et al., Tetrahedron Leiters 2010, 51 (35), 4609-4611. The N-linked carbazole derivative is then introduced at this chlorine atom in a nucleophilic aromatic substitution (Scheme 2).

Scheme 2

Ar = aromatic or heteroaromatic ring system

The compounds shown in the schemes above can be substituted with any organic radicals at the positions shown unsubstituted.

The present application therefore furthermore relates to a process for the preparation of a compound of the formula (I), characterized in that it comprises the following steps:

i) Preparation of a cyclic lactam from two aromatics, by Suzuki coupling and formation of an amide;

ii) Ullmann coupling of an aromatic to the N atom of the lactam group of the cyclic lactam;

iii) Nucleophilic substitution of a halogen atom on the lactam backbone by the carbazole nitrogen atom of a carbazole derivative.

Steps i) to iii) are preferably carried out in the order given. It is further preferred that the cyclic lactam initially has an alkyl thioether group, which in a later step is exchanged for a halogen atom, preferably CI, the nucleophilic substitution reaction taking place at the halogen atom mentioned.

In the context of the syntheses described above, the term “aromatic” encompasses both heteroaromatic and purely aromatic systems.

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 form a cycloaddition, for example a 1, 3 dipolar cycloaddition, enter how

for example 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 to any one in the formula (I) with R ¹ , R ² or R ³ substituted positions can be localized. Depending on the linkage of the compound according to formula (I), the compound is part of a side chain of the oligomer or polymer 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, oligomers or dendrimers according to the invention 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 above apply to the repeat units of the formula (I) in oligomers, dendrimers and polymers

Compounds according to formula (I) described.

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-indofluorenes, ketones,

Phenanthrenes or several of these units. The polymers, oligomers and dendrimers usually contain further 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 monomers, of which at least one monomer in the polymer leads to repeat 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 necessary 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, Ethyl benzoate, 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 furthermore relates to a formulation, in particular a solution, dispersion or emulsion, comprising at least one compound of the 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. A person skilled in the art knows how such solutions can be prepared.

According to a preferred embodiment of the invention, the formulation also contains the compound according to the application

at least one other matrix material and at least one

phosphorescent emitter. The at least one further matrix material and the at least one phosphorescent emitter are each selected from those given below as preferred

Embodiments. After the solvent has been applied and evaporated from the formulation, the mixture of materials remains as

phosphorescent emitting layer with a mixed matrix.

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

used. Another object of the invention is therefore the use of the connections according to the application in electronic devices.

The electronic devices are 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 photoreceptors, organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and particularly preferably organic electroluminescent devices (OLEDs).

Another object of the invention, as already stated above, is an electronic device containing at least one connection as defined above. The electronic device is preferred

selected from the above devices.

It is particularly preferably an organic electroluminescent device (OLED) containing anode, cathode and at least one emitting layer, characterized in that at least one organic layer, which is preferably selected from emitting layers,

Electron transport layers and hole blocking layers, and which is particularly preferably selected from emitting layers, very particularly phosphorescent emitting layers, contains at least one compound as defined above.

In addition to the cathode, anode and at least one emitting layer, the organic electroluminescent 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 and / or organic or inorganic p / n transitions.

The sequence of the layers of the organic electroluminescent device is preferred:

Anode / hole injection layer / hole transport layer / optionally further hole transport layer (s) / electron blocking layer / emitting layer / hole blocking layer / electron transport layer / optionally further

Electron transport layer (s) / electron injection layer / cathode. Additional layers can also be present in the OLED.

It is preferred if at least one hole-transporting layer of the device is p-doped, that is to say contains at least one p-dopant. P-

Dopants are preferably selected from electron acceptor compounds. Particularly preferred p-dopants are selected from

Quinodimethane compounds, azaindenofluorodione, azaphenalenes, azatriphenylenes, I2, metal halides, are preferred

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. Are also preferred

Transition metal oxides as dopants, preferably oxides of rhenium, molybdenum and tungsten, particularly preferably Re2Ü7 _, M0O3, WO3 and Re03. Also preferred are bismuth complexes, in particular Bi (III) complexes, in particular bismuth complexes with benzoic acid derivatives as complex ligands.

The organic electroluminescent device according to the invention can contain several emitting layers. Point particularly preferably these emission layers have a total of a plurality of emission maxima between 380 nm and 750 nm, so that a total of white emission results, ie different emitting layers are emitted in the emitting layers

Compounds 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, with one of the three layers showing blue, one of the three layers green and one of the three layers showing orange or red emission. The invention

Compounds are preferred in the emitting layer

available. Instead of several color-emitting emitter connections, an individually used emitter connection can also be suitable for generating white light

Wavelength range emitted.

It is preferred according to the invention if the compounds are used in an electronic device which contains one or more phosphorescent emitting compounds in an emitting layer. The compounds are preferred in the

contain emitting layer in combination with the phosphorescent emitting compound, particularly preferably in a mixture with at least one further matrix material. This is preferably selected from hole-conducting matrix materials, electron-conducting matrix materials and matrix materials which have both hole-conducting properties and electron-conducting properties (bipolar matrix materials), particularly preferably from electron-conducting matrix materials and bipolar matrix materials, very particularly preferably

electron-conducting matrix materials. The term phosphorescent emitting compounds preferably includes those compounds in which the light is emitted by a spin-prohibited transition, for example a transition from an excited triplet state or a state with a higher spin quantum number, for example a quintet state.

In a preferred embodiment of the present invention, the compound of the formula (I) is in an emitting layer as

Matrix material in combination with one or more

phosphorescent emitting compounds used. The phosphorescent emitting compound is preferably a red or green phosphorescent emitter.

The total proportion of all matrix materials in the phosphorescent 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 phosphorescent emitting compound is between 0.1 and 50.0% by volume, preferably between 0.5 and 20.0% by volume and particularly preferably for between 3.0 and 15.0% by volume. The emitting layer of the organic electroluminescent device preferably comprises two or more matrix materials (mixed matrix systems). The mixed matrix systems preferably comprise two or three different matrix materials, particularly preferably two different matrix materials.

According to a preferred embodiment, one of the two matrix materials has the function of a hole-transporting material, and the other of the two matrix materials has the function of an electron-transporting material. The compound of the formula (I) is particularly preferably the electron-transporting material, and the further compound which is mixed with the compound of the formula (I) in the emitting layer is the hole-transporting material. According to a further preferred embodiment of the invention, one of the two materials is a wide-band gap material, and there are one or two further matrix materials in the emitting layer, by means of which an electron-transporting function and / or a hole-transporting function of the mixed matrix are fulfilled . According to a preferred embodiment, this can be done in that, in addition to the wide-bandgap material, a further matrix material is present in the emitting layer, which has electron-transporting properties, and another matrix material is present in the emitting layer, which is hole-transporting

Has properties. Alternatively and particularly preferably, this can be done in that in addition to the wide-band gap material, there is a single further matrix material in the emitting layer which is both electron-transporting and hole-transporting

Has properties. Such matrix materials are also referred to as bipolar matrix materials.

According to a further alternative embodiment, in addition to the wide-bandgap matrix material, only a single further matrix material can be present in the emitting layer, which either

predominantly hole-transporting properties or predominantly electron-transporting properties. In the preferred case that two different matrix materials are present in the emitting layer, these can be in a volume 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 compound of formula (I) is preferably in the same proportion as the other

Matrix connection, or it is present in a higher proportion than the further matrix connection. The absolute proportion of the compound of the formula (I) in the mixture of the emitting layer, when used as a matrix material in a phosphorescent emitting layer, is preferably 10% by volume to 85% by volume, more preferably 20% by volume to 85 % By volume, even more preferably 30% by volume to 80% by volume, very particularly preferably 20% by volume to 60% by volume and most preferably 30% by volume to 50% by volume. The absolute proportion of the second matrix compound in this case is preferably 15% by volume to 90% by volume, more preferably 15% by volume to 80% by volume, even more preferably 20% by volume to 70% by volume. %, very particularly preferably 40% by volume to 80% by volume, and most preferably 50% by volume to 70% by volume.

In accordance with a preferred embodiment of the invention, a solution comprising the phosphorescent emitter and the two or more matrix materials can be produced to produce phosphorescent emitting layers of the mixed-matrix type. This can be applied by means of spin coating, printing processes or other processes. In this case, after the solvent has evaporated, the phosphorescent emitting layer of the mixed matrix type remains. According to an alternative, more preferred embodiment of the

According to the invention, the phosphorescent emitting layer of the mixed matrix type is produced by gas phase deposition. There are two ways in which the layer can be applied. On the one hand, each of the at least two different matrix materials can be presented in one material source, whereupon the two or more different material sources are evaporated simultaneously (“co-evaporation”). On the other hand, the at least two matrix materials can be premixed and the mixture obtained can be placed in a single material source from which it is finally evaporated. The latter

The process is known as the premix process. The present application therefore also relates to a mixture comprising a compound of the formulas given above and at least one further compound which is selected from

Matrix connections. For this purpose, the preferred embodiments specified in this application with regard to proportions of the

Matrix compounds and their chemical structure are also preferred.

In an alternative preferred embodiment of the invention, the connection is used as an electron-transporting material. This applies in particular if the compound has at least one group selected from electron-poor heteroaryl groups, preferably azine groups, in particular triazine groups, pyrimidine groups and pyridine groups, and

Contains benzimidazole groups. If the compound is used as an electron transporting material, then it is preferably in a hole blocking layer, one

Electron transport layer or used in an electron injection layer. In a preferred embodiment, the layer containing the compound of the formula (I) is then n-doped, or it is present in a mixture with a further electron-transporting compound. The

Compound of formula (I) can be selected in the layer

Hole blocking layer, electron transport layer and

Electron injection layer but also as a pure material. In the present case, an n-dopant is an organic or

understood inorganic compound that is able to donate electrons (electron donor), i.e. a connection that as

Reducing agent works. The compounds used for n-doping can be used as precursors, these precursor compounds releasing n-dopants by activation. N-dopants are preferably selected from electron-rich metal complexes; P = N compounds; N-heterocycles, particularly preferred Naphthylene carbodiimides, pyridines, acridines and phenazines; Fluorenes and radical compounds.

The following are preferred embodiments for the

different 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 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 chrysenediamines are defined analogously, the diarylamino groups on

Pyrene are preferably bonded 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. Benzoindenofluorene amines and benzofluorene amines are also preferred Benzoindenofluorenes, phenoxazines, and fluorene derivatives associated with furan units or with thiophene units.

Preferred matrix materials for fluorescent emitters are selected from the classes of the oligoarylenes (e.g. 2,2 ', 7,7'-tetraphenylspirobifluorene), 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, oligoarylene vinylenes, ketones, phosphine oxides and 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. For the purposes of this invention, an oligoarylene is to be understood as a compound in which at least three aryl or arylene groups are bonded to one another.

Suitable phosphorescent emitting compounds (= triplet emitters) are, in particular, 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 . Compounds which contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium are preferably used as phosphorescent emitting compounds, in particular compounds which contain iridium, platinum or copper. For the purposes of the present invention, all luminescent iridium, platinum or copper complexes as

viewed phosphorescent emissive compounds.

In general, all phosphorescent complexes are suitable, as they 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. Explicit examples of particularly suitable complexes are listed in the following table.

30th

In addition to the compounds according to the application, preferred matrix materials for phosphorescent emitters are aromatic ketones, aromatic 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, carboxylate derivatives, dibenzazolazole derivatives, dibenzazole derivatives, dicarboxyl derivatives, Derivatives,

Triphenylene derivatives, or lactams. The is particularly preferred

Compound of formula (I) used in the emitting layer in combination with a phosphorescent emitter and another matrix material, which is preferably selected from the above

preferred matrix materials and particularly preferably selected from carbazole compounds, biscarbazole compounds,

Indolocarbazole compounds and indenocarbazole compounds.

Suitable charge transport materials, such as those in the hole injection or hole transport layer or electron blocking layer or in the Electron transport layer of the electronic device according to the invention can be used, for example, in Y.

Shirota et al., Chem. Rev. 2007, 107 (4), 953-1010

Compounds or other materials as are used in these layers according to the prior art.

As materials for the electron transporting layers of the

Device are particularly suitable aluminum complexes, for example Alq3, zirconium complexes, 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, diazaphosphole derivatives and phosphine oxide derivatives. Particularly preferred compounds for use in

Electron transporting layers are shown in the following table:

Preferred materials for hole-transporting layers of OLEDs 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-bis-acrylonitrile, x-bisanthrine-10-bisacridene-10 - Spiro compounds with diarylamino groups are used. The following compounds are particularly suitable for this:

30th

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, for example, alkaline earth metals, alkali metals, main group metals or lanthanoids (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Alloys made 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, other metals can also be used in addition to the metals mentioned, 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 can also be preferred to introduce 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, L12O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). Lithium quinolinate (LiQ) can also be used. The

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

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. 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.

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

In a preferred embodiment, the electronic device is characterized in that one or more layers are coated using 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 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 structured in this way (e.g. BMS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301). An electronic device is also 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 connections 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. Electronic devices containing one or more connections as defined above are preferred in displays as light sources in

Illumination applications and as light sources in medical and / or cosmetic applications (e.g. light therapy). Embodiments

A) Synthesis examples

Unless otherwise stated, the following syntheses are carried out in an inert gas atmosphere in dried solvents. The compounds of the invention can by means of

Synthesis methods known to those skilled in the art can be represented. a) 5-Bromo-2-methylsulfanylpyrimidine-4-carboxylic acid methyl ester [50593-92-5]

7.4 g (30 mmol) of 5-bromo 2-methylsulfanylpyrimidine-4-carboxylic acid are placed in 100 ml of CH2Cl2. 2.9 ml (33 mmol) of oxalyl chloride are added dropwise to this solution, and two drops of DMF are added and the mixture is stirred at room temperature overnight. The mixture is concentrated in vacuo and heated with 50 ml of MeOH under reflux for two hours. The mixture is then concentrated and purified by chromatography (EA: heptane,

2: 8).

Yield: 3.2 g (12.1 mmol), 42% of theory. Th .; Purity: 97% by HPLC.

The following connections can be made analogously:

b) 3-methylsulfanyl-6H-pyrimido [4,5-c] quinolin-5-one

G863753-30-41

15.2 g (58 mmol) of 5-bromo-2-methylsulfanylpyrimidine-4-carboxylic acid methyl ester and 10 g (58 mmol) of 2-aminophenylboronic acid hydrochloride are dissolved in 100 ml of DMF and the mixture is saturated with N2. 19 g (230 mmol) sodium acetate and 2.1 g (2.9 mmol) 1, 1’-bis

(Diphenylphosphine) ferrocene-palladium (II) chloride are added and heated to boiling for 18 h. The mixture is poured into 300 ml of a saturated NaCl solution and extracted with CH2Cl2. After concentration in vacuo, the residue is recrystallized from toluene / n-heptane.

Yield: 2.8 g (4.1 mmol), 20% of theory. Th .; Purity: 95% by HPLC.

The following connections can be made analogously:

c) 3-Methylsulfanyl-6- (3-phenylphenyl) pyrimido [4,5-quinolin-5-one

6 g (25 mmol, 1.00 eq.) 3-methylsulfanyl-6H-pyrimido [4,5-c] quinolin-5-one, 21 3 ml (128 mmol, 5.2 eq.) 3-bromobiphenyl and 7.20 g potassium carbonate (52.1 mmol , 2.10 eq.) Are placed in 220 ml of dry DMF and mixed with

Inert argon. Then 0.62 g (2.7 mmol, 0.11 eq) 1, 3-di (2-pyridyl) -1, 3-propanedione and 0.52 g (2.7 mmol, 0.11 eq) copper (I) iodide are added and the mixture for three days heated at 140 ° C. After the reaction is complete, the batch is carefully concentrated on a rotary evaporator, the precipitated solid is suctioned off and washed with water and

Washed ethanol. The crude product is purified twice using a extractor (toluene / fleptan 1: 1) and the solid obtained from toluene recrystallized. After sublimation, 3.9 g (810.1 mmol, 42%) of the desired target compound are obtained.

The following connections can be made analogously:

d) 2-methylsulfanyl-4,5-diphenyl-pyrimido [5,4-c] isoquinolin-6-one

0.1 ml of trifluoroacetic acid are added to a solution of 2-methylsulfanyl-5-phenylpyrimido [5,4-c] isoquinolin-6-one (7.9 g, 25 mmol, 1.0 equiv.) In 125 ml of dichloromethane (25 mmol, 1.0 equiv.) Added. Then 37.5 mmol of phenylboronic acid and 75 ml of water are added. Then 8.5 g (5 mmol) of silver (1) nitrate dissolved in 50 ml of water are added. Finally, K2S2O8 (0.2 g, 75 mmol) is added and the mixture is stirred vigorously at room temperature for 4 hours. The same amount of silver nitrate and potassium persulfate as in the previous steps is then added again and the mixture is stirred for a further 24 hours.

Then 300 ml of dichloromethane and 200 ml of 2M NaOH solution are added to the mixture, and the organic phase is separated off. The crude product is purified by column chromatography using the specified eluent cleaned. The identity and purity of the product is confirmed by GC-MC, 1 H-NMR and 13C-NMR. Yield: 8.8 g (20 mmol), 90% of theory. Th .; Purity: 98% by HPLC.

The following connections can be made analogously:

e) 3-chloro-6- (3-phenylphenyl) pyrimido [4,5-c] quinolin-5-one

10 g (26 mmol) 3-methylsulfanyl-6- (3-phenylphenyl) pyrimido [4,5-c] quinolin-5-one, 34 g (88 mmol) KOH are dissolved in 50 ml EtOH and boiled for 1 h heated. After cooling, the mixture is concentrated in vacuo and mixed with HCl solution until a pH of 4 is reached. The mixture is then mixed with 30 ml of POCI3 and 30 ml of thionyl chloride and heated under reflux for 2 hours. The solvent is then removed by distillation and the product is recrystallized from toluene.

Yield: 8.9 g (23 mmol), 92% of theory. Th .; Purity: 95% by NMR.

The following connections can be made analogously:

25 f) Nucleophilic substitution

30th 16.5 g (61 mmol) of 14H-13-thia-14-aza-benzo [c] indeno [2,1-a] fluorene are dissolved in 300 ml of dimethylformamide under a protective gas atmosphere and with 3 g of NaH, 60% in mineral oil , 75 mmol. After 1 h at room temperature, a solution of 24 g (63 mmol) of 3-chloro-6- (3-phenylphenyl) pyrimido [4,5-c] quinolin-5-one in 150 ml of dimethylformamide is added dropwise. The reaction mixture is then stirred at room temperature for 12 h. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na2SÜ4 and concentrated. The residue is recrystallized twice with toluene and finally fractionally sublimed (p about 10- ⁶ mbar, T = 395- 420 ° C).

Yield: 22 g (40 mmol), 80% of theory. Th .; Purity: 99.9% by HPLC.

The following connections can be made analogously:

25th

30th

B) Device examples

The use of the materials according to the invention in OLEDs is presented in the following examples E1 to E6 (see Table 1).

Glass plates that are coated with structured ITO (indium tin oxide) with a thickness of 50 nm are first treated with an oxygen plasma, followed by an argon plasma, before the coating. This with Plasma-treated glass plates form the substrates to which the OLEDs are applied.

The OLEDs have the following layer structure: substrate / hole

injection layer (HIL) / hole transport layer (HTL) / electrons

blocking layer (EBL) / emission layer (EML) / hole blocking layer (HBL) / 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 Tables 1 a and 1 b. The data of the OLEDs are listed in Tables 2a and 2b. The materials required to manufacture the OLEDs are shown in Table 3.

All materials are thermally evaporated in a vacuum chamber. The emission layer always consists of at least one matrix 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 EG1: IC2: TEG1 (45%: 45%: 10%) means that the material EG1 in a volume fraction of 45%, IC2 in a volume fraction of 45% and TEG1 in a volume fraction of 10% in the layer is present. Analogously, the electron transport layer can also consist of one

Mix of two materials.

The OLEDs are characterized by default. For this, the electroluminescence spectra, the operating voltage and the external

Quantum efficiency (EQE, measured in%) as a function of luminance, calculated from current-voltage-luminance characteristics, assuming a Lambertian radiation characteristic. The

Electroluminescence spectra are determined at a luminance of 1000 cd / m ² and the CIE 1931 x and y color coordinates are calculated therefrom. The specification U1000 in Table 3 denotes the voltage required for a Luminance of 1000 cd / m ^{2 is} required. EQE1000 describes the external quantum efficiency that is achieved at 1000cd / m ² .

The materials EG1 and EG2 according to the invention are in the

Examples E1 and E2 are used as matrix material in the emission layer of green phosphorescent OLEDs.

Very good results for the external quantum efficiency are obtained for both compounds according to the invention.

The materials EG1 and EG3 to EG5 according to the invention are used in Examples E3 to E6 as matrix material in the emission layer of red-phosphorescent OLEDs.

Table 1 b: Structure of the OLEDs

Very good results for the external quantum efficiency are obtained for all four compounds according to the invention.

Table 2: Structural formulas of the materials for the OLEDs

30th

Claims

Expectations

1. Compound of a formula (I)

Formula (I),

where for the variables that occur:

Formula (G-1),

which is attached via the dashed bond, wherein in formula (G-1) W is the same or different CR ² or N at each occurrence; or one or more units from two adjacent groups W are selected the same or different from units of the formulas (W-1) to (W-2) for each occurrence

wherein the dashed bonds are the bonds to the rest of the formula (G-1); where U is chosen the same or different for each occurrence from O, S, NR ³ and C (R ³ ) ₂ ; and wherein in formulas (W-1) to (W-2) V is the same or different CR ² or N at each occurrence; or one or more units from two adjacent groups V are the same or different with each occurrence

where the dashed bonds are the bonds to the rest of formulas (W-1) to (W-2); where Z is the same or different N or CR ² on each occurrence;

T is a single bond that connects the relevant groups X; Each occurrence of R ¹ is the same or different from H, D, F, CI, Br, I, C (= 0) R ⁴ , CN, Si (R ⁴ ) ₃ , N (R ⁴ ) ₂ , P (= 0) (R ⁴ ) ₂ , OR ⁴ , S (= 0) R ⁴ , S (= 0) ₂ R ⁴ , straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 up 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 R ¹ 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 R ⁴ ; and wherein one or more CH ₂ groups in said alkyl, alkoxy, alkenyl and alkynyl groups are represented by -R ⁴ C = CR ⁴ -, -C ^ C-, Si (R ⁴ ) ₂ , C = 0, C = NR ⁴ , -C (= 0) 0-, -C (= 0) NR ⁴ -, NR ⁴ , P (= 0) (R ⁴ ), -O-, -S-, SO or S0 ₂ can;

Each occurrence of R ² is the same or different from H, D, F, CI, Br, I, C (= 0) R ⁴ , CN, Si (R ⁴ ) ₃ , N (R ⁴ ) ₂ , P (= 0) (R ⁴ ) ₂ , OR ⁴ , S (= 0) R ⁴ , S (= 0) ₂ R ⁴ , straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 up 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 R ² 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 R ⁴ ; and wherein one or more CFI ₂ groups in said alkyl, alkoxy, alkenyl and alkynyl groups are represented by -R ⁴ C = CR ⁴ -, -C ^ C-, Si (R ⁴ ) ₂ , C = 0, C = NR ⁴ , -C (= 0) 0-, -C (= 0) NR ⁴ -, NR ⁴ , P (= 0) (R ⁴ ), -O-, -S-, SO or

S0 ₂ can be replaced; Each occurrence of R ³ is the same or different from H, D, F, CI, Br, I, CN, Si (R ⁴ ) 3, N (R ⁴ ) 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; where two or more radicals R ^{3 may} be linked to one another and form a ring; wherein said alkyl groups and said aromatic ring systems and heteroaromatic

Ring systems are each substituted with radicals R ⁴ ;

Each occurrence of R ⁴ is the same or different from H, D, F, CI, Br, I, C (= 0) R ⁵ , CN, Si (R ⁵ ) ₃ , N (R ⁵ ) ₂ , P (= 0) (R ⁵ ) ₂ , OR ⁵ , S (= 0) R ⁵ , S (= 0) ₂ R ⁵ , straight-chain alkyl or alkoxy groups with 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups with 3 up 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 R ⁴ 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 R ⁵ ; and wherein one or more CFI ₂ groups in said alkyl, alkoxy, alkenyl and alkynyl groups are represented by -R ⁵ C = CR ⁵ -, -C ^ C-, Si (R ⁵ ) ₂ , C = 0, C = NR ⁵ , -C (= 0) 0-, -C (= 0) NR ⁵ -, NR ⁵ , P (= 0) (R ⁵ ), -O-, -S-, SO or S0 ₂ can;

Each occurrence of R ⁵ is selected identically or differently from Fl, 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 two or more radicals R ⁵ can be linked to one another and form a ring; and 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 or 1, where if k is 0, T is absent and the relevant groups X are not linked; Each occurrence of m, n, o is the same or different from 0 and 1, with at least one of the indices m, n and o being equal to 1; wherein in at least one of the rings to which a group G is bound, at least one group X is N.

2. Connection according to claim 1, characterized in that one, two, three or four; preferably two or three; two groups X in formula (I) are very particularly preferably equal to N.

3. A compound according to claim 1 or 2, characterized in that in a ring to which a group G binds, exactly one or two, preferably two, groups X are N.

4. A compound according to one or more of claims 1 to 3, characterized in that in a ring to which a group G binds, one or two groups X, which are adjacent for binding to G, are equal to N.

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

6. A compound according to one or more of claims 1 to 5, characterized in that the sum of the indices m, n and o is 1.

7. Compound according to one or more of claims 1 to 6, characterized in that one of the indices m and n is 1 and the other of the indices m and n is 0 and that the index o is 0.

8. A compound according to one or more of claims 1 to 7, characterized in that in a ring in formula (I) to which a group G binds, all radicals R ¹ are selected from aromatic

Ring systems with 5 to 40 aromatic ring atoms which are substituted with one or more R ⁴ radicals.

9. A compound according to one or more of claims 1 to 8, characterized in that

R ¹ is chosen the same or different for each occurrence from H,

aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted with R ⁴ radicals and heteroaromatic ring systems with 5 to 40 aromatic ring atoms which are substituted with R ⁴ radicals; and R ^{2 is selected the} same or different for each occurrence from H, aromatic ring systems with 6 to 40 aromatic ring atoms, which are substituted with radicals R ⁴ , and heteroaromatic ring systems with 5 to 40 aromatic ring atoms, which are substituted with radicals R ⁴ ; and

Each occurrence of R ^{3 is the} same or different 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 to 40 aromatic ring atoms; where two radicals R ³ , which are identical to phenyl, which is substituted by radicals R ⁴ , and which are components of a group U, which is identical to C (R ³ ) ₂ , can be linked to one another and form a ring, so that one Spirobifluorene unit is formed; and wherein said alkyl groups and said aromatic ring systems and heteroaromatic ring systems are each substituted with radicals R ⁴ ; and

Each occurrence of R ^{4 is selected} identically or differently from H, aromatic ring systems with 6 to 40 aromatic ring atoms which are substituted with radicals R ⁵ , and heteroaromatic ring systems with 5 to 40 aromatic ring atoms which are substituted with radicals R ⁵ .

10. A compound according to one or more of claims 1 to 9, characterized in that groups of the formula (G-1) correspond to one of the following formulas

- wherein in formula (G-1 -1) W is defined as in claim 1, and preferably W is CR ² or N, particularly preferably equal to CR ² ; and wherein the unsubstituted positions in formula (G-1 -1) are substituted with radicals R ⁴ ; - wherein in formula (G-1-2) a unit W ¹ -W ^{1 is} selected from the formula below, the dashed lines being the bonds of the unit to the rest of the formula (G-1 -2), and wherein remaining groups W ^{1 are selected} identically or differently from CR ² and N, and are preferably equal to CR ² ; and wherein W is as defined in claim 1, and is preferably equal to CR ² or N, particularly preferably equal to CR ² ; and wherein U is defined as in claim 1, and is preferably selected from O, NR ³ and C (R ³ ) ₂ , particularly preferably from NR ³ ; and wherein V is defined as in claim 1, and is preferably equal to N or CR ² , particularly preferably equal to CR ² ;

- wherein in formula (G-1-3) a unit W ¹ -W ^{1 is} selected from the middle formula, the dashed lines being the bonds of the unit to the rest of the formula (G-1 -3), and wherein the remaining groups W ^{1 are selected} identically or differently from CR ² and N, and are preferably equal to CR ² ; and wherein W is as defined in claim 1, and preferably W is CR ² or N, particularly preferably CR ² ; and wherein in formula (G-1 -3) a unit VV is selected from the formula below, where the dashed lines represent the bonds of

Are units to the rest of the formula (G-1-3), and the remaining groups V being selected identically or differently from CR ² and N, and preferably being equal to CR ² ; and wherein U is as defined in claim 1, and is preferably selected from O, NR ³ and C (R ³ ) ₂ ; and wherein Z is defined as in claim 1 and is preferably CR ² ;

- wherein in formula (G-1-4) a unit W ¹ -W ^{1 is} selected from the middle formula, the dashed lines being the bonds of the unit to the rest of the formula (G-1 -4), and wherein remaining groups W ^{1 are selected} identically or differently from CR ² and N, and are preferably equal to CR ² ; and wherein a unit W ² -W ^{2 is} selected from the formula below, where the dashed lines represent the bonds of Are unit to the rest of the formula (G-1-4), and wherein the remaining groups W ^{2 are selected} identically or differently from CR ² and N, and are preferably equal to CR ² ; and wherein V is as defined in claim 1, and preferably V is selected identically or differently from CR ² and N, and is preferably equal to CR ² ; and where U is as defined in claim

1, and is preferably selected from O, NR ³ and C (R ³ ) 2;

- wherein in formula (G-1-5) W is defined as in claim 1, and preferably W is CR ² or N, particularly preferably equal to CR ² ; and wherein U is as defined in claim 1, and is preferably selected from S; and wherein V is defined as in claim 1, and is preferably equal to N or CR ² , particularly preferably equal to CR ² ;

- Wherein in formula (G-1-6) a unit W ¹ -W ^{1 is} selected from the middle formula, the broken lines the bonds of the unit to the

Are radicals of the formula (G-1-6), and the remaining groups W ¹ being chosen identically or differently from CR ² and N, and preferably being equal to CR ² ; and wherein W is as defined in claim 1, and preferably W is CR ² or N, particularly preferably CR ² ; and wherein in formula (G-1-6) a unit VV is selected from the formula below, the dashed lines being the bonds of the unit to the rest of formula (G-1-6), and wherein the remaining groups V are the same or are selected differently from CR ² and N, and are preferably equal to CR ² ; and wherein U is as defined in claim 1, and is preferably selected from C (R ³ ) 2; and where Z is defined as in

Claim 1 and preferably CR ² ;

- wherein in formula (G-1-7) a unit W ¹ -W ^{1 is} selected from the middle formula, the broken lines being the bonds of the unit to the rest of the formula (G-1 -7), and wherein the remaining groups W ^{1 are selected} identically or differently from CR ² and N, and are preferably equal to CR ² ; and wherein in formula (G-1-7) a unit W ² -W ² is selected from the formula below, the dashed lines being the bonds of the unit to the rest of the formula (G-1-7), and the remaining groups W ² being chosen identically or differently from CR ² and N, and preferably the same Are CR ² ; and wherein U is as defined in claim 1, and is preferably equal to C (R ³ ) 2; and wherein V is as defined in claim 1, and is preferably the same or different CR ² or N on each occurrence, particularly preferably CR ² .

11. A compound according to one or more of claims 1 to 10, characterized in that the compound of formula (I) corresponds to one of the following formulas:

wherein R ^{1 1 is} defined as R ¹ and wherein the symbols are defined as in one or more of claims 1 to 11.

12. A method for producing a compound according to one or more of claims 1 to 11, characterized in that it comprises the following steps:

13. oligomer, polymer or dendrimer containing one or more compounds of the formula (I) according to one or more of claims 1 to 11, wherein the bond (s) to the polymer, oligomer or dendrimer any positions in formula (I) substituted with R ¹ , R ² or R ³ can be located.

14. Formulation containing at least one compound according to one or more of claims 1 to 1 1 or at least one polymer, oligomer or dendrimer according to claim 13, and at least one solvent.

15. Electronic device containing at least one compound according to one or more of claims 1 to 1 1, or at least one polymer, oligomer or dendrimer according to claim 13.

16. Electronic device according to claim 15, characterized in that it is an organic electroluminescent device and contains anode, cathode and at least one emitting layer, and that the compound is contained in an emitting layer together with at least one phosphorescent emitter, or that

Connection in one layer selected from hole blocking layers,

Electron transport layers and electron injection layers are included.

17. The organic electroluminescent device as claimed in claim 16, characterized in that the compound is contained in an emitting layer of the device together with at least one phosphorescent emitter and at least one further compound, the further compound being a matrix material, and the further one

Connection is preferably selected from hole-transporting

Matrix materials, particularly preferably carbazole compounds, Biscarbazole compounds, indolocarbazole compounds and

Indenocarbazole compounds.

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

Claims 1 to 11 in an electronic device.

19. Mixture containing at least one compound according to one or more of claims 1 to 11, and at least one further

Compound selected from matrix materials for phosphorescent emitters.