WO2016079667A1

WO2016079667A1 - Indole derivatives for electronic applications

Info

Publication number: WO2016079667A1
Application number: PCT/IB2015/058877
Authority: WO
Inventors: Yuki Nakano; Takushi Shiomi
Original assignee: Idemitsu Kosan Co Ltd
Current assignee: Idemitsu Kosan Co Ltd
Priority date: 2014-11-17
Filing date: 2015-11-17
Publication date: 2016-05-26
Anticipated expiration: 2017-05-17

Abstract

The present invention relates to compounds of formula (I), a process for their production and their use in electronic devices, especially electroluminescent devices. When used as charge transport material and/or host material for phosphorescent emitters in electroluminescent devices, the compounds of formula I may provide improved efficiency and reduced driving voltage of electro- luminescent devices.

Description

indole derivatives for electronic applications

Description

The present invention relates to compounds of formula I, a process for their production and their use in electronic devices, especially electroluminescent devices. When used as charge transport material and/or host material for phosphorescent emitters in electroluminescent devices, the compounds of formula I may provide improved efficiency and reduced driving voltage of electroluminescent devices.

US2002117662 discloses a light-emitting device comprising: a pair of electrodes formed on a substrate; and at least one organic compound layer containing a light-emitting layer provided between the electrodes, wherein the at least one organic compound layer comprises a host material, a layer of the host material has an energy gap of not less than 3.6 eV and an ionization potential of the host material is from 5.4 eV to 6.3 eV.

Preferably, the host material compri prising a partial structure repre-

sented by the following formula (II): , wherein

wherein L¹² represents one of a from 2- to 6-valent connecting group having a heteroaryl group and a from 2- to 6-valent connecting group comprising a non-conjugate connecting group having an arylene group; n represents an integer of from 2 to 6; R represents one of an alkyl group having from 1 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, a heteroaryl group having from 2 to 20 carbon atoms and a silyl group having from 3 to 20 carbon atoms; and m represents an integer of from 0 to 6. The examples given for L¹²

do not include a group of formula

WO08066196 is directed to an organic electroluminescent device comprising: a pair of electrodes; and at least one organic layer between the pair of electrodes, the at least one organic layer including a light-emitting layer containing a light-emitting material, wherein the at least one organic layer includes at least one layer containing an indole derivative represented by formula (1):

n ⁰ , wherein Ri<" , R102, RKH Rio4 _anc| Rios _each independently represents a hydrogen atom or a substituent; R¹⁰⁶ represents an alkyl group having a tertiary or quaternary carbon atom; R¹⁰¹ and R¹⁰⁶ may be bonded to each other to form a ring; L¹⁰¹ represents a linking group; and n¹⁰¹ represents an integer of 2 or higher. T ude a group of formula

JP2003277744 relates to a material for an organic electroluminescent element which comprises a compound comprising a group bearing an indole skeleton and, bonded thereto, a group bearing a cycloalkane skeleton or a meta-aromatic ring group. The organic electroluminescent element comprises a monolayered or multi-layered organic thin film layers sandwiched between a cathode and an anode, where at least one layer of the organic thin film layers contains the material for the organic electroluminescent element. JP2009049318 relates to an electroluminescent device which comprises an indole deriva

tive represented by a general formula ⁿ (1). R¹⁰⁶ denotes a silyl substituent.

JP2012089777 relates to an electroluminescence element which is characterized in that at least one of the organic compound layers contains a compound represented by following

KR20140087805A discloses compounds for organic optoelectronic devices, including or

ganic light-emitting devices, represented by the following formula

n is an integer of 1 to 3 and, R¹ is hydrogen, deuterium, halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1-C20 amine group, a nitro group, a carboxyl group, a ferrocenyl group, a substituted or unsubstituted C1- C20alkyl group, a substituted or unsubstituted C6-C30arylgroup, a substituted or unsubstituted C2 to C30heteroaryl group ...

L may be a group of formula (X is O, or S), which is bonded to the indole skeleton by a C-C bond. KR20140103842 discloses an organic light emitting device including a compound repre-

sented by the formula

J. Keruckas et al. Dyes and Pigments 100 (2014) 66-72 disclose3,6-bis(indol-1-yl)-9- phenylcarbazoles as electroactive materials for electrophosphorescent diodes:

BIPC (Ri = R₂ =H), BIPC1 (Ri = OCH₃, R₂ =H), BIPC2 (R₂ = OCH3, Ri =H), BIPC3 (Ri = R₂ = OCH3). Notwithstanding these developments, there remains a need for organic light emitting devices comprising new charge transport materials to provide improved efficiency, stability, manufacturability, and/or spectral characteristics of electroluminescent devices.

Accordingly, it is an object of the present invention, with respect to the aforementioned prior art, to provide further materials suitable for use in OLEDs and further applications in organic electronics. More particularly, it should be possible to provide charge transport materials, charge/exciton blocker materials and matrix materials for use in OLEDs. The materials should be suitable especially for OLEDs which comprise at least one phosphorescence emitter, especially at least one green emitter or at least one blue emitter. Furthermore, the materials should be suitable for providing OLEDs which ensure good efficiencies, good operative lifetimes and a high stability to thermal stress, and a low use and operating voltage of the OLEDs.

Certain indole derivatives are found to be suitable for use in organo-electroluminescent devices. In particular, said derivatives are suitable charge transport materials, or host materials for phosphorescent emitters with low driving voltage, good efficiency and good operative lifetimes.

S

(I), wherein m is 0, 1 or 2, n is 0, 1 or 2,

Ar¹ and Ar² are independently of each other a C6-C24arylen group, which can optionally be substituted by G, a C2-C3oheteroarylen group, which can optionally be substituted by G, Bi is N, or CR³,

B3 is N, or CRs,

B⁴ is N, or CR⁶,

with the proviso that not more than two of B¹, B², B³ and B⁴ are N;

Bii is N, or CRsi,

with the proviso that not more than two of B¹¹, B¹², B¹³ and B¹⁴ are N;

Bi6 is N, or CRse,

Bi⁸ is N, or CRss,

with the proviso that not more than two of B¹⁵, B¹⁶, B¹⁷ and B¹⁸ are N;

R¹ and R² are independently of each other -H, -F, CN, a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24aryloxy group, which can optionally be substituted by G;

Xⁱ is O, S, Se or NR⁷,

with the proviso that, if at least one of R¹, R², R³, R⁴, R⁵, and R⁶ is -CN, then A is -NR¹⁰R¹¹, or -Si(R¹ )(R¹³)(R¹⁴), _a C₆-C₂4aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;

R3, R4, R5 , R6, R5i _ R52₇ 53, 54, R55, R56, R57, _anc| R58 _are independently of each other -H, -F, CN, a C2-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24 aryloxy group, which can optionally be substituted by G;

R⁷ is a Ci-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C25cycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G;

R¹⁰ and R¹¹ are independently of each other H, a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G; R¹², R¹³ and R¹⁴ are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by L; a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G; with the proviso that, if all of R¹, R², R³, R⁴, R⁵ and R⁶ are different from -CN, then

A is a C6-C24arylen group, which can optionally be substituted by G, a Ci3-C3oheteroarylen group, which can optionally be substituted by G, an azacarbazolyl, which can optionally be substituted by G, an azaindolyl, which can optionally be substituted by G, a dibenzofuranyl, which can optionally be substituted by G, a dibenzothiophenyl, which can optionally be substituted by G, a benzofuranyl, which can optionally be substituted by G, a benzothio- phenyl, which can optionally be substituted by G, a pyridyl, which can optionally be substituted by G, a pynmidinyl, which can optionally be substituted by G, a pyrazinyl, which can optionally be substituted by G, a triazinyl, which can optionally be substituted by G, a naph- , or a group represented by formula

(IV),

B¹⁹ is N or CR⁶¹, preferably CR⁶¹,

B²⁰ is N or CR⁶², preferably CR⁶²,

B²ⁱ is N or CR6³, preferably CR6³,

B²² is N or CR⁶⁴, preferably CR⁶⁴,

with the proviso that not more than two of B¹⁹, B²⁰, B²¹ and B²² are N;

B²³ is N or CR⁶⁵, preferably CR⁶⁵,

B²⁴ is N or CR⁶⁶, preferably CR⁶⁶,

B²5 is N or CR6⁷, preferably CR6⁷,

B²⁶ is N or CR⁶⁸, preferably CR⁶⁸,

with the proviso that not more than two of B²³, B²⁴, B²⁵ and B²⁶ are N;

B²⁷ is N or CR⁶⁹, preferably CR⁶⁹,

B²⁸ is N or CR⁷⁰, preferably CR⁷⁰, B²⁹ is N or CR⁷¹ , preferably CR⁷¹ ,

B³⁰ is N or CR⁷², preferably CR⁷²,

B3ⁱ is N or CR⁷3, preferably CR⁷3,

B³² is N or CR⁷⁴, preferably CR⁷⁴,

with the proviso that not more than two of B²⁹, B³⁰, B³¹ and B³² are N;

with the proviso that N in the groups of formula (III) and (IV) chemically binds to one of B¹⁵, B¹⁶, B¹⁷, or B¹⁸, or Ar¹ , or Ar², if present;

R61 , R6², R⁶³, R6⁴, Res, R66, R67₇ es, 69, /o, R71 , R72, R73 _anc| R74 _are independently of each other -H, -F, -C≡N, a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2- C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24aryloxy group, which can optionally be substituted by G;

D is -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -NR²S -POR²⁴-, -CR²s=CR²6-, or -C≡C-,

E is -ORS1 , -SR³¹ , -NR³²R³³, -COR³⁴, -COOR³⁴, -CONR³²R³³, -C≡N, or -F,

L is D, or -SiR²²R²³-,

G is E, or a Ci-Cisalkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by -F, Ci-Cisalkyl, or Ci-Cisalkyl which is interrupted by -0-; a C2-C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by -F, Ci-Cisalkyl, or Ci-Cisalkyl which is inter- rupted by O;

R²¹ , R³² and R³³ are independently of each other a C6-Cisaryl group; a C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O-; or R³² and R³³ together form a five or six membered ring, R²² and R²³ are independently of each other a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl,

R²⁴ is a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl,

R²⁵ and R²⁶ are independently of each other H, C6-Cisaryl; C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; Ci-Cisalkyl; or Ci-Cisalkyl which is interrupted by -0-, R³¹ is a C6-Cisaryl; a C6-Cisaryl, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci- Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O- and

R³⁴ is a C6-Cisaryl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, or Ci- Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-. The combination of the hole transporting indole group with the dibenzofuranyl group gives rise to materials that are highly suitable in devices that emit green, or blue light. Moreover, the improved amipolar characteristics give rise to more balanced charge transport in devices resulting in lower voltages and higher external quantum efficiencies (EQE's). The compounds of the present invention may be used for electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaics), switching elements, such as organic transistors, for example, organic FETs and organic TFTs, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers and electroluminescent devices, such as, for example, organic light-emitting diodes (OLEDs). Accordingly, a further subject of the present invention is directed to an electronic device, comprising a compound according to the present invention. The electronic device is preferably an electroluminescent device. The compounds of formula I can in principal be used in any layer of an EL device, but are preferably used as host, charge transport and/or charge/exciton blocking material. Particularly, the compounds of formula I are used as host material for green, especially blue light emitting phosphorescent emitters. Hence, a further subject of the present invention is directed to a charge transport layer, comprising a compound of formula I according to the present invention.

A further subject of the present invention is directed to an emitting layer, comprising a compound of formula I according to the present invention. In said embodiment a compound of formula I is preferably used as host material in combination with a phosphorescent emitter.

A further subject of the present invention is directed to a charge/exciton blocking layer, comprising a compound of formula I according to the present invention. D is preferably -CO-, -COO-, -S-, -SO-, -S0₂-, -0-, -NR21-, wherein R21 is Ci-Ci₈alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or Ce-C aryl, such as phenyl, tolyl, naphthyl, or biphenylyl, or C2-C3oheteroaryl, such as, for example, benzimid-

azo[1 ,2-a]benzimidazo-2-yl ( ), carbazolyl, dibenzofuranyl, which can be unsubstituted or substituted especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl; or C2-Ci3heteroaryl.

E is preferably -OR31 ; -SR3i ; -NR32R33; -COR34; -COOR34; -CONR32R33; ₀r -CN; wherein R3i , R32, R33 _anc| R34 _are independently of each other Ci-Cisalkyl, such as methyl, ethyl, n- propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or Ce-C aryl, such as phenyl, tolyl, naphthyl, or biphenylyl.

G is preferably -OR³¹; -SR3ⁱ ; -NR32R33; _a Ci-Ci₈alkyl group, a C₆-Ci₄aryl group, a Ce- C aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Ci3heteroaryl group, or a C2- Ci₃heteroaryl group, which is substituted by F, or Ci-Cisalkyl; wherein R³¹, R³2, R33 and R³4 are independently of each other Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n- butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-Ci₄aryl, such as phenyl, tolyl, naphthyl, or biphenylyl. A C2-Ci3heteroaryl group is for example, benzimidazo[1 ,2-a]benzimidazo-5-yl

(

), benzim- idazolo[2,1-b][1 ,3]benzothiazolyl, carbazolyl, dibenzofuranyl, or dibenzotihophenyl, which can be unsubstituted or substituted, especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl ; or C2-Ci3heteroaryl.

Specific examples of the compound represented by the formula (I) are given below. The compound represented by the formula (I) is not limited to the following specific examples. re shown

(A-2),

Among the compounds of formula (I), compounds of formula

(la) are more pi ferred, wherein R¹ , R², R³, R⁴, R5, R6, en, B¹², B¹³, B¹⁴, B¹⁵, B¹⁶, B¹⁷, B¹8, χι, Ar¹, Ar², A, and n are defined above and below.

Among the compounds of formula (la), compounds of formula

ferred, wherein R¹, R², R³, R⁴, R⁵, R⁶, X¹ , Ar¹, Ar², A, m and n are defined above and below. unds of formula

are more preferred, wherein R¹, R², R³, R⁴, R⁵, R⁶, X¹ , Ar¹, Ar², A, m and n are defined above and below. Among the compounds of formula (lc), compounds of formula

(Id) are more preferred, wherein

Xⁱ is NR⁷, O, or S,

R¹, R², R³, R⁴, Rs, Re, R7, Ar¹ and A are defined above and below, and

m is 0 or 1. Among the compounds of formula (Id), compounds of formula

In a preferred embodiment of the present invention m is 0.

Examples of compounds of formula (I), wherein at least one of R¹, R², R³, R⁴, R⁵ and R⁶ is a carbazolyl group, a diaryl amino group, or an indolyl group are shown below:

Compounds of formula (I), wherein at least one of R¹, R², R³, R⁴, R⁵ and R⁶ is a Ci-C2salkyl group; and/or at least a group Ar¹ , Ar² and/or A is substituted by a Ci-C2salkyl group; are suitable materials for solution processable organic light emitting devices (OLEDs). Exam

Preferably, R¹ , R², R³, R⁴, R⁵ and R⁶ are independently of each other -H, or -CN. Ar¹ and Ar² are independently of each other a C6-C24arylen group, which can optionally be substituted by G, a C2-C3oheteroarylen group, which can optionally be substituted by G,

The C6-C24arylen groups Ar¹ and Ar², which optionally can be substituted by G, are typically phenylene, 4-methylphenylene, 4-methoxyphenylene, naphthylene, especially 1- naphthylene, or 2-naphthylene, biphenylylene, terphenylylene, pyrenylene, 2- or 9- fluorenylene, phenanthrylene, or anthrylene, which may be unsubstituted or substituted.

The C2-C3oheteroarylen groups Ar¹ and Ar², which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms havi ated-electrons such as, for example, benzofu-

ro[2,3-b]pyridylene ( ), benzothiopheno[2,3-b]pyridylene

( ), thienylene, benzothiophenylene, thianthrenylene, furylene, furfu- rylene, 2H-pyranylene, benzofuranylene, isobenzofuranylene, dibenzofuranylene

( ), dibenzothiophenylene ( ), phenoxythienylene, pyrrolylene, imidazolylene, pyrazolylene, pyridylene, bipyridylene, triazinylene, pyrimidi- nylene, pyrazinylene, pyndazinylene, indolizinylene, isoindolylene, indolylene, indazolylene, purinylene, quinolizinylene, chinolylene, isochinolylene, phthalazinylene, naphthyndinylene, chinoxalinylene, chinazolinylene, cinnolinylene, pteridinylene, carbolinylene, benzotriazol- ylene, benzoxazolylene, phenanthridinylene, acridinylene, pyrimidinylene, phenanthroli- nylene, phenazinylene, isothiazolylene, phenothiazinylene, isoxazolylene, furazanylene,

carbazolylene ( , or ), benzimidazo[1 ,2-

a]benzimidazo-2,5-ylene ( ), benzimidazo-1 ,2-ylene ( ), or phenoxazinylene, which can be unsubstituted or substituted. R^24' is a C6-C24aryl group, or a C2-C3oheteroaryl group, which can optionally be substituted by G, wherein G is as defined in above.

A further example for a C2-C3oheteroarylen group Ar¹ and Ar² is 2-phenyl pyrimidinylene.

Preferred C6-C24arylen groups are 1 ,3-phenylene, 1 ,4-phenylene, 3,3'-biphenylylene, 3,3'- m-teφhenylene, 2- or 9-fluorenylene, phenanthrylene, which may be unsubstituted or substituted, especially by C6-Cioaryl , C6-Cioaryl which is substituted by Ci-C4alkyl ; or C2- C heteroaryl.

Preferred C2-C3oheteroarylen groups are pyridylene, triazinylene, pyrimidinylene, benzofu- ro[2,3-b]pyridylene, benzothiopheno[2,3-b]pyridylene , pyrido[2,3-b]indolylene , benzofu- ro[2,3-c]pyridylene, benzothiopheno[2,3-c]pyridylene , pyrido[2,3-c]indolylene, furo[3,2- b:4,5-b']dipyridylene, thieno[3,2-b:4,5-b']dipyridylene, pyrrolo[3,2-b:4,5-b']dipyridylene, dibenzofuranylene, dibenzothiophenylene , carbazolylene and benzimidazo[1 ,2- a] benzimidazo-2,5-ylene, benzofuro[3,2-b]pyridylene, indolylene, benzothiopheno[3,2- b] pyridylene, or benzimidazo-1 ,2-ylene, which can be unsubstituted or substituted , espe- cially by C6-Ci4aryl , C6-Ci4aryl which is substituted by Ci-C4alkyl ; or C2-Ci3heteroaryl . The C6-C24arylen and C2-C3oheteroarylen groups may be substituted by G.

G is preferably Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, -CF3, a C6-Ci4aryl group, a Ce-C aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Ci3heteroaryl group, or a C2-Ci3heteroaryl group, which is substituted by F, or Ci-Cisalkyl.

Benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimidazo[1 ,2-a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are examples of a C2-Ci3heteroaryl group. Phenyl, 1-naphthyl and 2- naphthyl are examples of a Ce-C aryl group.

Preferably, Ar¹ and Ar² are independently of each other a group of formula

Further preferred groups Ar¹ and Ar² are:

If at least one of Ri, R2, R3, R4, R5 and R6 is -CN, then A is -NRi°Rii, or -Si(Ri2)(Ri3)(Ri4), a C6-C24ar l group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G. The C6-C24aryl group A, which optionally can be substituted by G, is typically phenyl, 4- methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, or anthryl, or triphenylenyl (especially triphenylen-2-yl), which may be unsubstituted or substituted. The C2-C3oheteroaryl group A, which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated π-electrons such as 9H-pyrido[2,3-b]indolyl, benzofuro[2,3- b]pyridyl, benzothiopheno[2,3-b]pyridyl, 9H-pyrido[2,3-c]indolyl, benzofuro[2,3-c]pyridyl, benzothiopheno[2,3-c]pyridyl, furo[3,2-b:4,5-b']dipyridyl, pyrrolo[3,2-b:4,5-b']dipyridyl, thieno[3,2-b:4,5-b']dipyridyl, thienyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrol- yl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, in- dolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothia- zolyl, phenothiazinyl, isoxazolyl, furazanyl, benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimid- azo[1 ,2-a]benzimidazo-2-yl, benzimidazolo[2,1-b][1 ,3]benzothiazolyl, carbazolyl, 9- phenylcarbazolyl, azabenzimidazo[1 ,2-a]benzimidazolyl, or phenoxazinyl, which can be unsubstituted or substituted.

The C6-C24aryl and C2-C3oheteroaryl groups may be substituted by G.

G is preferably Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl; -CF3, a C6-Ci4aryl group, a Ce-C aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Ci3heteroaryl group, or a C2-Ci3heteroaryl group, which is substituted by F, or Ci-Cisalkyl.

Prefered C2-C3oheteroaryl groups are pyridyl, triazinyl, pyrimidinyl, especially 9H-pyrido[2,3- b]indolyl, benzofuro[2,3-b]pyridyl, benzothiopheno[2,3-b]pyridyl, 9H-pyrido[2,3-c]indolyl, benzofuro[2,3-c]pyridyl, benzothiopheno[2,3-c]pyridyl, furo[3,2-b:4,5-b']dipyridyl, pyr- rolo[3,2-b:4,5-b']dipyridyl, thieno[3,2-b:4,5-b']dipyridyl, benzimidazo[1 ,2-a]benzimidazo-5-yl

R

), benzimidazo[1 ,2-a]benzimidazo-2-yl ( R" is

C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl), benzimid-

azolo[2,1-b][1 ,3]benzothiazolyl ( , or ), carba- zolyl, dibenzofuranyl, or dibenzothiophenyl, which can be unsubstituted or substituted especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl .

; wherein R³⁷, R³⁸, R³⁹, R⁴⁰ and

R⁴¹ are independently of each other -H, -CN, or a phenyl group.

If all of R¹, R2, R³, R⁴, Rs and R⁶ are different from -CN, then A is a C₆-C₂4aryl group, which can optionally be substituted by G, a Ci3-C3oheteroaryl group, which can optionally be sub- stituted by G, an azacarbazolyl, which can optionally be substituted by G, an azaindolyl, which can optionally be substituted by G, a dibenzofuranyl, which can optionally be substituted by G, a dibenzothiophenyl, which can optionally be substituted by G, a benzofuranyl, which can optionally be substituted by G, a benzothiophenyl, which can optionally be substituted by G, a pyridyl, which can optionally be substituted by G, a pyrimidinyl, which can optionally be substituted by G, a pyrazinyl, which can optionally be substituted by G, a tria- zinyl, which can optionally be substituted by G, a naphtyridinyl, which can optionally be substituted by G, or a group represented by formula

(III), or (IV), wherein

B13 B14, Bis, Bis, B17, Bis, Bis, B2o, B21, B22, B23, B2 , B25 and B26are defined above.

The group of formula (III) is preferably a group of formula

R⁴¹ are independently of each other -H, -CN, or a phenyl group. In a preferred embodiment the present invention relates to compounds of formula (I), wherein R¹, R², R³, R⁴, R⁵ and R⁶ are H. In said embodiment compounds of formula

Examples of compounds, wherein R¹, R², R³, R⁴, R⁵ and R⁶ are H and X¹ is NR⁷, are shown below.

(C-27), (C-28), (C-29),

In said embodiment compounds of formula (I) are more preferred, wherein R¹, R², R³, R⁴, R5 and R⁶ are H and X¹ is S.

In said embodiment compounds of formula (I) are most preferred, wherein R¹, R², R³, R⁴,

,

In another preferred embodiment the present invention relates to compounds of formula (I), wherein at least one of R¹, R², R³, R⁴, R⁵ and R⁶ is -CN. Examples of compounds, wherein R¹, R2, R3, R5, or R⁶ is -CN, are shown below.



Further examples of compounds, wherein one of R¹, R², R³, R⁵, or R⁶ is -CN and X¹ is O or S, are shown below.

I

S, Ar¹ and A are defined above and m is 0 or 1.

Further preferred groups Ar¹ are:

In said embodiment compounds of formula (I) are more preferred, wherein R⁴ is -CN. Examples of compounds, wherein R⁴ is -CN and X¹ is NR⁷, are shown below.

In said embodiment compounds of formula (I) are more preferred, wherein R⁴ is -CN and Xⁱ is S.

In said embodiment compounds of formula (I) are most preferred, wherein R⁴ is -CN and Xⁱ is O.

Compounds of formula (ld-1a), (ld-1b), (ld-2a) and (ld-2b) are preferred. Compounds of formula (ld-1a) and (ld-1 b) are most preferred.

Examples of preferred compounds of formula I are compounds (D-33), (D-34), (D-35), (D- 36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) shown above. As well as compounds (D74) to (D131) shown above. Compounds (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) are particularly preferred. Also, compounds (D74) to

(D131 ) are particularly preferred.

Halogen is fluorine, chlorine, bromine and iodine. Ci-C25alkyl (Ci-Cisalkyl) is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3- pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1 -methyl hexyl, 1,1 ,3,3,5,5- hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyl- heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, oroctadecyl. Ci-Csalkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2- ethylhexyl. Ci-C4alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, iso- butyl, tert.-butyl.

Ci-C25alkoxy groups (Ci-Cisalkoxy groups) are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, un- decyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. Examples of Ci-Csalkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2- dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1,1,3,3-tetramethylbutoxy and 2- ethylhexyloxy, preferably Ci-C4alkoxy such as typically methoxy, ethoxy, n-propoxy, iso- propoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy.

The term "cycloalkyl group" is typically C5-Ci2cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted.

C6-C24aryl (C6-Cisaryl), which optionally can be substituted, is typically phenyl, 4- methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, oranthryl, which may be unsubstituted or substituted. Phenyl, 1-naphthyl and 2-naphthyl are examples of a C6-Cioaryl group.

C6-C24aryloxy, which optionally can be substituted, is typically C6-Cioaryloxy, which optionally can be substituted by one, or more Ci-Csalkyl and/or Ci-Csalkoxy groups, such as, for example, phenoxy, 1-naphthoxy, or 2-naphthoxy. C₇-C25aralkyl is typically benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-co-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, co-phenyl-eicosyl or ω-phenyl-docosyl, preferably C₇-Cisaralkyl such as benzyl, 2-benzyl-2- propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-co-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, and particularly preferred C₇-Ci2aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, or ω,ω-dimethyl-co-phenyl-butyl, in which both the aliphatic hydrocarbon group and aromatic hydrocarbon group may be unsubstituted or substituted. Preferred examples are benzyl, 2- phenylethyl, 3-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl. C2-C3oheteroaryl represents a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen , oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated π-electrons such as thienyl , benzothiophenyl , dibenzothiophenyl, thianthrenyl , furyl , furfuryl , 2H-pyranyl, benzo- furanyl , isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl , pyrazolyl , pyridyl , bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl , indolizinyl , isoindolyl , indolyl , indazolyl , purinyl , quinolizinyl, chinolyl, isochinolyl, phthalazinyl , naphthyridinyl , chinoxalinyl, chinazolinyl , cinnolinyl, pteridinyl, carbazolyl , carbolinyl , benzotriazolyl , benzoxazolyl , phe- nanthridinyl , acridinyl , pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl , phenothiazinyl , isoxazolyl , furazanyl, 4-imidazo[1 ,2-a]benzimidazoyl, 5-benzimidazo[1 ,2-a]benzimidazoyl , benzimidazolo[2, 1-b][1 ,3]benzothiazolyl, carbazolyl, or phenoxazinyl , which can be unsubstituted or substituted. Benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimidazo[1 ,2- a]benzimidazo-2-yl , carbazolyl and dibenzofuranyl are examples of a C2-Ci4heteroaryl group.

C6-C24arylen groups, which optionally can be substituted by G, are typically phenylene, 4- methylphenylene, 4-methoxyphenylene, naphthylene, especially 1-naphthylene, or 2- naphthylene, biphenylylene, terphenylylene, pyrenylene, 2- or 9-fluorenylene, phenan- thrylene, or anthrylene, which may be unsubstituted or substituted. Preferred C6-C24arylen groups are 1 ,3-phenylene, 3,3'-biphenylylene, 3,3'-m-terphenylene, 2- or 9-fluorenylene, phenanthrylene, which may be unsubstituted or substituted.

C2-C3oheteroarylen groups, which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen , oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated -electrons such as thienylene, benzothiophenylene, dibenzothio- phenylene, thianthrenylene, furylene, furfurylene, 2H-pyranylene, benzofuranylene, isoben- zofuranylene, dibenzofuranylene, phenoxythienylene, pyrrolylene, imidazolylene, pyrazol- ylene, pyridylene, bipyridylene, triazinylene, pyrimidinylene, pyrazinylene, pyridazinylene, indolizinylene, isoindolylene, indolylene, indazolylene, purinylene, quinolizinylene, chinol- ylene, isochinolylene, phthalazinylene, naphthyridinylene, chinoxalinylene, chinazolinylene, cinnolinylene, pteridinylene, carbolinylene, benzotriazolylene, benzoxazolylene, phenan- thridinylene, acridinylene, pyrimidinylene, phenanthrolinylene, phenazinylene, isothiazol- ylene, phenothiazinylene, isoxazolylene, furazanylene, carbazolylene, benzimidazo[1 ,2- a]benzimidazo-2,5-ylene, or phenoxazinylene, which can be unsubstituted or substituted . Preferred C2-C3oheteroarylen groups are pyridylene, triazinylene, pyrimidinylene, carbazolyl ene and benzimidazo[1 ,2-a]benzimidazo-2,5-ylene

( ), which can be unsubstituted or substituted, especially by C6-Cioaryl ,

C6-Cioaryl which is substituted by Ci-C4alkyl ; or C2-Ci4heteroaryl. Possible substituents of the above-mentioned groups are Ci-Csalkyl, a hydroxyl group, a mercapto group, Ci-Csalkoxy, Ci-Csalkylthio, halogen, halo-Ci-Csalkyl, or a cyano group. The C6-C24aryl (C6-Cisaryl) and C2-C3oheteroaryl groups are preferably substituted by one, or more Ci-Csalkyl groups.

If a substituent occurs more than one time in a group, it can be different in each occurrence.

Halo-Ci-Csalkyl is an alkyl group where at least one of the hydrogen atoms is replaced by a halogen atom. Examples are -CF₃, -CF2CF3, -CF2CF2CF3, -CF(CF₃)₂, -(CF₂)₃CF₃, and -C(CF₃)₃.

The wording "substituted by G" means that one, or more, especially one to three substituents G might be present.

As described above, the aforementioned groups may be substituted by E and/or, if desired, interrupted by D. Interruptions are of course possible only in the case of groups containing at least 2 carbon atoms connected to one another by single bonds; C6-Cisaryl is not interrupted; interrupted arylalkyl contains the unit D in the alkyl moiety. Ci-Cisalkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (Ch Ch OJi-g- R^x, where R* is H or Ci-Cioalkyl or C₂-Ci₀alkanoyl (e.g. CO-CH(C2H₅)C₄H9), CH₂-CH(OR^y')- CH2-0-R^y, where R^y is Ci-Cisalkyl, C5-Ci2cycloalkyl, phenyl, Cz-Cisphenylalkyl, and R^y' embraces the same definitions as R^y or is H;

Ci-C₈alkylene-COO-R^z, e.g. CH₂COOR_z, CH(CH₃)COOR^z, C(CH₃)₂COOR^z, where R^ is H, Ci-Cisalkyl, (Ch Ch OJi-g-R*, and R^x embraces the definitions indicated above;

CH₂CH₂-0-CO-CH=CH₂; CH₂CH(OH)CH₂-0-CO-C(CH₃)=CH₂.

An alkyl group substituted by E is, for example, an alkyl group where at least one of the hydrogen atoms is replaced by F. Examples are -CF₃, -CF2CF₃,

-CF₂CF₂CF₃, -CF(CF₃)₂, -(CF₂)₃CF₃, and -C(CF₃)₃.

The synthesis of is described, for example, in Achour, Reddouane;

Zniber, Rachid, Bulletin des Societes Chimiques Beiges 96 (1987) 787-92.

Suitable base skeletons of the formula are either commercially available

(especially in the cases when X is S, O, NH), or can be obtained by processes known to those skilled in the art. Reference is made to WO2010079051 and EP1885818.

The halogenation can be performed by methods known to those skilled in the art. Preference is given to brominating or iodinating in the 3 and 6 positions (dibromination) or in the 3 or 6 positions (monobromination) of the base skeleton of the formula 2,8 positions (diben- zofuran and dibenzothiophene) or 3,6 positions (carbazole). Optionally substituted dibenzofurans, dibenzothiophenes and carbazoles can be dibromin- ated in the 2,8 positions (dibenzofuran and dibenzothiophene) or 3,6 positions (carbazole) with bromine or NBS in glacial acetic acid or in chloroform. For example, the bromination with Br2 can be effected in glacial acetic acid or chloroform at low temperatures, e.g. 0°C. Suitable processes are described, for example, in M. Park, J.R. Buck, C.J. Rizzo, Tetrahedron, 54 (1998) 12707-12714 for X= NPh, and in W. Yang et al., J. Mater. Chem. 13 (2003) 1351 for X= S. In addition, 3,6-dibromocarbazole, 3,6-dibromo-9-phenylcarbazole, 2,8- dibromodibenzothiophene, 2,8-dibromodibenzofuran, 2-bromocarbazole, 3- bromodibenzothiophene, 3-bromodibenzofuran, 3-bromocarbazole, 2- bromodibenzothiophene and 2-bromodibenzofuran are commercially available.

Monobromination in the 4 position of dibenzofuran (and analogously for dibenzothiophene) is described, for example, in J. Am. Chem. Soc. 1984, 106, 7150. Dibenzofuran (diben- zothiophene) can be monobrominated in the 3 position by a sequence known to those skilled in the art, comprising a nitration, reduction and subsequent Sandmeyer reaction.

Monobromination in the 2 position of dibenzofuran or dibenzothiophene and monobromination in the 3 position of carbazole are effected analogously to the dibromination, with the exception that only one equivalent of bromine or NBS is added.

Alternatively, it is also possible to utilize iodinated dibenzofurans, dibenzothiophenes and carbazoles. The preparation is described, inter alia, in Tetrahedron. Lett. 47 (2006) 6957- 6960, Eur. J. Inorg. Chem. 24 (2005) 4976-4984, J. Heterocyclic Chem. 39 (2002) 933-941 , J. Am. Chem. Soc. 124 (2002) 1 1900-1 1907, J. Heterocyclic Chem, 38 (2001) 77-87.

For the nucleophilic substitution, CI- or F-substituted dibenzofurans, dibenzothiophenes and carbazoles are required. The chlorination is described, inter alia, in J. Heterocyclic

Chemistry, 34 (1997) 891-900, Org. Lett., 6 (2004) 3501-3504; J. Chem. Soc. [Section] C: Organic, 16 (1971) 2775-7, Tetrahedron Lett. 25 (1984) 5363-6, J. Org. Chem. 69 (2004)

8177-8182. The fluorination is described in J. Org. Chem. 63 (1998) 878-880 and J. Chem.

Soc, Perkin Trans. 2, 5 (2002) 953-957.

H

The introduction of the group ¾ is performed in the presence of a base.

Suitable bases are known to those skilled in the art and are preferably selected from the group consisting of alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca(OH)2, alkali metal hydrides such as NaH, KH, alkali metal amides such as NaNH2, alkali metal or alkaline earth metal carbonates such as K2CO3 or CS2CO3, and alkali metal alkox- ides such as NaOMe, NaOEt. In addition, mixtures of the aforementioned bases are suitable. Particular preference is given to NaOH, KOH, NaH or K2CO3.

The synthesis of of the compounds of formula (I) can be done in analogy to methods known in the literature. Heteroarylation of can be affected, for

example, by copper-catalyzed coupling of (R⁴ = H, or CN; Ullmann reaction). Indole and 5-cyanoindole derivatives are commercially available. The synthesis

2-bromo-8-iodo-dibenzofurane, and 2-bromo-8-iodo-

dibenzofurane, , is described in EP1885818. er-catalyzed coupling of

to the brominated com

(R⁴ = H, or CN; Ullmann reaction).

The N-arylation is, for example, disclosed in H. Gilman and D. A. Shirley, J. Am. Chem. Soc. 66 (1944) 888; D. Li et al., Dyes and Pigments 49 (2001) 181 - 186 and Eur. J. Org. Chem. (2007) 2147-2151. The reaction can be performed in solvent or in a melt. Suitable solvents are, for example, (polar) aprotic solvents such as dimethyl sulfoxide, dimethylfor- mamide, N-methyl-2-pyrrolidone (NMP), tridecane or alcohols.

Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and car- bazoles can be readily prepared by an increasing number of routes. An overview of the synthetic routes is, for example, given in Angew. Chem. Int. Ed. 48 (2009) 9240 - 9261.

By one common route diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes, and carbazoles can be obtained by reacting halogenated dibenzofurans, dibenzothiophenes and carbazoles with (Y¹0)2B-B(OY¹)2,

^Υ ο^'Β"Β^^γ

or in the presence of a catalyst, such as, for example, [1 ,1'- bis(diphenylphosphino)ferrocene]dichloropalladium(ll), complex (Pd(CI)2(dppf)), and a base, such as, for example, potassium acetate, in a solvent, such as, for example, dimethyl formamide, dimethyl sulfoxide, dioxane and/or toluene (cf. Prasad Appukkuttan et al., Syn- lett 8 (2003) 1204), wherein Y¹ is independently in each occurrence a C1-C1 sal kylg roup and Y² is independently in each occurrence a C2-Cioalkylene group, such as -CY³Y⁴-CY⁵Y⁶-, or -CY7Y8-CY9Y10- CY11Y12-, wherein Y3, Y⁴, Y¾, γ^β, γ , γ^β_ γ9 γιο_ γιι and Y^ are independently of each other hydrogen, or a Ci-Cisalkylgroup, especially -C(CH3)2C(CH3)2-, - C(CH₃)2CH₂C(CH3)2-, or -CH₂C(CH₃)2CH2-, and Y« and Y^ are independently of each other hydrogen, or a Ci-Cisalkylgroup.

Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting halogenated dibenzofurans, dibenzothiophenes and carbazoles with alkyl lithium reagents, such as, for example, n-butyl lithium, or t-buthyl lithium, followed nic esters, such as, for example, B(isopropoxy)3,

B(methoxy)₃, or

(cf. Synthesis (2000) 442-446).

Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting dibenzofurans, dibenzothiophenes and carbazoles with lithium amides, such as, for example, lithium diisopropylamide (LDA) followed by reaction with boronic esters such as, for example, B(isopropoxy)3, B(methoxy)3, or

,

(J. Org. Chem. 73 (2008) 2176-2181 ).

Compounds of formula

(ID are starting materials in the synthesis of the compounds of formula (I) and form a further subject of the present invention. A is CI, Br, or I. R¹, R², R³, R⁴, R⁵, R⁶, X¹, Ar¹, Ar², m and n are defined above.

Xⁱ is NR⁷, O, or S,

A' is CI, Br, or I,

R¹, R2, R3, R4, R5, R6₇ R7 _anc| Ari are defined above, and

m is 0 or 1. For R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and Ar¹ the same preferences apply as described above for the compounds of formula (I).

It has been found that the compounds of the formula I are particularly suitable for use in applications in which charge carrier conductivity is required, especially for use in organic electronics applications, for example selected from switching elements such as organic transistors, e.g. organic FETs and organic TFTs, organic solar cells and organic light- emitting diodes (OLEDs), the compounds of the formula I being particularly suitable in OLEDs for use as matrix material in a light-emitting layer and/or as electron and/or exciton blocker material and/or as hole and/or exciton blocker material, especially in combination with a phosphorescence emitter. In the case of use of the inventive compounds of the formula I in OLEDs, OLEDs which have good efficiencies and a long lifetime and which can be operated especially at a low use and operating voltage are obtained. The inventive compounds of the formula I are suitable especially for use as matrix and/or charge/exciton blocker materials for blue and green emitters, for example light blue or deep blue emitters, these being especially phosphorescence emitters. Furthermore, the compounds of the formula I can be used as conductor/complementary materials in organic electronics applica- tions selected from switching elements and organic solar cells.

The compounds of the formula I can be used as matrix material and/or charge/exciton blocker material and/or charge transport material (charge conductor material). The inventive compounds of the formula I are preferably used as matrix materials in organic elec- tronics applications, especially in OLEDs.

In the emission layer or one of the emission layers of an OLED, it is also possible to combine an emitter material with a matrix material of the compound of the formula I and a further matrix material. This may achieve a high quantum efficiency of this emission layer.

When a compound of the formula I is used as matrix (host) material in an emission layer and additionally as charge/exciton blocker material, owing to the chemical identity or similarity of the materials, an improved interface between the emission layer and the adjacent charge/exciton blocker material, which can lead to a decrease in the voltage with equal luminance and to an extension of the lifetime of the OLED. Moreover, the use of the same material for charge/exciton blocker material and for the matrix of an emission layer allows the production process of an OLED to be simplified, since the same source can be used for the vapor deposition process of the material of one of the compounds of the formula I. Suitable structures of organic electronic devices are known to those skilled in the art and are specified below.

The organic transistor generally includes a semiconductor layer formed from an organic layer with charge transport capacity; a gate electrode formed from a conductive layer; and an insulat- ing layer introduced between the semiconductor layer and the conductive layer. A source electrode and a drain electrode are mounted on this arrangement in order thus to produce the transistor element. In addition, further layers known to those skilled in the art may be present in the organic transistor. The organic solar cell (photoelectric conversion element) generally comprises an organic layer present between two plate-type electrodes arranged in parallel. The organic layer may be configured on a comb-type electrode. There is no particular restriction regarding the site of the organic layer and there is no particular restriction regarding the material of the electrodes. When, however, plate-type electrodes arranged in parallel are used, at least one electrode is preferably formed from a transparent electrode, for example an ITO electrode or a fluorine-doped tin oxide electrode. The organic layer is formed from two sublayers, i.e. a layer with p-type semiconductor properties or hole transport capacity, and a layer formed with n-type semiconductor properties or charge transport capacity. In addition, it is possible for further layers known to those skilled in the art to be present in the organic solar cell. The layers with charge transport capacity may com- prise the compounds of formula I. It is likewise possible that the compounds of the formula I are present both in the light- emitting layer (preferably as matrix material) and in the blocking layers (as charge/exciton blockers).

The present invention further provides an organic light-emitting diode comprising an anode (a) and a cathode (i) and a light-emitting layer (e) arranged between the anode (a) and the cathode (i), and if appropriate at least one further layer selected from the group consisting of at least one blocking layer for holes/excitons, at least one blocking layer for elec- trons/excitons, at least one hole injection layer, at least one hole transport layer, at least one electron injection layer and at least one electron transport layer, wherein the at least one compound of the formula I is present in the light-emitting layer (e) and/or in at least one of the further layers. The at least one compound of the formula I is preferably present in the light-emitting layer and/or the charge/exciton blocking layers.

In a preferred embodiment of the present invention, at least one compound of the formula I, especially a compound of formula (ld-1a), (ld-1b), (ld-2a), or (ld-2b), very especially a compound of the formula (ld-1b), or (ld-2b) is used as charge transport material. Examples of preferred compounds of formula I are compounds (D-33), (D-34), (D-35), (D-36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) shown above. As well as compounds (D74) to (D131) shown above. Compounds (D-44), (D-45), (D-49), (D- 50), (D-51 ), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) are particularly preferred. Also, compounds (D74) to (D131) are particu- lariy preferred.

In another preferred embodiment of the present invention, at least one compound of the formula I, especially a compound of formula (ld-1a), (ld-1b), (ld-2a), or (ld-2b), very especially a compound of the formula (ld-1b), or (ld-2b), is used as charge/exciton blocker mate- rial. Examples of preferred compounds of formula I are compounds (D-33), (D-34), (D-35), (D-36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) shown above. As well as compounds (D74) to (D131) shown above. Compounds (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) are particularly preferred. Also, compounds (D74) to

(D131 ) are particularly preferred.

The present application further relates to a light-emitting layer comprising at least one compound of the formula I.

Structure of the inventive OLED

The inventive organic light-emitting diode (OLED) thus generally has the following structure: an anode (a) and a cathode (i) and a light-emitting layer (e) arranged between the anode (a) and the cathode (i). The inventive OLED may, for example - in a preferred embodiment - be formed from the following layers:

1. Anode (a)

2. Hole transport layer (c)

3. Light-emitting layer (e)

4. Blocking layer for holes/excitons (f)

5. Electron transport layer (g)

6. Cathode (i)

Layer sequences different than the aforementioned structure are also possible, and are known to those skilled in the art. For example, it is possible that the OLED does not have all of the layers mentioned; for example, an OLED with layers (a) (anode), (e) (light-emitting layer) and (i) (cathode) is likewise suitable, in which case the functions of the layers (c) (hole transport layer) and (f) (blocking layer for holes/excitons) and (g) (electron transport layer) are assumed by the adjacent layers. OLEDs which have layers (a), (c), (e) and (i), or layers (a), (e), (f), (g) and (i), are likewise suitable. In addition, the OLEDs may have a blocking layer for electrons/excitons (d) between the hole transport layer (c) and the Light- emitting layer (e).

It is additionally possible that a plurality of the aforementioned functions (electron/exciton blocker, hole/exciton blocker, hole injection, hole conduction, electron injection, electron conduction) are combined in one layer and are assumed, for example, by a single material present in this layer. For example, a material used in the hole transport layer, in one em- bodiment, may simultaneously block excitons and/or electrons.

Furthermore, the individual layers of the OLED among those specified above may in turn be formed from two or more layers. For example, the hole transport layer may be formed from a layer into which holes are injected from the electrode, and a layer which transports the holes away from the hole-injecting layer into the light-emitting layer. The electron conduction layer may likewise consist of a plurality of layers, for example a layer in which electrons are injected by the electrode, and a layer which receives electrons from the electron injection layer and transports them into the light-emitting layer. These layers mentioned are each selected according to factors such as energy level, thermal resistance and charge carrier mobility, and also energy difference of the layers specified with the organic layers or the metal electrodes. The person skilled in the art is capable of selecting the structure of the OLEDs such that it is matched optimally to the organic compounds used in accordance with the invention. In a preferred embodiment the OLED according to the present invention comprises in this order:

(a) an anode,

(b) optionally a hole injection layer,

(c) optionally a hole transport layer,

(d) optionally an exciton blocking layer (e) an emitting layer,

(f) optionally a hole/ exciton blocking layer

(g) optionally an electron transport layer,

(h) optionally an electron injection layer, and

(i) a cathode.

In a particularly preferred embodiment the OLED according to the present invention comprises in this order:

(a) an anode,

(b) optionally a hole injection layer,

(c) a hole transport layer,

(d) an exciton blocking layer

(e) an emitting layer,

(f) a hole/ exciton blocking layer

(g) an electron transport layer, and

(h) optionally an electron injection layer, and

(i) a cathode.

The properties and functions of these various layers, as well as example materials are known from the prior art and are described in more detail below on basis of preferred embodiments.

Anode (a):

The anode is an electrode which provides positive charge carriers. It may be composed, for example, of materials which comprise a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides. Alternatively, the anode may be a conductive polymer. Suitable metals comprise the metals of groups 1 1 , 4, 5 and 6 of the Periodic Table of the Elements, and also the transition metals of groups 8 to 10. When the anode is to be transparent, mixed metal oxides of groups 12, 13 and 14 of the Periodic Table of the Elements are generally used, for example indium tin oxide (ITO). It is likewise possible that the anode (a) comprises an organic material, for example polyaniline, as described, for example, in Nature, Vol. 357, pages 477 to 479 (June 11 , 1992). Preferred anode materials include conductive metal oxides, such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AlZnO), and metals. Anode (and substrate) may be sufficiently transparent to create a bottom-emitting device. A preferred transparent substrate and anode combination is commercially available ITO (anode) deposited on glass or plastic (substrate). A reflective anode may be preferred for some top-emitting devices, to increase the amount of light emitted from the top of the device. At least either the anode or the cathode should be at least partly transparent in order to be able to emit the light formed. Other anode materials and structures may be used.

Hole injection layer (b):

Generally, injection layers are comprised of a material that may improve the injection of charge carriers from one layer, such as an electrode or a charge generating layer, into an adjacent organic layer. Injection layers may also perform a charge transport function. The hole injection layer may be any layer that improves the injection of holes from anode into an adjacent organic layer. A hole injection layer may comprise a solution deposited material, such as a spin-coated polymer, or it may be a vapor deposited small molecule material, such as, for example, CuPc or MTDATA. Polymeric hole-injection materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers, such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]- 2,5-diyl) (Plexcore^® OC Conducting Inks commercially available from Plextronics), and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PEDOT/PSS.

Hole transport layer (c):

Either hole-transporting molecules or polymers may be used as the hole transport material. Suitable hole transport materials for layer (c) of the inventive OLED are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996, US20070278938, US2008/0106190, US2011/0163302 (triarylamines with (di)benzothiophen/(di)benzofuran; Nan-Xing Hu et al. Synth. Met. 111 (2000) 421 (in- dolocarbazoles), WO2010002850 (substituted phenylamine compounds) and

WO2012/16601 (in particular the hole transport materials mentioned on pages 16 and 17 of WO2012/16601 ). Combination of different hole transport material may be used. Reference

is m (HTL1-1)

and

(HTL2-1 ) constitute the hole transport layer.

Customarily used hole-transporting molecule sisting of

(4-phenyl-N-(4-phenylphenyl)-N-[4-[4-(N-[4-(4-phenyl- phenyl)phenyl]anilino)phenyl]phenyl]aniline),

(4-phenyl-N-(4- (4-phenyl-N-(4-phenylphenyl)anilino)phenyl]phenyl]anilin

(4-phenyl-N-[4-(9-phenylcarbazol-3-yl)phenyl]-N-(4-

phenylphenyl)aniline), diazasilole-

2,2'-3a,7a-dihydro-1 ,3,2

-benzodiazasilole]),

(N2,N2,N2\N2\N7,N7,N7\N7'-octakis(p olyl)-9,9'-spirobi[fluorene]-2,2\7J' etramine), 4,4'- bis[N-(1-naphthyl)-N-phenylamino]biphenyl (a-NPD), N,N'-diphenyl-N,N'-bis(3- methylphenyl)-[1 ,1 '-biphenyl]-4,4'-diamine (TPD), 1 ,1-bis[(di-4-tolylamino)phenyl]- cyclohexane (TAPC), N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1 ,1 '-(3,3'-dimethyl)- biphenyl]-4,4'-diamine (ETPD), tetrakis(3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA), a-phenyl-4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehyde diphe- nylhydrazone (DEH), triphenylamine (TPA), bis[4-(N,N-diethylamino)2-methylphenyl](4- methylphenyl)methane (MPMP), 1-phenyl-3-[p-(diethylamino)styryl]5-[p- (diethylamino)phenyl]pyrazoline (PPR or DEASP), 1 ,2-trans-bis(9H-carbazol9-yl)- cyclobutane (DCZB), N,N,N',N'-tetrakis(4-methylphenyl)-(1 ,1 '-biphenyl)-4,4'-diamine (TTB), fluorine compounds such as 2,2',7J'-tetra(N,N-di-tolyl)amino9,9-spirobifluorene (spiro- TTB), N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)9,9-spirobifluorene (spiro-NPB) and 9,9- bis(4-(N,N-bis-biphenyl-4-yl-amino)phenyl-9Hfluorene, benzidine compounds such as Ν,Ν'- bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine and porphyrin compounds such as copper phthalocyanines. In addition, polymeric hole-injection materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers, such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]-2,5- diyl) (Plexcore® OC Conducting Inks commercially available from Plextronics), and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PE- DOT/PSS. Preferred examples of a material of the hole injecting layer are a porphyrin compound, an aromatic tertiary amine compound, or a styrylamine compound. Particularly preferable examples include an aromatic tertiary amine compound such as hexacyanohex- aazatriphenylene (HAT).

In a preferred embodiment it is possible to use metal carbene complexes as hole transport materials. Suitable carbene complexes are, for example, carbene complexes as described in WO2005/019373A2, WO2006/056418 A2, WO2005/113704, WO2007/115970,

WO2007/115981 , WO2008/000727 and PCT/EP One example of a suitable

carbene complex is lr(DPBIC)3 with the formula:

(HTM-1). Another exa ne complex is lr(ABIC)3 with the formu-

la:

M-2).

The hole-transporting layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device. Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, 2003, 359 (p-doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 2003, 4495 and Pfeiffer et al., Organic Electronics 2003, 4, 89 - 103 and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233. For ex- ample it is possible to use mixtures in the hole-transporting layer, in particular mixtures which lead to electrical p-doping of the hole-transporting layer. p-Doping is achieved by the addition of oxidizing materials. These mixtures may, for example, be the following mixtures: mixtures of the abovementioned hole transport materials with at least one metal oxide, for example M0O2, M0O3, WO_x, Re03 and/or V2O5, preferably M0O3 and/or Re03, more pref- erably M0O3, or mixtures comprising the aforementioned hole transport materials and one or more compounds selected from 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6- tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), 2,5-bis(2-hydroxyethoxy)-7,7,8,8- tetracyanoquinodimethane, bis(tetra-n-butylammonium)tetracyanodiphenoquinodimethane, 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene, 1 1 ,11 ,12, 12- tetracyanonaphtho2,6-quinodimethane, 2-fluoro-7,7,8,8-tetracyanoquino-dimethane, 2,5- difluoro-7,7,8,8etracyanoquinodimethane, dicyanomethylene-1 ,3,4,5,7,8-hexafluoro-6H- naphthalen-2-ylidene)malononitrile (F6-TNAP), Mo(tfd)3 (from Kahn et al., J. Am. Chem. Soc. 2009, 131 (35), 12530-12531), compounds as described in EP1988587, US2008265216, EP2180029, US20100102709, WO2010132236, EP2180029 and quinone compounds as mentioned in EP2401254. Preferred mixtures comprise the aforementioned carbene complexes, such as, for example, the carbene complexes HTM-1 and HTM-2, and M0O3 and/or ReC>3, especially M0O3. In a particularly preferred embodiment the hole transport layer comprises from 0.1 to 10 wt % of M0O3 and 90 to 99.9 wt % carbene complex, especially of the carbene complex HTM-1 and HTM-2, wherein the total amount of the M0O3 and the carbene complex is 100 wt %.

Exciton blocking layer (d):

Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer. An electron/exciton blocking layer (d) may be disposed between the first emitting layer (e) and the hole transport layer (c), to block electrons from emitting layer (e) in the direction of hole transport layer (c). Blocking layers may also be used to block excitons from diffusing out of the emissive layer. Suitable metal com- plexes for use as electron/exciton blocker material are, for example, carbene complexes as described in WO2005/019373A2, WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981 , WO2008/000727 and PCT/EP2014/055520. Explicit reference is made here to the disclosure of the WO applications cited, and these disclosures shall be considered to be incorporated into the content of the present application. One example of a suita- ble carbene complex is compound HTM-1 and HTM-2.

Emitting layer (e)

The light-emitting layer (e) comprises at least one emitter material. In principle, it may be a fluorescence or phosphorescence emitter, suitable emitter materials being known to those skilled in the art. The at least one emitter material is preferably a phosphorescence emitter. The phosphorescence emitter compounds used with preference are based on metal complexes, and especially the complexes of the metals Ru, Rh, Ir, Pd and Pt, in particular the complexes of Ir, have gained significance. The compounds of the formula I can be used as the matrix in the light-emitting layer.

Suitable metal complexes for use in the inventive OLEDs are described, for example, in documents WO 02/60910 A1 , US 2001/0015432 A1 , US 2001/0019782 A1 ,

US 2002/0055014 A1 , US 2002/0024293 A1 , US 2002/0048689 A1 , EP 1 191 612 A2, EP 1 191 613 A2, EP 1 21 1 257 A2, US 2002/0094453 A1 , WO 02/02714 A2,

WO 00/70655 A2, WO 01/41512 A1 , WO 02/15645 A1 , WO 2005/019373 A2,

WO 2005/113704 A2, WO 2006/115301 A1 , WO 2006/067074 A1 , WO 2006/056418, WO 200612181 1 A1 , WO 2007095118 A2, WO 2007/115970, WO 2007/1 15981 ,

WO 2008/000727, WO2010129323, WO2010056669, WO10086089, US2011/0057559, WO2011/106344, US2011/0233528, WO2012/048266 and WO2012/172482.

Further suitable metal complexes are the commercially available metal complexes tris(2- phenylpyridine)iridium(lll), iridium(lll) tris(2-(4-tolyl)pyridinato-N,C²'), bis(2- phenylpyridine)(acetylacetonato)iridium(lll), iridium(lll) tris(l-phenylisoquinoline), iridium(lll) bis(2,2'-benzothienyl)pyridinato-N,C³')(acetylacetonate), tris(2-phenylquinoline)iridium(lll), iridium(lll) bis(2-(4,6-difluorophenyl)pyridinato-N,C²)picolinate, iridium(lll) bis(1- phenylisoquinoline)(acetylacetonate), bis(2-phenylquinoline)(acetylacetonato)iridium(lll), iridium(lll) bis(di-benzo[f,h]quinoxaline)(acetylacetonate), iridium(lll) bis(2-methyldi- benzo[f,h]quinoxaline)(acetylacetonate) and tris(3-methyl-1-phenyl-4-trimethylacetyl-5- pyrazolino)terbium(lll), bis[1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinoline](acetyl- acetonato)iridium(lll), bis(2-phenylbenzothiazolato)(acetylacetonato)iridium(lll), bis(2-(9,9- dihexylfluorenyl)-1-pyridine)(acetylacetonato)iridium(lll), bis(2-benzo[b]thiophen-2-yl- pyridine)(acetylacetonato)iridium(lll).

In addition, the following commercially available materials are suitable:

tris(dibenzoylacetonato)mono(phenanthroline)europium(lll), tris(dibenzoylmethane)- mono(phenanthroline)europium(lll), tris(dibenzoylmethane)mono(5-aminophenanthroline)- europium(lll), tris(di-2-naphthoylmethane)mono(phenanthroline)europium(lll), tris(4- bromobenzoylmethane)mono(phenanthroline)europium(lll), tris(di(biphenyl)methane)- mono(phenanthroline)europium(lll), tris(dibenzoylmethane)mono(4J-diphenyl- phenanthroline)europium(lll), tris(dibenzoylmethane)mono(4J-di-methyl- phenanthroline)europium(lll), tris(dibenzoylmethane)mono(4J-dimethylphenan- throlinedisulfonic acid)europium(lll) disodium salt, tris[di(4-(2-(2-ethoxyethoxy)ethoxy)- benzoylmethane)]mono(phenanthroline)europium(lll) and tris[di[4-(2-(2-ethoxy- ethoxy)ethoxy)benzoylmethane)]mono(5-aminophenanthroline)europium(lll), osmium(ll) bis(3-(trifluoromethyl)-5-(4-tert-butylpyridyl)-1 ,2,4-triazolato)diphenylmethylphosphine, os- mium(ll) bis(3-(trifluoromethyl)-5-(2-pyridyl)-1 ,2,4-triazole)dimethylphenylphosphine, osmi- um(ll) bis(3-(trifluoromethyl)-5-(4-tert-butylpyridyl)-1 ,2,4- triazolato)dimethylphenylphosphine, osmium(ll) bis(3-(trifluoromethyl)-5-(2-pyridyl)- pyrazolato)dimethylphenylphosphine, tris[4,4'-di-tert-butyl(2,2')-bipyridine]ruthenium(lll), osmium(ll) bis(2-(9,9-dibutylfluorenyl)-1-isoquinoline(acetylacetonate).

Preferred phosphorescence emitters are carbene complexes. Suitable phosphorescent blue emitters are specified in the following publications: WO2006/056418A2,

WO2005/113704, WO2007/1 15970, WO2007/115981 , WO2008/000727, WO2009050281 , WO2009050290, WO201 1051404, US2011/057559 WO201 1/073149, WO2012/121936A2, US2012/0305894A1 , WO2012/170571 , WO2012/170461 , WO2012/170463,

WO2006/121811 , WO2007/095118, WO2008/156879, WO2008/156879, WO2010/068876, US201 1/0057559, WO201 1/106344, US201 1/0233528, WO2012/048266,

WO2012/172482, PCT/EP2014/064054 and PCT/EP2014/066272.

Preferably, the light emitting layer (e) comprises at least one carbine complex as phosphorescence emitter. Suitable carbine complexes are, for example, compounds of the

M[carbene]_{n 1}

formula ⁰ (IX), which are described in WO 2005/019373 A2, wherein the symbols have the following meanings:

M is a metal atom selected from the group consisting of Co, Rh, Ir, Nb, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re, Cu, Ag and Au in any oxidation state possible for the respective metal atom; Carbene is a carbene ligand which may be uncharged or monoanionic and monodentate, bidentate or tridentate, with the carbene ligand also being able to be a biscarbene or triscarbene ligand;

L is a monoanionic or dianionic ligand, which may be monodentate or bidentate;

K is an uncharged monodentate or bidentate ligand selected from the group consisting of phosphines; phosphonates and derivatives thereof, arsenates and derivatives thereof; phosphites; CO; pyridines; nitriles and conjugated dienes which form a π complex with M¹; n1 is the number of carbene ligands, where n1 is at least 1 and when n1 > 1 the carbene ligands in the complex of the formula I can be identical or different;

ml is the number of ligands L, where ml can be 0 or≥ 1 and when ml > 1 the ligands L can be identical or different;

o is the number of ligands K, where o can be 0 or≥ 1 and when o > 1 the ligands K can be identical or different;

where the sum n1 + ml + o is dependent on the oxidation state and coordination number of the metal atom and on the denticity of the ligands carbene, L and K and also on the charge on the ligands, carbene and L, with the proviso that n1 is at least 1. lexes of the general formula

IXa), which are described in WO2011/073149, where M is Ir, or Pt,

n1 is an integer selected from 1 , 2 and 3,

Y is N R51^', O, S or C(R25')₂,

A^2', A^3', A^4', and A^5'are each independently N or C, where 2 A = nitrogen atoms and at least one carbon atom is present between two nitrogen atoms in the ring,

R^51' is a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,

R^52', R^53', R^54' and R^55' are each, if A^2', A^3', A^4' and/or A^5' is N, a free electron pair, or, if A^2', A^3', A^4' and/or A^5' is C, each independently hydrogen, linear or branched alkyl radical op- tionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 car- bon atoms and/or heteroatoms, group with donor or acceptor action, or

R^53' and R^54' together with A^3' and A^4' form an optionally substituted, unsaturated ring optionally interrupted by at least one further heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms,

R^56', R^57', R^58' and R^59' are each independently hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, cycloheteroalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or un- substituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms, group with donor or acceptor action, or

R^56' and R^57', R^57' and R^58' or R^58' and R^59', together with the carbon atoms to which they are bonded, form a saturated, unsaturated or aromatic, optionally substituted ring optionally interrupted by at least one heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms, and/or

if A^5' is C, R^55' and R^56' together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, an aromatic unit, heteroaromatic unit and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which is optionally fused a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms,

R^25' is independently a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,

K is an uncharged mono- or bidentate ligand,

L is a mono- or dianionic ligand, preferably monoanionic ligand, which may be mono- or bidentate,

ml is 0, 1 or 2, where, when ml is 2, the K ligands may be the same or different, o1 is 0, 1 or 2, where, when o1 is 2, the L ligands may be the same or different.

The compound of formula IX is preferably a compound of the formula:

-81), (BE-82),

(BE-94), (BE-95),

(BE-104), (BE-105),

18),

(BE-125), or (BE-126). The compound of formula IX is more preferably a compound (BE-1), (BE-2), (BE-7), (BE- 12), (BE-16), (BE-64), or (BE-70). The most preferred phosphorescent blue emitters are compounds (BE-1 ) and (BE-12). The homoleptic metal-carbene complexes may be present in the form of facial or meridional isomers, preference being given to the facial isomers.

Suitable carbene complexes of formula (IX) and their preparation process are, for example, described in WO2011/073149.

The compounds of the present invention can also be used as host for phosphorescent green emitters. Suitable phosphorescent green emitters are, for example, specified in the following publications: WO2006014599, WO20080220265, WO2009073245, WO2010027583, WO2010028151 , US201 10227049, WO201 1090535, WO2012/08881 , WO20100056669, WO20100118029, WO20100244004, WO201 1109042, WO2012166608, US20120292600, EP2551933A1 ; US6687266, US20070190359, US20070190359, US20060008670; WO2006098460, US20110210316, WO2012053627; US6921915, US20090039776; JP2007123392 and European patent application no. 14180422.9.

Host (matrix) materials

The light-emitting layer may comprise further components in addition to the emitter material. For example, a fluroescent dye may be present in the light-emitting layer in order to alter the emission color of the emitter material. In addition - in a preferred embodiment - a matrix material can be used. This matrix material may be a polymer, for example poly(N- vinylcarbazole) or polysilane. The matrix material may, however, be a small molecule, for example 4,4'-N,N'-dicarbazolebiphenyl (CDP=CBP) or tertiary aromatic amines, for example TCTA. In another preferred embodiment of the present invention, at least one compound of the formula I, especially a compound of formula (ld-1a), (ld-1b), (ld-2a), or (ld-2b), very especially a compound of the formula (ld-1a), or (ld-2a), is used as matrix material. Examples of preferred compounds of formula I are compounds (D-33), (D-34), (D-35), (D-36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) shown above. As well as compounds (D74) to (D131) shown above. Compounds (D-44), (D-45), (D-49), (D- 50), (D-51 ), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) are particularly preferred. Also, compounds (D74) to (D131) are particularly preferred.

In a preferred embodiment, the light-emitting layer is formed from 2 to 40% by weight, preferably 5 to 35% by weight, of at least one of the aforementioned emitter materials and 60 to 98% by weight, preferably 75 to 95% by weight, of at least one of the aforementioned matrix materials - in one embodiment at least one compound of the formula I - where the sum total of the emitter material and of the matrix material adds up to 100% by weight.

In particularly preferred embod r comprises a compound of for-

mula I, such as, for example,

(C-80), and two carbene complexes, preferably BE-1 and HTM-1 , or HTM-2. In said embodiment, the light-emitting layer is formed from 2 to 40% by weight, preferably 5 to 35% by weight, of BE-1 and 60 to 98% by weight, preferably 65 to 95% by weight, of a compound of the formula I and and HTM-1 , or HTM-2, where the sum total of the carben complexes and of the compound of formula I adds up to 100% by weight.

Suitable metal complexes for use together with the compounds of the formula I as matrix material in OLEDs are, for example, also carbene complexes as described in

WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/113704, WO 2007/1 15970,

WO 2007/115981 and WO 2008/000727.

Further suitable host materials, which may be small molecules or (co)polymers of the small molecules mentioned, are specified in the following publications: WO2007108459 (H-1 to H-37), preferably H-20 to H-22 and H-32 to H-37, most preferably H-20, H-32, H-36, H-37, WO2008035571 A1 (Host 1 to Host 6), JP2010135467 (compounds 1 to 46 and Host-1 to Host-39 and Host-43), WO2009008100 compounds No.1 to No.67, preferably No.3, No.4, No.7 to No. 12, No.55, No.59, No. 63 to No.67, more preferably No. 4, No. 8 to No. 12, No. 55, No. 59, No.64, No.65, and No. 67, WO2009008099 compounds No. 1 to No. 110, WO2008140114 compounds 1-1 to 1-50, WO2008090912 compounds OC-7 to OC-36 and the polymers of Mo-42 to Mo-51 , JP2008084913 H-1 to H-70, WO2007077810 compounds 1 to 44, preferably 1 , 2, 4-6, 8, 19-22, 26, 28-30, 32, 36, 39-44, WO201001830 the polymers of monomers 1-1 to 1-9, preferably of 1-3, 1-7, and 1-9, WO2008029729 the (poly- mens of) compounds 1-1 to 1-36, WO20100443342 HS-1 to HS-101 and BH-1 to BH-17, preferably BH-1 to BH-17, J P2009182298 the (co)polymers based on the monomers 1 to 75, JP2009170764, JP2009135183 the (co)polymers based on the monomers 1-14, WO2009063757 preferably the (co)polymers based on the monomers 1-1 to 1-26, WO2008146838 the compounds a-1 to a-43 and 1-1 to 1-46, JP2008207520 the

(co)polymers based on the monomers 1-1 to 1-26, JP2008066569 the (co)polymers based on the monomers 1-1 to 1-16, WO2008029652 the (co)polymers based on the monomers 1-1 to 1-52, WO20071 14244 the (co)polymers based on the monomers 1-1 to 1-18, JP2010040830 the compounds HA-1 to HA-20, HB-1 to HB-16, HC-1 to HC-23 and the (co)polymers based on the monomers HD-1 to HD-12, JP2009021336, WO2010090077 the compounds 1 to 55, WO2010079678 the compounds H1 to H42, WO2010067746, WO2010044342 the compounds HS-1 to HS-101 and Poly-1 to Poly-4, JP2010114180 the compounds PH-1 to PH-36, US2009284138 the compounds 1 to 11 1 and H1 to H71 , WO2008072596 the compounds 1 to 45, JP2010021336 the compounds H-1 to H-38, pref- erably H-1 , WO2010004877 the compounds H-1 to H-60, JP2009267255 the compounds 1-1 to 1-105, WO2009104488 the compounds 1-1 to 1-38, WO2009086028,

US2009153034, US2009134784, WO2009084413 the compounds 2-1 to 2-56,

JP2009114369 the compounds 2-1 to 2-40, JP20091 14370 the compounds 1 to 67, WO2009060742 the compounds 2-1 to 2-56, WO2009060757 the compounds 1-1 to 1-76, WO2009060780 the compounds 1-1 to 1-70, WO2009060779 the compounds 1-1 to 1-42, WO2008156105 the compounds 1 to 54, JP2009059767 the compounds 1 to 20,

JP2008074939 the compounds 1 to 256, JP2008021687 the compounds 1 to 50,

WO20071 19816 the compounds 1 to 37, WO2010087222 the compounds H-1 to H-31 , WO2010095564 the compounds HOST-1 to HOST-61 , WO2007108362, WO2009003898, WO2009003919, WO2010040777, US2007224446, WO06128800, WO2012014621 ,

WO2012105310, WO2012/130709 and European patent applications EP12175635.7 and EP12185230.5. and EP12191408.9 (in particular page 25 to 29 of EP12191408.9).

The above-mentioned small molecules are more preferred than the above-mentioned (co)polymers of the small molecules.

Further suitable second host materials, are described in WO201 1137072 (for example,

In a particularly preferred embodiment, one or more compounds of the general formula (X) specified hereinafter are used as second host material.

224

(X), wherein

X is NR, S, O or PR;

R is aryl, heteroaryl, alkyl, cycloalkyi, or heterocycloalkyi;

A200 j_S .N R206 207, _p(O)R208R209 _pR210R211 _ -S(0)₂R²¹², -S(0)R213, -SR214, ₀r -OR215;

R221 R222 _anc| R223 _are independently of each other aryl, heteroaryl, alkyl, cycloalkyi, or heterocycloalkyi, wherein at least on of the groups R²²¹, R²²², or R²²³ is aryl, or heteroaryl; R²²⁴ and R²²⁵ are independently of each other alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl, a group A²⁰⁰, or a group having donor, or acceptor characteristics;

n2 and m2 are independently of each other 0, 1 , 2, or 3;

R²⁰⁶ and R²⁰⁷ form together with the nitrogen atom a cyclic residue having 3 to 10 ring at- oms, which can be unsubstituted, or which can be substituted with one, or more substitu- ents selected from alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl and a group having donor, or acceptor characteristics; and/or which can be annulated with one, or more further cyclic residues having 3 to 10 ring atoms, wherein the annulated residues can be unsubstituted, or can be substituted with one, or more substituents selected from alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl and a group having donor, or acceptor characteristics; and 208, 209, R2io_ 2ii _ 212_ 213_ R214 _{u nc}| R215 _are independently of each other aryl, het, for exam-

(SH-5), or

(SH-6), are described in WO2010079051 (in particular pages on 19 to 26 and in tables on pages 27 to 34, pages 35 to 37 and pages 42 to 43).

Additional host materials on basis of dibenzofurane are, for example, described in

US2009066226, EP1885818B1 , EP1970976, EP1998388, EP2034538 and European pa- tent application no. 14160197.1. Examples of particularly preferred host materials are shown below:

In the above-mentioned compounds T is O, or S, preferably O. If T occurs more than one time in a molecule, all groups T have the same meaning. T¹ is O, or S preferably O. T¹ and

independently of each other

Hole/exciton blocking layer (f):

Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer. The hole blocking layer may be disposed between the emitting layer (e) and electron transport layer (g), to block holes from leaving layer (e) in the direction of electron transport layer (g). Blocking layers may also be used to block excitons from diffusing out of the emissive layer.

Additional hole blocker materials typically used in OLEDs are 2,6-bis(N-carbazolyl)pyridine (mCPy), 2,9-dimethyl-4J-diphenyl-1 ,10-phenanthroline (bathocuproin, (BCP)), bis(2- methyl-8-quinolinato)-4-phenylphenylato)aluminum(lll) (BAIq), phenothiazine S,S-dioxide derivates and 1 ,3,5-tris(N-phenyl-2-benzylimidazolyl)benzene) (TPBI), TPBI also being suitable as electron-transport material. Further suitable hole blockers and/or electron conductor materials are 2,2',2"-(1 ,3,5-benzenetriyl)tris(1-phenyl-1-H-benzimidazole), 2-(4- biphenylyl)-5-(4-tert-butylphenyl)-1 ,3,4-oxadiazole, 8-hydroxyquinolinolatolithium, 4- (naphthalen-1-yl)-3,5-diphenyl-4H-1 ,2,4-triazole, 1 ,3-bis[2-(2,2'-bipyridin-6-yl)-1 ,3,4- oxadiazo-5-yl]benzene, 4,7-diphenyl-1 ,10-phenanthroline, 3-(4-biphenylyl)-4-phenyl-5-tert- butylphenyl-1 ,2,4-triazole, 6,6'-bis[5-(biphenyl-4-yl)-1 ,3,4-oxadiazo-2-yl]-2,2'-bipyridyl, 2- phenyl-9,10-di(naphthalene-2-yl)anthracene, 2,7-bis[2-(2,2'-bipyridin-6-yl)-1 ,3,4-oxadiazo- 5-yl]-9,9-dimethylfluorene, 1 ,3-bis[2-(4-tert-butylphenyl)-1 ,3,4-oxadiazo-5-yl]benzene, 2- (naphthalene-2-yl)-4J-diphenyl-1 ,10-phenanthroline, tris(2,4,6-trimethyl-3-(pyridin-3- yl)phenyl)borane, 2, 9-bis(naphthalene-2-yl)-4,7-diphenyl-1 ,10-phenanthroline, 1-methyl-2- (4-(naphthalene-2-yl)phenyl)-1 H-imidazo[4,5-f][1 ,10]phenanthroline. In a further embodiment, it is possible to use compounds which comprise aromatic or heteroaromatic rings joined via groups comprising carbonyl groups, as disclosed in WO2006/100298, disilyl compounds selected from the group consisting of disilylcarbazoles, disilylbenzofurans, dis- ilylbenzothiophenes, disilylbenzophospholes, disilylbenzothiophene S-oxides and dis- ilylbenzothiophene S,S-dioxides, as specified, for example, in PCT applications

WO2009/003919 and WO2009003898 and disilyl compounds as disclosed in

WO2008/034758, as a blocking layer for holes/excitons (f). In another preferred embodiment compounds (SH-1), (SH-2), (SH-3), SH-4, SH-5, SH-6, (SH-7), (SH-8), (SH-9), (SH-10) and (SH-11) may be used as hole/exciton blocking materials. Electron transport layer (g):

Electron transport layer may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Suitable electron-transporting materials for layer (g) of the inventive OLEDs comprise metals chelated with oxinoid compounds, such as tris(8- hydroxyquinolato)aluminum (Alq3), compounds based on phenanthroline such as 2,9- dimethyl-4J-diphenyl-1 ,10-phenanthroline (DDPA = BCP), 4,7-diphenyl-1 ,10- phenanthroline (Bphen), 2,4,7,9-tetraphenyl-1 ,10-phenanthroline, 4,7-diphenyl-1 ,10- phenanthroline (DPA) or phenanthroline derivatives disclosed in EP1786050, in

EP1970371 , or in EP1097981 , and azole compounds such as 2-(4-biphenylyl)-5-(4-t- butylphenyl)-1 ,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4phenyl-5-(4-t-butylphenyl)-1 ,2,4- triazole (TAZ).

It is likewise possible to use mixtures of at least two materials in the electron-transporting layer, in which case at least one material is electron-conducting. Preferably, in such mixed electron-transport layers, at least one phenanthroline compound is used, preferably BCP, or at least one pyridine compound according to the formula (VIII) below, preferably a compound of the formula (Vlllaa) below. More preferably, in mixed electron-transport layers, in addition to at least one phenanthroline compound, alkaline earth metal or alkali metal hy- droxyquinolate complexes, for example Liq, are used. Suitable alkaline earth metal or alkali metal hydroxyquinolate complexes are specified below (formula VII). Reference is made to WO2011/157779.

The electron-transport layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device. Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1 , 1 July 2003 (p- doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 23 June 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89 - 103 and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233. For example, it is possible to use mixtures which lead to electrical n-doping of the electron- transport layer. n-Doping is achieved by the addition of reducing materials. These mixtures may, for example, be mixtures of the abovementioned electron transport materials with alkali/alkaline earth metals or alkali/alkaline earth metal salts, for example Li, Cs, Ca, Sr, CS2CO3, with alkali metal complexes, for example 8-hydroxyquinolatolithium (Liq), and with Y, Ce, Sm, Gd, Tb, Er, Tm, Yb, Li₃N, Rb₂C0₃, dipotassium phthalate, W(hpp)₄ from

EP1786050, or with compounds described in EP1837926B1 , EP1837927, EP2246862 and WO2010132236. In a preferred embodiment, the electron-transport layer comprises at least one compound of the general formula (VII)

, in which

R^32' and R^33' are each independently F, Ci-Cs-alkyl, or C6-Ci4-aryl, which is optionally substituted by one or more Ci-Cs-alkyl groups, or

two R^32' and/or R^33' substituents together form a fused benzene ring which is optionally substituted by one or more Ci-Cs-alkyl groups;

a and b are each independently 0, or 1 , 2 or 3,

M¹ is an alkaline metal atom or alkaline earth metal atom,

p is 1 when M¹ is an alkali metal atom, p is 2 when M¹ is an earth alkali metal atom.

A very particularly preferred compound of the formula (VII) is

(Liq), which may be present as a single species, or in other forms such as Li_gQ_g in which g is an integer, for example LkQe- Q is an 8-hydroxyquinolate ligand or an 8-hydroxyquinolate derivative.

In a further preferred embodiment, the electron-transport layer comprises at least one compound of the formula (VIII),

(VIII), in which

R^34", Rss", RS6", R^37", R^34', R^35', R³6' and R^37'are each independently H, Ci-Cis-alkyl, C1-C18- alkyl which is substituted by E' and/or interrupted by D', C6-C24-aryl, C6-C24-aryl which is substituted by G', C2-C2o-heteroaryl or C2-C2o-heteroaryl which is substituted by G', Q is an arylene or heteroarylene group, each of which is optionally substituted by G';

D' is -CO-; -COO-; -S-; -SO-; -S0₂-; -0-; -NR⁴°^'-; -SiR⁴5^'R⁴6'-; -POR^47'-;

or - C≡C-;

E' is -OR^44'; -SR^44'; -NR⁴°^'R⁴1^'; -COR^43'; -COOR^42'; -CONR⁴°^'R⁴i'; -CN; or F;

G' is E', Ci-Cis-alkyl, Ci-Cis-alkyl which is interrupted by D', Ci-Ci8-perfluoroalkyl, C1-C18- alkoxy, or Ci-Cis-alkoxy which is substituted by E' and/or interrupted by D', in which R^38' and R^39' are each independently H, C6-Cis-aryl; C6-Cis-aryl which is substituted by Ci-Cis-alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-; R^40' and R^{41 '} are each independently C6-Cis-aryl; C6-Cis-aryl which is substituted by C1-C18- alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-; or

R^40' and R^{41 '} together form a 6-membered ring;

R^42' and R^43' are each independently C6-Cis-aryl; C6-Cis-aryl which is substituted by Ci-Cis- alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-,

R^44' is C6-Ci8-aryl; C6-Cis-aryl which is substituted by Ci-Cis-alkyl or Ci-Cis-alkoxy; C1-C18- alkyl; or Ci-Cis-alkyl which is interrupted by -0-,

R^45' and R^46' are each independently Ci-Cis-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cis-alkyl,

R^47' is Ci-Cis-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cis-alkyl.

Preferred compounds of the formula (VIII) are compounds of the formula (Villa)

(Villa)

R^48' is H or Ci-Cis-alkyl and

R^48" is H, Ci-Cis-alkyl or or

Particular preferenc

(ETM-2).

In a further, very particularly preferred embodiment, the electron-transport layer comprises a compound Liq and a compound ETM-2.

In a preferred embodiment, the electron-transport layer comprises the compound of the formula (VII) in an amount of 99 to 1 % by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, where the amount of the compounds of the formulae (VII) and the amount of the compounds of the formulae (VIII) adds up to a total of 100% by weight. The preparation of the compounds of the formula (VIII) is described in J. Kido et al., Chem. Commun. (2008) 5821-5823, J. Kido et al., Chem. Mater. 20 (2008) 5951-5953 and JP2008/127326, or the compounds can be prepared analogously to the processes dis- closed in the aforementioned documents.

It is likewise possible to use mixtures of alkali metal hydroxyquinolate complexes, preferably Liq, and dibenzofuran compounds in the electron-transport layer. Reference is made to WO2011/157790. Dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described in WO2011/157790 are preferred, wherein dibenzofuran compound

(A-10; = ETM-1) is most preferred.

In a preferred embodiment, the electron-transport layer comprises Liq in an amount of 99 to 1 % by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, where the amount of Liq and the amount of the dibenzofuran compound(s), especially ETM-1 , adds up to a total of 100% by weight.

In a preferred embodiment, the electron-transport layer comprises at least one phenanthro- line derivative and/or pyridine derivative.

In a further preferred embodiment, the electron-transport layer comprises at least one phe- nanthroline derivative and/or pyridine derivative and at least one alkali metal hydroxyquinolate complex. In a further preferred embodiment, the electron-transport layer comprises at least one of the dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described in WO2011/157790, especially ETM-1.

In a further preferred embodiment, the electron-transport layer comprises a compound de- scribed in WO2012/1 11462, WO2012/147397, WO2012014621 , such as, for example, a

compound of formula (ETM-3), US2012/0261654, such as, for example, a compound of

Electron injection layer (h):

The electron injection layer may be any layer that improves the injection of electrons into an adjacent organic layer. Lithium-comprising organometallic compounds such as 8- hydroxyquinolatolithium (Liq), CsF, NaF, KF, CS2CO3 or LiF may be applied between the electron transport layer (g) and the cathode (i) as an electron injection layer (h) in order to reduce the operating voltage.

Cathode (i):

The cathode (i) is an electrode which serves to introduce electrons or negative charge carriers. The cathode may be any metal or nonmetal which has a lower work function than the anode. Suitable materials for the cathode are selected from the group consisting of alkali metals of group 1 , for example Li, Cs, alkaline earth metals of group 2, metals of group 12 of the Periodic Table of the Elements, comprising the rare earth metals and the lanthanides and actinides. In addition, metals such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof, may be used.

In general, the different layers, if present, have the following thicknesses:

anode (a): 500 to 5000 A (angstrom), preferably 1000 to 2000 A;

hole injection layer (b): 50 to 1000 A, preferably 200 to 800 A,

hole-transport layer (c): 50 to 1000 A, preferably 100 to 800 A,

exciton blocking layer (d): 10 to 500 A, preferably 50 to 100 A,

light-emitting layer (e): 10 to 1000 A, preferably 50 to 600 A,

hole/ exciton blocking layer (f): 10 to 500 A, preferably 50 to 100 A,

electron-transport layer (g): 50 to 1000 A, preferably 200 to 800 A,

electron injection layer (h): 10 to 500 A, preferably 20 to 100 A,

cathode (i): 200 to 10 000 A, preferably 300 to 5000 A. The person skilled in the art is aware (for example on the basis of electrochemical studies) of how suitable materials have to be selected. Suitable materials for the individual layers are known to those skilled in the art and are disclosed, for example, in WO 00/70655.

In addition, it is possible that some of the layers used in the inventive OLED have been surface-treated in order to increase the efficiency of charge carrier transport. The selection of the materials for each of the layers mentioned is preferably determined by obtaining an OLED with a high efficiency and lifetime.

The inventive OLED can be produced by methods known to those skilled in the art. In general, the inventive OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate. Suitable substrates are, for example, glass, inorganic semiconductors or polymer films. For vapor deposition, it is possible to use customary tech- niques, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others. In an alternative process, the organic layers of the OLED can be applied from solutions or dispersions in suitable solvents, employing coating techniques known to those skilled in the art. Use of the compounds of the formula I in at least one layer of the OLED, preferably in the light-emitting layer (preferably as a matrix material), charge transport layer and/or in the charge/exciton blocking layer makes it possible to obtain OLEDs with high efficiency and with low use and operating voltage. Frequently, the OLEDs obtained by the use of the compounds of the formula I additionally have high lifetimes. The efficiency of the OLEDs can additionally be improved by optimizing the other layers of the OLEDs. For example, high-efficiency cathodes such as Ca or Ba, if appropriate in combination with an intermediate layer of LiF, can be used. Moreover, additional layers may be present in the OLEDs in order to adjust the energy level of the different layers and to facilitate electroluminescence. The OLEDs may further comprise at least one second light-emitting layer. The overall emission of the OLEDs may be composed of the emission of the at least two light-emitting layers and may also comprise white light.

The OLEDs can be used in all apparatus in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile visual display units and illumination units. Stationary visual display units are, for example, visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations and information panels. Mobile visual display units are, for example, visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains. Further devices in which the inventive OLEDs can be used are, for example, keyboards; items of clothing; furniture; wallpaper. In addition, the present invention relates to a device selected from the group consisting of stationary visual display units such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations, information panels, and mobile visual display units such as visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising at least one inventive organic light-emitting diode or at least one inventive light-emitting layer.

The following examples are included for illustrative purposes only and do not limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight.

Examples

Example 1

1 ,2-Diaminocyclohexane

1 ,4-Dioxane

a) 15.7 g of indole (134mmol) were combined with 2-bromo-8-iododibenzofuran (50.0 g, 134 mmol), Cul (0.255 g, 1.34 mmol), K3PO4 (59.7 g, 281 mmol) and 1 ,2- diaminocyclohexane (1.61 ml, 13.4 mmol) in 1 ,4-dioxane (615 ml.) and the resulting mixture was heated at 1 15 °C for 14 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with ethyl acetate. The resulting solution was evaporated to give a crude material as a red solid. The crude material was purified by chromatography on neutral silica gel using hexane/Ch C (4/1 ) as eluent to give 1 as a slightly yellow oil (25.5 g, 54 % yield). Product confirmed by LCMS m/z = 362 (

b) 2.60 g of Indole (22.2 mmol) were combined with 1 (8.04 g, 22.2 mmol), Cul (0.211 g, 1.1 1 mmol), K3PO4 (9.90 g, 46.6 mmol) and 1 ,2-diaminocyclohexane (0.533 ml, 4.44 mmol) in 1 ,4-dioxane (30 ml.) and the resulting mixture was heated at 1 15 °C for 72 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with CH₂CI₂. The resulting solution was evaporated to give a crude material as a red solid. The crude material was purified by chromatography on neutral silica gel using hexane/Ch C (4/1) as eluent to give C-79 as a white solid (7.19 g, 81 % yield) in 99.6 % purity by HPLC. Product confirmed by LCMS m/z = 399 (M+1). Ή NMR (300 MHz, Chloroform-d) δ 8.09 (dd, J = 2.1 , 0.6 Hz, 1 H), 7.83-7.72 (m, 2H), 7.68 (dd, J = 8.7, 2.1 Hz, 1 H), 7.60-7.54 (m, 1 H), 7.43 (d, J = 3.3 Hz, 1 H), 7.33-7.15 (m, 2H), 6.75 (dd, J = 3.3, 0.9 Hz, 1 H).

Example 2

3.71 g of carbazole (22.2 mmol) were combined with 1 (8.04 g, 22.2 mmol), Cul (0.21 1 g, 1.1 1 mmol), K3PO4 (9.90 g, 46.6 mmol) and 1 ,2-diaminocyclohexane (0.533 ml, 4.44 mmol) in 1 ,4-dioxane (30 mL) and the resulting mixture was heated at 1 15 °C for 48 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with CH2CI2. The resulting solution was evaporated to give a crude material as a red solid. The crude material was purified by chromatography on neutral silica gel using hexane/Ch C (4/1 ) as eluent and was then recrystallized by toluene to give B-2 as a white solid (7.48 g, 76 % yield) in 99.8 % purity by HPLC. Product confirmed by LCMS m/z = 449 (M+1 ). ¹H NMR (300 MHz, Chloroform-d) δ 8.21 (m, 1 H), 8.19 (m, 1 H), 8.16 (dd, J = 2.2, 0.6 Hz, 1 H), 8.07 (dd, J = 2.2, 0.6 Hz, 1 H), 7.87 (dd, J = 8.7, 0.6 Hz, 1 H), 7.81 (dd, J = 8.7, 0.6 Hz, 1 H), 7.76-7.65 (m, 3H), 7.60-7.54 (m, 1 H), 7.50-7.12 (m, 9H), 6.74 (dd, J = 3.3, 0.8 Hz, 1 H). Example 3

3.16 g of 5-cyanoindole (22.2 mmol) were combined with 1 (8.04 g, 22.2 mmol), Cul (0.211 g, 1.11 mmol), K3PO4 (9.90 g, 46.6 mmol) and 1 ,2-diaminocyclohexane (0.267 ml, 2.22 mmol) in 1 ,4-dioxane (25 mL) and the resulting mixture was heated at 1 15 °C for 30 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with CH2CI2. The resulting solution was evaporated to give a crude material as a slightly yellow oil. The crude material was purified by chromatography on neutral silica gel using toluene/ethyl acetate (100/1 ) as eluent and was then recrystallized by toluene to give 3 as a white solid (6.58 g, 70 % yield) in 99.5 % purity by HPLC. Product confirmed by LCMS m/z = 424 (M+1 ). Ή NMR (300 MHz, Chloroform-d) δ 8.11-8.08 (m, 2H), 8.06 (dd, J = 2.1 , 0.6 Hz, 1 H), 7.85-7.67 (m, 4H), 7.63 (dd, J = 8.7, 2.1 Hz, 1 H), 7.59- 7.52 (m, 3H), 7.48 (dd, J = 8.7, 1.5 Hz, 1 H), 7.42 (d, J = 3.3 Hz, 1 H), 7.33 - 7.16 (m, 2H), 6.83 (dd, J = 3.3, 0.8 Hz, 1 H), 6.76 (dd, J = 3.3, 0.8 Hz, 1 H). Example 4

1 ,2-Diaminocyclohexane

1 ,4-Dioxane

a) 13.3 g of 5-cyanoindole (93.8 mmol) were combined with 2-bromo-8-iododibenzofuran (35.0 g, 93.8 mmol), Cul (0.179 g, 0.938 mmol), K3PO4 (41.8 g, 197 mmol) and 1 ,2- diaminocyclohexane (1 .13 ml, 9.38 mmol) in 1 ,4-dioxane (120 ml.) and the resulting mixture was heated at 1 15 °C for 5 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with CH2CI2. The resulting solution was evaporated to give a crude material as a grey solid. The crude material was purified by chromatography on neutral silica gel using hexane/toluene (1/1 ) to hex- ane/Ch C (1/1 ) as eluent to give 2 as a colorless oil (23.1 g, 64 % yield). Product confirmed b LCMS m/z = 387 (M+1 ).

b) 4.00 g of 5-cyanoindole (28.1 mmol) were combined with 5 (10.9 g, 28.1 mmol), Cul (0.268 g, 1.41 mmol), K3PO4 (12.5 g, 59.0 mmol) and 1 ,2-diaminocyclohexane (0.676 ml, 5.62 mmol) in 1 ,4-dioxane (100 ml.) and the resulting mixture was heated at 1 15 °C for 10 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with CH2CI2. The resulting solution was evaporated to give a crude material as a grey solid. The crude material was purified by chromatography on neu- tral silica gel using Ch C /MeOH (10/1 ) as eluent and was then recrystallized by xylene to give D-58 as a slightly yellow solid (3.20 g, 25 % yield) in 99.6 % purity by HPLC. Product confirmed by LCMS m/z = 449 (M+1 ). Ή NMR (300 MHz, Chloroform-d) δ 8.1 1-8.08 (m, 1 H), 8.07 (dd, J = 2.2, 0.6 Hz, 1 H), 7.84 (dd, J = 8.7, 0.6 Hz, 1 H), 7.66 (dd, J = 8.7, 2.2 Hz, 1 H), 7.60-7.43 (m, 3H), 6.83 (dd, J = 3.3, 0.8 Hz, 1 H)

4.71 g of carbazole (28.1 mmol) were combined with 5 (10.9 g, 28.1 mmol), Cul (0.268 g, 1.41 mmol), K3PO4 (12.5 g, 59.0 mmol) and 1 ,2-diaminocyclohexane (0.676 ml, 5.62 mmol) in 1 ,4-dioxane (100 mL) and the resulting mixture was heated at 1 15 °C for 40 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with CH2CI2. The resulting solution was evaporated to give a crude material as a grey solid. The crude material was purified by chromatography on neutral silica gel using toluene to ethyl acetate as eluent and was then recrystallized by toluene to give B-5 as a white solid (4.00 g, 30 % yield) in 99.8 % purity by HPLC. Product confirmed by LCMS m/z = 474 (M+1 ). Ή NMR (300 MHz, Chloroform-d) δ 8.23-8.20 (m, 1 H), 8.20-8.17 (m, 1 H), 8.17 (dd, J = 2.2, 0.6 Hz, 1 H), 8.09-8.06 (m, 1 H), 8.05 (dd, J = 2.2, 0.6 Hz, 1 H), 7.89 (dd, J = 8.7, 0.5 Hz, 1 H), 7.85 (dd, J = 8.7, 0.5 Hz, 1 H), 7.74 (dd, J = 8.7, 2.2 Hz, 1 H), 7.65 (dd, J = 8.7, 2.2 Hz, 1 H), 7.59-7.30 (m, 9H), 6.81 (dd, J = 3.3, 0.8 Hz, 1 H).

Example 6

a) 6.27 g of B-5 (14.0 mmol) was combined with /V-iodosuccinimide (3.15 g, 14.0 mmol) in THF (140 ml_). The resulting mixture was heated at 60 °C over night. The reaction was allowed to cool to room temperature and added 10% aqueous sodium thiosulfate solution (200 ml.) and extracted with toluene (3 x 100 ml_). The combined organic phase was washed with saturated aqueous sodium hydrogencarbonate solution (100 ml.) and then water (100 ml_). The organic phase was dried over anhydrous MgS0₄ and the solvent was evaporated to give the crude product as a light brown solid. The crude product was washed with heptane and filtered off. 7.04 g of 3 was collected as a light brown solid (87.5% yield). Product confirmed by LCMS m/z = 575 (M+1 ).

b) 1.84 g of carbazole (1 1 .0 mmol) was combined with 3 (6.32 g, 1 1.0 mmol), Cul (2.10 g, 1 1.0 mmol), K3PO4 (7.00 g, 33.0 mmol) and 1 ,2-diaminocyclohexane (2.64 ml, 22.0 mmol) in 1 ,4-dioxane (70 ml.) and the resulting mixture was heated at 100 °C for a day. The mix- ture was filtered through a pad of Celite washing well with toluene and the solvent was evaporated to give the crude product as a brown solid. The crude material was purified by chromatography on neutral silica gel using heptane/toluene (9/1 to 4/1 ) as eluent to give B- 1 as a colorless solid (2.48 g, 36.7 % yield) in 99.6 % purity by HPLC. Product confirmed by LCMS m/z = 614 (M+1 ). Ή NMR (400 MHz, Chloroform-d) δ 8.22 (m, 2H), 8.22 (m, 2H), 8.20 (m, 1 H), 8.20 (m, 1 H), 7.90 (d, J = 8.8 Hz, 1 H), 7.89 (d, J = 8.8 Hz, 1 H), 7.82 (dd, J = 8.8, 2.0 Hz, 1 H), 7.75 (m, 1 H), 7.74 (dd, J = 8.8, 2.0 Hz, 1 H), 7.71 (m, 1 H), 7.48-7.16 (m, 15H).

Comparative Application Example 1

A glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode used as an anode is first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate is exposed to an ultraviolet light and ozone for further 30 min. This treatment also improves the hole injection properties of the ITO. The cleaned substrate is mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below are applied by vapor deposition to the ITO substrate a A/sec at about 10 ⁶ -10 ⁸ mbar. As a hole injection layer,

compound

with 30 nm thickness is applied. Then compound a hole transporting layer. As an

e

xciton and electron blocker, comp (HTM-1 ; for preparation, see Ir complex (7) in the application WO2005/019373) is then applied with a thickness of 10 nm.

Subsequently, a mixture of 20% by weight of emitter compound, (BE-

1 pound (HTM-1) and 65% by weight of host

(SH-1) are applied by vapor deposition in a thickness of 40 nm. Subsequently, material (SH-1) is applied by vapour

5 nm as an exciton and hole blocker. Thereafter, compound

with 20 nm thickness is deposited as an electron transport layer. Finally, 1 nm-thick LiF is deposited as an electron injection layer and 80 nm-thick Al is then deposited as a cathode to complete the device. The device is sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen. OLED characterization

To characterize the OLED, electroluminescence spectra are recorded at various currents and voltages. In addition, the current-voltage characteristic is measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). Driving voltage U and EQE are given at luminance (L) = 1000 cd/m² and Commission In- ternationale de I'Eclairage (CIE) coordinate are given at 5mA/cm² except otherwise stated. Furthermore, 50% lifetime (LT50), the time spent until the initial luminance of 4Ό00 cd/m² is reduced to 50% (2Ό00 cd/m²), is recorded. Application Example 1 , 2 and 3

Comparative Application Example 1 is repeated except and the exciton

(C-79),

pound

device results are shown in Table 1.

Table 1

The results shown in Table 1 demonstrate that the driving voltage and EQE are improved when compounds (C-79), (C-80), or (D-51) are used as a host and an exciton blocker instead of reference compound (SH-1). Application Example 4, 5, 6 and 7

Comparative Application Example 1 is repeated except that the exciton and hole blocker,

(D-50), compound

(D-58), or compound (D-51) compound

(B-1 ) (see preparation example 6) for example 4,

6, or 7, respectively. The device results are shown in Table 2.

Table 2

The results shown in Table 2 demonstrate that the driving voltage, EQE and lifetime are improved when compounds (D-50), (B-51), (D-58), or (B-1) are used as an exciton and hole blocker instead of reference compound (SH-1).

Claims

1. A compound of the formula

(I), wherein m is 0, 1 or 2, n is 0, 1 or 2,

Ar¹ and Ar² are independently of each other a C6-C24arylen group, which can optionally be substituted by G, a C2-C3oheteroarylen group, which can optionally be substituted by G,

Bⁱ is N, or CR3,

B² is N, or CR⁴,

B³ is N, or CRs,

B⁴ is N, or CR⁶,

with the proviso that not more than two of B¹ , B², B³ and B⁴ are N;

B^{i i} is N, or CRsⁱ ,

Bis is N, or CRss,

with the proviso that not more than two of B¹¹ , B¹², B¹³ and B¹⁴ are N;

Bi6 is N, or CRse,

Xⁱ is O, S, Se or NR⁷,

with the proviso that, if at least one of R¹ , R², R³, R⁴, R⁵, and R⁶ is -CN, then

A is -NR¹⁰R¹¹ , or -Si(R¹ )(R¹³)(R¹⁴), a C₆-C₂4aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G; R³, R⁴, R5 , R6, R5i , R52, 53, 54, 55, 56, R57, _anc| R58 _are independently of each other -H, -F, CN, a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C6-C2₄ ar- yloxy group, which can optionally be substituted by G;

R⁷ is a Ci-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C2₄aryl group, which can optionally be substituted by G;

R¹⁰ and R¹¹ are independently of each other H, a C6-C2₄aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;

R¹², R¹³ and R¹⁴ are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by L; a C6-C2₄aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;

with the proviso that, if all of R¹ , R², R³, R⁴, R⁵ and R⁶ are different from -CN, then A is a C6-C2₄aryl group, which can optionally be substituted by G, a Ci3-C3oheteroaryl group, which can optionally be substituted by G, an azacarbazolyl, which can optionally be substituted by G, an azaindolyl, which can optionally be substituted by G, a dibenzofuranyl, which can optionally be substituted by G, a dibenzothiophenyl, which can optionally be substituted by G, a benzofuranyl, which can optionally be substituted by G, a benzothiophenyl, which can optionally be substituted by G, a pyridyl, which can optionally be substituted by G, a pyrimidinyl, which can optionally be substituted by G, a pyrazinyl, which can optionally be substituted by G, a triazinyl, which can optionally be substituted by G, a naphtyridinyl, which can optionally be substitute

(IV),

Bⁱs is N or CR61 , preferably CR61 ,

B²⁰ is N or CR⁶², preferably CR⁶²,

B²¹ is N or CR⁶³, preferably CR⁶³,

B²² is N or CR⁶⁴, preferably CR⁶⁴,

with the proviso that not more than two of B1⁹, B²°, B²ⁱ and B²² are N;

B²³ is N or CR⁶⁵, preferably CR⁶⁵,

B²⁴ is N or CR⁶⁶, preferably CR⁶⁶,

B²⁵ is N or CR⁶⁷, preferably CR⁶⁷,

B²⁶ is N or CR⁶⁸, preferably CR⁶⁸,

with the proviso that not more than two of B²³, B²⁴, B²5 and B²6 are N;

B²⁷ is N or CR⁶⁹, preferably CR⁶⁹,

B²⁸ is N or CR⁷⁰, preferably CR⁷⁰,

B²⁹ is N or CR⁷ⁱ , preferably CR⁷ⁱ ,

B³° is N or CR⁷², preferably CR⁷²,

B³¹ is N or CR⁷³, preferably CR⁷³, B³² is N or CR⁷⁴, preferably CR⁷⁴,

R61 , R6², R⁶³, R6⁴, Res, R66, R67, es, 69, /o, R 1 , R72, R73 _anc| R74 _are independently of each other -H, -F, -C≡N, a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24aryloxy group, which can optionally be substituted by G;

D is -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -N R²S -POR²⁴-, -CR²s=CR²6-, or -C≡C-, E is -OR31 , -SR³1 , -N R³²R³³, -COR³⁴, -COOR³⁴, -CONR³²R³³, -C≡N , or -F,

L is D, or -Si R²²R²³-,

G is E, or a Ci-Cisalkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by -F, Ci-Cisalkyl, or Ci-Cisalkyl which is interrupted by -0-; a C2- C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by -F, Ci- Cisalkyl , or Ci-Cisalkyl which is interrupted by O;

R²¹ , R³² and R³³ are independently of each other a C6-Cisaryl group; a C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci- Cisalkyl group, which is interrupted by -O-; or R³² and R³³ together form a five or six membered ring ,

R²² and R²³ are independently of each other a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl,

R²⁴ is a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl ,

R²⁵ and R²⁶ are independently of each other H , C6-Cisaryl ; C6-Cisaryl which is substituted by Ci-Cisalkyl , or Ci-Cisalkoxy; Ci-Cisalkyl; or Ci-Cisalkyl which is interrupted by -0-,

R³¹ is a C6-Cisaryl ; a C6-Cisaryl , which is substituted by Ci-Cisalkyl , or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O- and

R³⁴ is a C6-Cisaryl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl , or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-.

T

(la), wherein

Ri , R², R³, R⁴, R5, R6, B11 , B1², B1³, B1⁴, Bis, Bis, B1⁷, Ari , Ar², A, m and n are defined in claim 1.

3. The compound according to claim 2, which is a compound of formula

(lb), wherein

R2, R3, R4, R5 R6 χι A , Ar2, A, m and n are defined in claim 1.

4. T formula

(lc), wherein

R2, R3, R4, R5, 6_ χι, Ar¹, ΑΓ², A, m and n are defined in claim 1.

5. T s a compound of formula

(Id), wherein

Xⁱ is NR⁷, O, orS,

R¹, R2, R3, R4, R5, R6₇ R7₇ Ar¹ and A are defined in claim 1, and

m is 0 or 1.

6.

Xⁱ is NR⁷, O, orS,

R¹, R2, R3, R4, R5, R6₇ R7₇ Ar¹ and A are defined in claim 1, and m is 0 or 1.

pendently of each other -H, -CN, or a phenyl group.

9. The compound according to any of claims 1 to 8 or 21 or 22, wherein R¹, R², R³, R⁴, R⁵ and R⁶ are independently of each other -H, or -CN.

10. The compound according to any of claims 1 to 9 or 21 or 22, wherein at least one of Ri, R2, R3, R4, R5 and R6 is -CN. 11. The compound according to any of claims 1 to 10 or 21 or 22, wherein m is 0.

12. The compound according to any of claims 1 to 11 or 21 or 22, wherein X¹ is O, or S.

13. T ich is a compound of formula

(ld-1), wherein

Xi is O,

R⁴is CN and R¹, R², R³, R⁵ and R⁶are H, or

Ri, R2, R3, R4, R5 and RSare H,

m is 0 or 1.

An electronic device, comprising a compound according to any of claims 1 to 13 or

15. The electronic device according to claim 14, which is an electroluminescent device.

16. A charge transport layer, a charge/exciton blocker layer, or an emitting layer comprising a compound according to any of claims 1 to 13 or 21 to 23.

17. The emitting layer according to claim 16, comprising a compound according to any of claims 1 to 13 or 21 to 23 as host material in combination with a phosphorescent emitter.

18. An apparatus selected from the group consisting of stationary visual display units; mobile visual display units; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising the organic electronic device according to claim 14, or 15, or the charge transport layer, the charge/exciton blocker layer, or the emitting layer according to claim 16, or 17.

19. Use of the compounds according to any of claims 1 to 13 or 21 to 23 for electrophotographic photoreceptors, photoelectric converters, organic solar cells, switching elements, organic light emitting field effect transistors, image sensors, dye lasers and electroluminescent devices.

(II), wherein

A' is CI, Br, or I, and

R³, R⁴, R⁵ and R⁶ are independently of each other -H , -F, CN , a Ci-C₂₅alkyl group, which can optionally be substituted by E and or interrupted by D; a C3- C25cycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C2₄aryl group, which can optionally be substituted by G; a C2- C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24 aryloxy group, which can optionally be substituted by G;

Xⁱ is O, S, Se or NR⁷,

R⁷ is a Ci-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G;

m is 0, 1 or 2, n is 0, 1 or 2,

D is -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -NR²S -POR²⁴-, -CR²s=CR²6-, or -C≡C-, E is -OR31 , -SR31 , -NR3²R33, -COR34, -COOR34, -CONR3²R33, -C≡N, or -F,

G is E, or a Ci-Cisalkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by -F, Ci-Cisalkyl, or Ci-Cisalkyl which is interrupted by -0-; a C2- C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by -F, Ci- Cisalkyl, or Ci-Cisalkyl which is interrupted by O;

R²¹ , R³² and R³3 are independently of each other a C6-Cisaryl group; a C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci- Cisalkyl group, which is interrupted by -O-; or R³² and R³³ together form a five or six membered ring,

R²⁵ and R²⁶ are independently of each other H, C6-Cisaryl; C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; Ci-Cisalkyl; or Ci-Cisalkyl which is interrupted by -0-, R³¹ is a Ce-Cisaryl; a Ce-Cisaryl, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O- and

R³⁴ is a C6-Cisaryl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-.

The compound according to any of claims 1 to 6 wherein Ar¹ and Ar² are inde

22. la

23. ich is a compound of formula

(ld-1), wherein

Xⁱ is O,

R4is CN and Ri Rz, R3, R5 and R6are H,

110

111