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WO2015014791A1 - Benzimidazolo[2,1-b][1,3]benzothiazoles pour des applications électroniques - Google Patents

Benzimidazolo[2,1-b][1,3]benzothiazoles pour des applications électroniques Download PDF

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Publication number
WO2015014791A1
WO2015014791A1 PCT/EP2014/066174 EP2014066174W WO2015014791A1 WO 2015014791 A1 WO2015014791 A1 WO 2015014791A1 EP 2014066174 W EP2014066174 W EP 2014066174W WO 2015014791 A1 WO2015014791 A1 WO 2015014791A1
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Prior art keywords
group
substituted
formula
optionally
cisalkyl
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PCT/EP2014/066174
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English (en)
Inventor
Thomas Schäfer
Peter Murer
Ute HEINEMEYER
Julia KOHLSTEDT
Heinz Wolleb
Annemarie Wolleb
Soichi Watanabe
Hideaki Nagashima
Toshio Sakai
Christian Lennartz
Gerhard Wagenblast
Original Assignee
Basf Se
Idemitsu Kosan Co., Ltd.
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Application filed by Basf Se, Idemitsu Kosan Co., Ltd. filed Critical Basf Se
Publication of WO2015014791A1 publication Critical patent/WO2015014791A1/fr
Priority to EP15747561.7A priority Critical patent/EP3174885B1/fr
Priority to PCT/IB2015/055667 priority patent/WO2016016791A1/fr

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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/12Light sources with substantially two-dimensional radiating surfaces
    • H05B33/20Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the material in which the electroluminescent material is embedded
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D513/00Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04Ortho-condensed systems
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D519/00Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/657Polycyclic condensed heteroaromatic hydrocarbons
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/657Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/657Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00Properties of the organic materials covered by group H10K85/00
    • H10K2101/10Triplet emission
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/15Hole transporting layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/16Electron transporting layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18Carrier blocking layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30Coordination compounds
    • H10K85/341Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to compounds of formula I, a process for their production and their use in electronic devices, especially electroluminescent devices.
  • the compounds of formula I may provide improved efficiency, stability, manufacturability and/or spectral characteristics of electroluminescent devices.
  • WO2012139692 relates to electronic devices which comprise an anode, a cathode and at least one organic layer, where the organic layer comprises one or more substituted ben
  • Y can be S and n can be 0 or 1 , Z is
  • R 1 can be an aromatic or hetero aromatic ring system.
  • DE102012000064 describes compounds of formula (1 ) and their use in organic light emitting devices (OLEDs). Among others X can be C. If X is C, n is 1.
  • WO20121 10182 describes compounds of formula (I),
  • X and Y can be S and Z is CR 2 , or N.
  • US20050074632 relates to compounds of formula (1 ), wherein
  • US20050079387 relates to compounds of formula Ai-A 2 -A 3 (1 ), wherein
  • X and X ' can be S, O, or Se.
  • the compounds of formula A1-A2-A3 CI ) are used as blue luminescent material or as hosts for phosphorescent, or fluorecent dopants.
  • US2790172 relates to compounds of formula , wherein R and R 1 are H, lower alkyl, lower alkoxy, or phenyl; or R 1 and R can form a 6 membered carbocylcle; and a process for their production.
  • EWG is an elecron withdrawing group, like CN, NO2, CI, F, or CF3 and R is NO2, or OMe.
  • WO201 1160757 relates to an electronic device comprising an anode, cathode and at least
  • WO2013/050401 describes 4H-imidazo[1 ,2-a]imidazoles of formula
  • WO2014/009317 relates to compounds of formula (I), a process for their production and their use in electronic devices, especially electroluminescent devices.
  • the compounds of formula I When used as host material for phosphorescent emitters in electroluminescent devices, the compounds of formula I may provide improved efficiency, stability, manufac- turability, or spectral characteristics of electrolumine
  • WO2014/044722 relates to compounds of formula (I), which are characterized in that they substituted by benzimidazo[1 ,2-a]benzimidazo-5-yl and/or benzimidazo[1 ,2-a]benzimidazo-2,5-ylene groups and in that at least one of the substitu- ents B 1 , B 2 , B 3 , B 4 , B 5 , B 6 , B 7 and B 8 represents N; a process for their production and their use in electronic devices, especially electroluminescent devices.
  • the present invention provides further materials suitable for use in OLEDs and further applications in organ- ic 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.
  • 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.
  • benzimidazolo[2,1-b][1 ,3]benzothiazole derivatives are found to be suitable for use in organo-electroluminescent devices.
  • said derivatives are suitable charge transport materials, or host materials for phosphorescent emitters with good efficiency and durability.
  • hole transporters and bipo- lar hosts hole transporting units are required.
  • electron transporting units are required.
  • the benzimidazolo[1 ,2- ajbenzimidazole basic skeleton described in WO2011160757 represents a hole transporter unit, which is responsible for good hole transport and hole injection. It has surprisingly been found that the benzimidazolo[2,1-b][1 ,3]benzothiazole basic skeleton described in the pre- sent application represents an electron transporting unit, which is responsible for good electron transport and electron injection.
  • Y 1 and Y 2 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interupted by D; a C6-C2 4 aryl group, which can optionally be substituted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C7- C25aralkyl group, which can optionally be substituted by G;
  • R 1 and R 6 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interupted by D; a C6-C2 4 aryl group, which can optionally be substituted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a group of formula -(AV(A 2 )p-(A 3 ) q -(A 4 ) r R 16 ,
  • o 0, or 1
  • p is 0, or 1
  • q is 0, or 1
  • r is 0, or 1
  • a 1 , A 2 , A 3 and A 4 are independently of each other a C6-C2 4 arylen group, which can optionally be substituted by G, or a C2-C3oheteroarylen group, which can optionally be substituted by G;
  • R 16 is H, -NR 10 R 11 , or -Si(R 12 )(R 13 )(R 14 ), a C 6 -C 24 aryl group, which can optionally be substi- tuted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
  • R 10 and R 11 are independently of each other a C6-C2 4 aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
  • R 12 , R 13 and R 14 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interupted by D;
  • a C6-C2 4 aryl group which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
  • E is -OR 69 , -SR 69 , -NR 65 R
  • G is E, or a d-dsalkyl group, a C6-C2 4 aryl group, a C6-C2 4 aryl group, which is substituted by F, Ci-Ci8alkyl, or C-i-C-isalkyl, which is substituted by F and/or interrupted by O; a C2- C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by F, Ci-Cisalkyl, - Si(R 2' )(R 3' )(R 14' ), or Ci-Ci 8 alkyl which is interrupted by O;
  • R14' a re independently of each other a d-dsalkyl group, which can optionally be interupted by O; a C6-Ci4arylgroup, which can optionally be substituted by d-dsalkyl ; or a C2-Cioheteroaryl group, which can optionally be substituted by d-dsalkyl ;
  • R 63 and R 64 are independently of each other H, d-dsaryl; d-dsaryl which is substituted by Ci-Cisalkyl, or d-dsalkoxy; Ci-Cisalkyl; or Ci-Cisalkyl which is interrupted by -0-; R 65 and R 66 are independently of each other a C6-Cisaryl group; a d-dsaryl which is substituted by Ci-Cisalkyl, or d-dsalkoxy; a Ci-Cisalkyl group; or a d-dsalkyl group, which is interrupted by -0-; or
  • R 65 and R 66 together form a five or six membered ring
  • R 67 is a Ce-Cisaryl group; a d-dsaryl group, which is substituted by d-dsalkyl, or Ci- dsalkoxy; a d-dsalkyl group; or a d-dsalkyl group, which is interrupted by -0-,
  • R 68 is H; a d-dsaryl group; a d-dsaryl group, which is substituted by d-dsalkyl, or Ci- dealkoxy; a d-dsalkyl group; or a d-dsalkyl group, which is interrupted by -0-,
  • R 69 is a C6-Ciearyl; a d-dsaryl, which is substituted by d-dsalkyl, or d-dsalkoxy; a d- dealkyl group; or a d-dsalkyl group, which is interrupted by -O-,
  • R 70 and R 71 are independently of each other a d-dsalkyl group, a d-dsaryl group, or a d-dsaryl group, which is substituted by d-dsalkyl, and
  • R 72 is a d-dsalkyl group, a d-dsaryl group, or a d-dsaryl group, which is substituted by d-dsalkyl, with the proviso that at least one of the substituents R 1 and R 6 represent a group of formula -(A ) 0 -(A 2 )p-(A 3 ) q -(A 4 ) r R 16 and with the further proviso that R 16 is different from H, if o is 0, p is 0, q is 0 and r is 0.
  • T I is preferably a compound of formula
  • R 1 , R 2 , R 3 , R 4 , R5, Re, R 7 and R 8 are independently of each other H, a d-dsalkyl group, which can optionally be substituted by E and or interupted by D; a d-dsaralkyl group, which can optionally be substituted by G, or a group of formula— (A 1 ) 0 -(A 2 )p-(A 3 )q-(A 4 ) r R 16 , o is 0, or 1 , p is 0, or 1 , q is 0, or 1 , r is 0, or 1 ,
  • a 1 , A 2 , A 3 and A 4 are independently of each other a d-d 4 arylen group, which can optionally be substituted by G, or a d-doheteroarylen group, which can optionally be substituted by G;
  • R 16 is H, -NR 10 R 11 , or -Si(R 12 )(R 13 )(R 14 ), a d-d 4 aryl group, which can optionally be substi- tuted by G; or a d-doheteroaryl group, which can optionally be substituted by G;
  • R 10 and R 11 are independently of each other a d-d 4 aryl group, which can optionally be substituted by G; or a d-doheteroaryl group, which can optionally be substituted by G;
  • R 12 , R 13 and R 14 are independently of each other a Ci-C25alkyl group, which can optionally be substituted by E and or interupted by D; a C6-C2 4 aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
  • E is -OR 69 , -SR 69 , -NR 65 R 66 , -COR 68 , -COOR 67 , -CONR 65 R 66 , -CN, or F,
  • G is E, or a Ci-Cisalkyl group, a C6-C2 4 aryl group, a C6-C2 4 aryl group, which is substituted by F, Ci-Ci8alkyl, or Ci-Cisalkyl which is substituted by F and/or interrupted by O; a C2- C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by F, Ci-Cisalkyl, - Si(R 2' )(R 3' )(R 14' ), or Ci-Ci 8 alkyl which is interrupted by O;
  • RI 4 ' are independently of each other a d-dsalkyl group, which can optionally be interupted by O; a C6-Ci 4 arylgroup, which can optionally be substituted by C-i-C-isalkyl ; or a C2-Cioheteroaryl group, which can optionally be substituted by Ci-Cisalkyl ;
  • R 63 and R 64 are independently of each other H, C6-Cisaryl; C6-Cisaryl which is substituted by Ci-Cisalkyl, or d-dsalkoxy; Ci-Cisalkyl; or C-i-C-isalkyl which is interrupted by -0-;
  • R 65 and R 66 are independently of each other a C6-Cisaryl group; a di-deary! which is substituted by Ci-Cisalkyl, or d-dsalkoxy; a Ci-Cisalkyl group; or a d-dsalkyl group, which is interrupted by -0-; or
  • R 65 and R 66 together form a five or six membered ring
  • R 67 is a Ce-Cisaryl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, or Ci- Ci8alkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-,
  • R 68 is H; a C6-Cisaryl group; a di-deary! group, which is substituted by Ci-Cisalkyl, or Ci- Ci8alkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O-,
  • R 69 is a C6-Ciearyl; a C6-Cisaryl, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci- Ciealkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-,
  • R 70 and R 71 are independently of each other a Ci-Cisalkyl group, a C6-Cisaryl group, or a Ce-Cisaryl group, which is substituted by Ci-Cisalkyl, and
  • R 72 is a Ci-Cisalkyl group, a C6-Cisaryl group, or a di-deary! group, which is substituted by Ci-Cisalkyl, with the proviso that at least one of the substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 represent a group of formula -(A 1 ) 0 -(A 2 )p-(A 3 )q-(A 4 ) r R 16 and with the further proviso that R 16 is different from H, if o is 0, p is 0, q is 0 and r is 0.
  • Certain compounds of the present invention have high triplet energy and can show, when used as host in combination with phosphorescent emitters, excellent power efficiencies.
  • 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 electrolumi- nescent devices, such as, for example, organic light-emitting diodes (OLEDs).
  • 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 electrolumi- nescent devices, such as, for example, organic light-emitting diodes (OLEDs).
  • 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.
  • 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 com- pound of formula I according to the present invention.
  • 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-, -SO2-, -0-, -NR 65 -, wherein R 65 is Ci-Ci 8 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C6-Ci 4 aryl, such as phenyl, tolyl, naphthyl, or biphenylyl, or C2-C3oheteroaryl, such as, for example, benzimid-
  • E is preferably -OR 69 ; -SR 69 ; -NR 6 5R 6 5; -COR 68 ; -COOR 67 ; -CON RssRss; or -CN; wherein R 65 , R 67 , R 68 and R 69 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-Ci 4 aryl, such as phenyl, tolyl, naphthyl, or biphenylyl.
  • Ci-Cisalkyl such as methyl, ethyl, n- propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, oc
  • G is preferably -OR 69 ; -SR 69 ; -NR 65 R 65 ; a d-dsalkyl group, a C 6 -Ci 4 aryl group, a C 6 - Ci 4 aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Cioheteroaryl group, or a C2- doheteroaryl group, which is substituted by F, or d-C-isalkyl; or -Si(R 2' )(R 3' )(R 14' ); wherein R 65 , R 67 , R 68 and R 69 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-C
  • R 1 , R 2 , R 3 and R 6 are independently of each other a group of formula— (A )o-(A 2 )p-(A 3 ) q -(A 4 )rR 16 , wherein o, p, q, r, A 1 , A 2 , A 3 , A 4 and R 16 as defined above;
  • Y 1 and Y 2 are independently of each other a Ci-C25alkyl group, which can optionally be substituted by E and or interupted by D; a C6-C2 4 aryl group, which can optionally be substi- tuted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C7- C25aralkyl group, which can optionally be substituted by G, wherein D, E and G are as defined above.
  • R 1 , R 2 , R 3 and R 6 are independently of each other a group of formula—(A 1 ), (A 3 )q-(A 4 ) r R 16 , wherein o, p, q, r, A 1 , A 2 , A 3 , A 4 and R 16 as defined above, or below.
  • formula (I) compounds of formula
  • R 3 and R 6 are independently of each other a group of formula— (A 1 ) 0 -(A 2 )p-(A 3 )q-(A 4 ) r R 16 , wherein o, p, q, r, A 1 , A 2 , A 3 , A 4 and R 16 as defined above; c is 0, or 1 ; d is 0, or 1 ; and
  • Y 1 and Y 2 are independently of each other a Ci-C25alkyl group, which can optionally be substituted by E and or interupted by D; a C6-C2 4 aryl group, which can optionally be substituted by G, a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C7- C25aralkyl group, which can optionally rein D, E and G are as de-
  • R 3 and R 6 are independently of each other a group of formula— (A 1 ) 0 -(A 2 ) p -(A 3 ) q - (A 4 )rR 16 , wherein o, p, q, r, A 1 , A 2 , A 3 , A 4 and R 16 as defined above, or below.
  • a 1 , A 2 , A 3 and A 4 are independently of each other a C6-C2 4 arylen group, which can optionally be substituted by G, or a C2-C3oheteroarylen group, which can optionally be substituted by G.
  • the C6-C2 4 arylen groups A 1 , A 2 , A 3 and A 4 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 A 1 , A 2 , A 3 and A 4 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, for example, benzofu- idylene
  • zothiophenylene phenoxythienylene, pyrrolylene, imidazolylene, pyrazolylene, pyridylene, bipyridylene, triazinylene, pyrimidinylene, pyrazinylene, pyridazi- nylene, indolizinylene, isoindolylene, indolylene, indazolylene, purinylene, quinolizinylene, chinolylene, isochinolylene, phthalazinylene, naphthyridinylene, chinoxalinylene, chinazoli- nylene, cinnolinylene, pteridinylene, carbolinylene, benzotriazolylene, benzoxazolylene, phenanthridinylene, acridinylene, pyrimidinylene, phenanthrolinylene, phenazinylene, iso- thiazolylene, phenothiazoly
  • 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, especially by C6-Cioaryl, C6-Cioaryl which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl.
  • Preferred C2-C3oheteroarylen groups are pyridylene, triazinylene, pyrimidinylene, especially benzofuro[2,3-b]pyridylene, benzothiopheno[2,3-b]pyridylene , pyrido[2,3-b]indolylene , benzofuro[2,3-c]pyridylene, benzothiopheno[2,3-c]pyridylene , pyrido[2,3-c]indolylene fu- ro[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 benzimid- azo[1 ,2-a]benzimidazo-2,5-ylene , which can be un
  • the C6-C2 4 arylen 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-Ci 4 aryl group, a C6-Ci 4 aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Cioheteroaryl group, or a C2-Cioheteroaryl group, which is substituted by F, or Ci-Cisalkyl.
  • Ci-Cisalkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, -CF3,
  • Benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimidazo[1 ,2-a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are examples of a C2-Cioheteroaryl group.
  • Phenyl, 1-naphthyl and 2- naphthyl are examples of a C6-Ci 4 aryl group.
  • a 1 , A 2 , A 3 and A 4 are independently of each other a group of the formula
  • X is O, S, or NR24
  • R 24 is a C6-C2 4 aryl group, which can optionally be substituted by G, or a C2-C3oheteroaryl group, which can optionally be substituted by G, wherein G is as defined above.
  • R 16 may be a C6-C2 4 aryl group, which can optionally be substituted by G, or a C2- C3oheteroaryl group, which can optionally be substituted by G.
  • the C6-C2 4 aryl group 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, which may be unsubstituted or substituted.
  • the C2-C3oheteroaryl group R 16 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 9H-pyrido[2,3-b]indolyl, benzofuro[2,3- bjpyridyl, 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']dipy
  • the C6-C2 4 aryl 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-C-i 4 aryl group, a C6-Ci 4 aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Cioheteroaryl group, or a C2-Cioheteroaryl 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, benzimi azo-5-yl
  • azolo[2,1-b][1 ,3]benzothiazolyl ( , or ), carbazolyl, dibenzofuranyl, and dibenzothiophenyl, which can be unsubstituted or substituted especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C 4 alkyl; or C2-Ci 4 heteroaryl.
  • R 16 is preferably H, or a group of the formula -Si(R 12 )(R 13 )(R 14 ),
  • R 12 , R 13 and R 14 are independently of each other a phenyl group, which can optionally be substituted by one, or more Ci-Cisalkyl groups;
  • R 21 and R 21 ' are independently of each other H, a phenyl group, or a Ci-Cisalkyl group;
  • X is O, S, or NR 24 ,
  • R 24 is a C6-C2 4 aryl group, which can optionally be substituted by G, or a C2-C3oheteroaryl group, which can optionally be substituted by G, wherein G is as defined above.
  • o 0, or 1
  • p is 0, or 1
  • q is 0, or 1
  • r is 0, or 1
  • a 1 , A 2 , A 3 and A 4 are independently of each oth
  • the group of the formula -(A 1 ) 0 -(A 2 )p-(A 3 )q-(A 4 ) r R 16 is a
  • the group of the formula -(A 1 ) 0 -(A 2 )p-(A 3 ) q -(A 4 ) r R 16 is a group of formula (Xlla), (Xllb), (Xllc), (Xllt), (Xlllb), (Xlllh), (Xllli), (Xlllj), (XlVb), (XIVc), (XIVo), (XIVp), (XlVq), (XIVo), (XIVp), (XlVq), (XIVz), (XVc), (XVd), (XVh), (XVI), (XVo), (XVq), (XVIc), (XVIe), (XVIf); (XVIIa), (XVIIe), (XVIIf), or (XVIIs).
  • the present invention is directed to compounds of formula (Xlla), (Xllb), (Xllc), (Xllt), (Xlllb), (Xlllh), (Xlll
  • R 16 is Si(Ph) 3 ,
  • R 1 , R 2 , R 3 and R 6 are a group of formula -(A ) 0 -(A 2 )p-(A 3 ) q -(A 4 )rR 16 , wherein 40
  • the present invention is directed to compounds of formula (la'), (lb'), (Ic'), or (Id'), wherein R 1 , R 2 , R 3 and R 6 are a group of formula -(Ai)o-(A2)p-(A3) q -(A4) r Ri6 , wherein -(Ai) 0 -(A 2 ) P -(A 3 ) q -(A4) r is a single bond, or a group of
  • R 3 and R 6 may be the same or different.
  • the present invention is directed to compounds of formula (le'), wherein R 3 and R 6 are the same, or different from each other and are a group of formula -(Ai) 0 -(A2) -(A 3 ) -(A4) r Ri 6 , wherein -(Ai) 0 -(A2) -(A 3 ) -(A4) r is a sin-
  • 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-methylhexyl, 1 ,1 ,3,3,5,5- hexa methyl hexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyl- heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl, n-non
  • d-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, isobutyl, tert.-butyl.
  • Ci-C25alkoxy 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 d-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, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy.
  • 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-C2 4 aryl which optionally can be substituted, is typically phenyl, 4- methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, or anthryl, which may be unsubstituted or substituted.
  • Phenyl, 1-naphthyl and 2-naphthyl are examples of a C6-Cioaryl group.
  • C7-C25aralkyl is typically benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, co-phenyl-butyl, ⁇ , ⁇ -dimethyl- o-phenyl-butyl, ⁇ -phenyl-dodecyl, ⁇ -phenyl-octadecyl, co-phenyl-eicosyl or ⁇ -phenyl-docosyl, preferably Cz-Cisaralkyl such as benzyl, 2-benzyl-2- propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, co-phenyl-butyl, ⁇ , ⁇ -dimethyl-co-phenyl-butyl, co-phenyl-dodecyl or ⁇ -phenyl-octadecyl, and particularly preferred C7-Ci2aral
  • 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 ⁇ -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,
  • Benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimidazo[1 ,2- a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are examples of a C2-Ci 4 heteroaryl group.
  • C6-C2 4 arylen 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-C2 4 arylen 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, indoly
  • C2-C3oheteroarylen groups are pyridylene, triazinylene, pyrimidinylene, carbazolylene, dibenzofuranylene and benzimidazo[1 ,2-a]benzimidazo-2,5-ylene
  • Ci-C4alkyl which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl.
  • Possible substituents of the above-mentioned groups are d-dalkyl, a hydroxyl group, a mercapto group, d-dalkoxy, d-dalkylthio, halogen, halo-d-dalkyl, or a cyano group.
  • the C6-C24aryl (d-dsaryl) and d-doheteroaryl groups are preferably substituted by one, or more d-dalkyl groups.
  • a substituent occurs more than one time in a group, it can be different in each occurrence.
  • Halo-d-dalkyl is an alkyl group where at least one of the hydrogen atoms is replaced by a halogen atom. Examples are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -(CF 2 ) 3 CF 3 , and -C(CF 3 ) 3 .
  • substituted by G means that one, or more, especially one to three substituents G might be present.
  • 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; d-dsaryl is not interrupted; interrupted arylalkyl contains the unit D in the alkyl moiety, d-dsalkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (Ch Ch O i-g- R x , where R* is H or d-doalkyl or d-doalkanoyl (e.g.
  • R y is d-dsalkyl, d-Ci2cycloalkyl, phenyl, C 7 -d 5 phenylalkyl, and R y ' embraces the same definitions as R y or is H ;
  • d-dalkylene-COO-R z e.g. CH 2 COOR z , CH(CH 3 )COOR z , C(CH 3 ) 2 COOR z , where R z is H , d-dsalkyl, (CH2CH20)i-9-R x , and R x embraces the definitions indicated above;
  • 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,
  • 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 (dibenzofuran 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.
  • the bromination with Br2 can be effected in glacial acetic acid or chloroform at low temperatures, e.g. 0°C.
  • 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.
  • 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.
  • 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
  • alkali metal alkox- ides such as NaOMe, NaOEt.
  • mixtures of the aforementioned bases are suitable. Particular preference is given to NaOH, KOH, NaH
  • Heteroarylation can be affected, for example, by copper-catalyzed coupling of
  • 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- apeloles 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.
  • diboronic acid or diboronate group containing dibenzofurans, diben- zothiophenes, and carbazoles can be obtained by reactin
  • a catalyst such as, for example, [1 ,1'- bis(diphenylphosphino)ferrocene]dichloropalladium(ll), complex (Pd(CI)2(dppf)
  • a base such as, for example, potassium acetate
  • a solvent such as, for example, dimethyl formamide, dimethyl sulfoxide, diox
  • Y 1 is independently in each occurrence a Ci-Ci8alkylgroup and Y 2 is independently in each occurrence a C2-Cioalkylene group, such as -CY 3 Y 4 -CY 5 Y 6 -, or -CY7Y8-CY9Y10- CY Y 12 -, wherein Y 3 , Y 4 , Ys, ⁇ ⁇ , ⁇ ?, ⁇ ⁇ _ ⁇ ⁇ .
  • ⁇ and ⁇ 12 are independently of each other hydrogen, or a Ci-Ci8alkylgroup, especially -C(CH3)2C(CH3)2-, - C(CH3)2CH 2 C(CH 3 )2-, or -CH 2 C(CH 3 )2CH 2 -, and Y 13 and Y 14 are independently of each other hydrogen, or a Ci-Ci8alkylgroup.
  • 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,
  • 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 esters such as, for example, B(isopropoxy)3, B(methoxy)3, or
  • lithium amides such as, for example, lithium diisopropylamide (LDA) followed by esters such as, for example, B(isopropoxy)3, B(methoxy)3, or
  • imidazo[1 ,2-a]imidazoles such as, for example and
  • the catalyst may be one of the ⁇ -halo(triisopropylphosphine)( ⁇ 3 -allyl)palladium(ll) type (see for example W099/47474).
  • the Suzuki reaction is carried out in the presence of an organic solvent, such as an aromatic hydrocarbon or a usual polar organic solvent, such as benzene, toluene, xylene, tetrahydrofurane, or dioxane, or mixtures thereof, most preferred toluene.
  • an organic solvent such as an aromatic hydrocarbon or a usual polar organic solvent, such as benzene, toluene, xylene, tetrahydrofurane, or dioxane, or mixtures thereof, most preferred toluene.
  • the amount of the solvent is chosen in the range of from 1 to 10 I per mol of boronic acid derivative.
  • the reaction is carried out under an inert atmosphere such as nitrogen, or argon.
  • an aqueous base such as an alkali metal hydroxide or carbonate such as NaOH, KOH, Na2C03, K2CO3, Cs2C03 and the like, preferably an aqueous K2CO3 solution is chosen.
  • the molar ratio of the base to boronic acid or boronic ester derivative is chosen in the range of from 0.5:1 to 50:1 , very especially 1 :1.
  • the reaction temperature is chosen in the range of from 40 to 180°C, preferably under reflux conditions.
  • the reaction time is chosen in the range of from 1 to 80 hours, more preferably from 20 to 72 hours.
  • a usual catalyst for coupling reactions or for polycondensation reactions is used, preferably Pd-based, which is described in WO2007/101820.
  • the palladium compound is added in a ratio of from 1 :10000 to 1 :50, preferably from 1 :5000 to 1 :200, based on the number of bonds to be closed. Preference is given, for example, to the use of palla- dium(ll) salts such as PdAc2 or Pd2dba3 d from the
  • the ligand is added in a ratio of from 1 : 1 to 1 :10, based on Pd.
  • the catalyst is added as in solution or suspension.
  • an appropriate organic solvent such as the ones described above, preferably benzene, toluene, xylene, THF, dioxane, more preferably toluene, or mixtures thereof, is used.
  • the amount of solvent usually is chosen in the range of from 1 to 10 I per mol of boronic acid derivative.
  • Organic bases such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Lead- beater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein).
  • phase transfer catalysts such as, for example TBAB
  • Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, G. Wegner in Macromol. Rap- id Commun. 17 (1996) 239-252 and G. A. Molander und B. Canturk, Angew. Chem. , 121 (2009) 9404 - 9425.
  • JP2011084531 describes, for example, the synthesis of benzofuro[3,2-b]pyridine in two steps starting from 2-bromopyridin-3-ol using a base catalyzed cyclisation. The brominated ation with bromine in the presence of silver sulfate.
  • US2010/0187984 describes, for example, the synthesis of 3,6-dichloro-benzofuro[2,3- b]pyridine in three steps starting from 2-amino-5-chloropyridine using a cyclisation of a dia- zoniumion salt.
  • JP2002284862 describes the syntheses of 2,7-dibromo-furo[3,2-b:4,5-b]dipyridine starting from 2-(3-amino-5-bromo-2-pyridyl)-5-bromo-pyridin-3-amine using an acid catalyzed cy- clisation of a diazoniumion salt.
  • the synthesis of the starting material is described by Y. F
  • halogenation can be performed by methods known to those skilled in the art.
  • 4-lodobenzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting enzimidazo- lo[2,1-b][1 ,3]benzothiazole with butyl lithium and I2 in tetra arylation can
  • 4-iodobenzimidazolo[2,1-b][1 ,3]benzothiazole Ullmann reaction.
  • 4-Chlorobenzimidazolo[2,1-b][1 ,3]benzothiazole can be prepared as described in Organic &
  • 2-lodobenzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting benzimidazo- lo[2,1-b][1 ,3]benzothiazole in CH 3 COOH and CF3COOH in the presence of N- iodosuccinimide (NIS).
  • NIS N- iodosuccinimide
  • 2-Bromobenzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting 2- mercaptobenzimidazole and 1 ,4-dibromo-2-nitro-benzene in the presence of caesiu bonate in DMSO (dimethyl sulfoxide).
  • 2-Bromo-9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole can be obtained by reacting 2- bromobenzimidazolo[2,1-b][1 ,3]benzothiazole with N-iodosuccinimide (NIS) in acetic acid in the presence of trifluoroacetic acid,
  • NIS N-iodosuccinimide
  • the above compound can also be prepared by Suzuki coupling of 9- iodobenzimidazolo[2,1-b][1 ,3]benzothiazole and 9-[8-(4,4,5,5-tetramethyl-1 ,3,2- dioxaborolan-2-yl)dibenzofuran-2-yl]carbazole (WO2012130709).
  • compounds of formula I can be obtained by reacting a compound of formula X with 1 ,3-dihydrobenzimidazole-2-thione in the presence of a base, such as, for example, CS2CO3, in a solvent, such as, for example, dimethylsulfoxide, at elevated temperatures, especially 130 to 170 °C.
  • a base such as, for example, CS2CO3
  • a solvent such as, for example, dimethylsulfoxide
  • Examples 1 to 3 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.
  • switching elements such as organic transistors, e.g. organic FETs and organic TFTs, organic solar cells and organic light- emitting diodes (OLEDs)
  • OLEDs organic light- emitting diodes
  • 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.
  • the compounds of the formula I can be used as conductor/complementary materials in organic electronics applications 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).
  • inventive compounds of the formula I are preferably used as matrix materials in organic electronics applications, especially in OLEDs.
  • an emitter material 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 which has, for example, a good hole transport property. This achieves a high quantum efficiency of this emission layer.
  • 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.
  • 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
  • the organic layer 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.
  • 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.
  • the layers with charge transport capacity may com- prise the compounds of formula I.
  • 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
  • At least one compound of the formula I is used as charge transport material.
  • a compound of the formula la, lb, Ic, Id, or le is used as charge transport material.
  • Examples of preferred compounds of formula I are compounds A-1 to A-29, B-1 to B-29, C-1 to C-31 , D-1 to D-30, E-1 to E-12, F-1 to F-11 and G-1 to E-20 shown above.
  • At least one compound of the formula I is used as charge/exciton blocker material.
  • a compound of the formula la, lb, Ic, Id, or le is used as charge/exciton blocker material.
  • preferred compounds of formula I are compounds A-1 to A-29, B-1 to B-29, C-1 to C-31 , D-1 to D-30, E-1 to E-12, F-1 to F-11 and G-1 to E-20 shown above.
  • the present application further relates to a light-emitting layer comprising at least one compound of the formula I.
  • the inventive organic light-emitting diode thus generally has the following structure:
  • the inventive OLED may, for example - in a preferred embodiment - be formed from the following layers:
  • Layer sequences different than the aforementioned structure are also possible, and are known to those skilled in the art.
  • 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.
  • the OLEDs may have a blocking layer for electrons/excitons (d) between the hole transport layer (c) and the Light- emitting layer (e).
  • a plurality of the aforementioned functions are combined in one layer and are assumed, for example, by a single material present in this layer.
  • a material used in the hole transport layer in one embodiment, may simultaneously block excitons and/or electrons.
  • the individual layers of the OLED among those specified above may in turn be formed from two or more layers.
  • 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.
  • 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 11 , 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.
  • 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.
  • 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.
  • PVK poly(N-vinylcarbazole)
  • polythiophenes polypyrrole
  • polyaniline polyaniline
  • self-doping polymers such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]- 2,5-di
  • hole transport material 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 ex- ample, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996, US20070278938, US2008/0106190, US201 1/0163302 (triarylamines with (di)benzothiophen/(di)benzofuran; Nan-Xing Hu et al. Synth. Met. 1 11 (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.
  • 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.
  • PVK poly(N-vinylcarbazole)
  • polythiophenes polypyrrole
  • polyaniline polyaniline
  • self-doping polymers such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]-2,5- diyl)
  • metal carbene complexes as hole transport materials.
  • Suitable carbene complexes are, for example, carbene complexes as described in WO2005/019373A2, WO2006/056418 A2, WO2005/1 13704, WO2007/115970,
  • 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.
  • 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 , ReCb and/or V2O5, preferably M0O3 and/or ReCb, 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 ,
  • 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 , wherein the total amount of the M0O3 and the carbene com- plex is 100 wt %.
  • 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 complexes for use as electron/exciton blocker material are, for example, carbene complexes as described in WO2005/019373A2, W02006/056418 A2, WO2005/113704, WO2007/115970, WO2007/115981 and WO2008/000727.
  • 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 com- plexes, 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 ,
  • WO 2005/113704 A2 WO 2006/1 15301 A1 , WO 2006/067074 A1 , WO 2006/056418, WO 2006121811 A1 , WO 2007095118 A2, WO 2007/115970, WO 2007/115981 ,
  • metal complexes are the commercially available metal complexes tris(2- phenylpyridine)iridium(lll), iridium(lll) tris(2-(4-tolyl)pyridinato-N,C 2 '), bis(2- phenylpyridine)(acetylacetonato)iridium(lll), iridium(lll) tris(l-phenylisoquinoline), iridium(lll) bis(2,2'-benzothienyl)pyridinato-N,C 3 ')(acetylacetonate), tris(2-phenylquinoline)iridium(lll), iridium(lll) bis(2-(4,6-difluorophenyl)pyridinato-N,C 2 )picolinate, iridium(lll) bis(1- phenylisoquinoline)(acetylacetonate), bis(2-phenylquinoline)(acett
  • Preferred phosphorescence emitters are carbine complexes. Suitable phosphorescent blue emitters are specified in the following publications: WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981 , WO2008/000727, WO2009050281 , WO2009050290, WO2011051404, US2011/057559 WO2011/073149, WO2012/121936A2,
  • the light emitting layer (e) comprises at least one carbine complex as phosphorescence emitter.
  • Suitable carbine complexes are, for example, compounds of the
  • 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 ⁇ complex with M 1 ; 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;
  • nl 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;
  • 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.
  • M is Ir, or Pt
  • n1 is an integer selected from 1 , 2 and 3,
  • Y is N R 51 , O, S or C(R25) 2 ,
  • 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 op- tionally 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,
  • R5s are eac h, jf 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 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 het- eroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms
  • 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, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, cycloheteroalkyi 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, 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
  • 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 at- oms, 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,
  • 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 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 WO201 1/073149.
  • 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 , US20110227049, WO201 1090535, WO2012/08881 , WO20100056669, WO20100118029, WO20100244004, WO201 1109042, WO2012166608, US20120292600, EP2551933A1 ; US6687266, US20070190359, US20070190359, US20060008670; WO2006098460, US20110210316, WO 2012053627; US6921915, US20090039776; and JP2007123392.
  • the light-emitting layer may comprise further components in addition to the emitter materi- al.
  • a fluroescent dye may be present in the light-emitting layer in order to alter the emission color of the emitter material.
  • a matrix material can be used. This matrix material may be a polymer, for example poly(N- vinylcarbazole) or polysilane.
  • At least one compound of the formula I is used as matrix material.
  • a compound of the formula la, lb, lc, Id, or le is used as matrix material.
  • preferred compounds of formula I are com- pounds A-1 to A-29, B-1 to B-29, C-1 to C-31 , D-1 to D-30, E-1 to E-12, F-1 to F-11 and G- 1 to E-20 shown above.
  • 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 ma- trix 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.
  • 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
  • WO2007108459 H-1 to H-37
  • 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.
  • WO2007119816 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 ,
  • the above-mentioned small molecules are more preferred than the above-mentioned (co)polymers of the small molecules. 72 (for example,
  • X is NR, S, O or PR
  • R is aryl, heteroaryl, alkyl, cycloalkyi, or heterocycloalkyi;
  • R221 R222 anc are independently of each other aryl, heteroaryl, alkyl, cycloalkyi, or heterocycloalkyi, wherein at least on of the groups R 221 , R 222 , or R 223 is aryl, or heteroaryl;
  • R 224 and R 225 are independently of each other alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl, a group A 200 , or a group having donor, or acceptor characteristics;
  • n2 and m2 are independently of each other 0, 1 , 2, or 3;
  • R 206 and R 207 form together with the nitrogen atom a cyclic residue having 3 to 10 ring atoms, 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 R208 i R209 i R2io_ 2i i _ 212_ 213_ R214 u nc
  • R215 are independently of each other aryl, het
  • T is O, or S, preferably O. If T occurs more than one time in a molecule, all groups T have the same meaning.
  • 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-4,7-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.
  • mCPy 2,6-bis(N-carbazolyl)pyridine
  • BCP 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline
  • BAIq bis(2- methyl-8-quinolinato)-4-phenylphenylato)aluminum(lll)
  • BAIq bis(
  • 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
  • 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
  • compounds (SH-1 ), (SH-2), (SH-3), SH-4, SH-5, SH-6, (SH-7), (SH-8), (SH-9) and (SH-10) may be used as hole/exciton blocking materials.
  • 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.
  • 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).
  • PBD 2-(4-biphenylyl)-5-(4-t- butylphenyl)-1 ,3,4-oxadiazole
  • TEZ 3-(4-biphenylyl)-4phenyl-5-(4-t-butylphenyl)-1 ,2,4- triazole
  • 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.
  • alkaline earth metal or alkali metal hy- droxyquinolate complexes for example Liq
  • 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.
  • n-Doping is achieved by the addition of reducing materials.
  • 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, Li 3 N, Rb 2 C0 3 , dipotassium phthalate, W(hpp) 4 from EP1786050, or with compounds described in EP1837926B1 , EP1837927, EP2246862 and WO2010132236.
  • 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)
  • the electron-transport layer comprises at least one compound of the general formula (VII)
  • R 32 and R 33 are each independently F, d-Cs-alkyl, or C6-Ci 4 -aryl, which is optionally substituted by one or more d-Cs-alkyl groups, or
  • R 32 and/or R 33 substituents together form a fused benzene ring which is optionally substituted by one or more d-Cs-alkyl groups;
  • a and b are each independently 0, or 1 , 2 or 3,
  • M 1 is an alkaline metal atom or alkaline earth metal atom
  • p is 1 when M 1 is an alkali metal atom, p is 2 when M 1 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 g Q g in which g is an integer, for example LkQe- Q is an 8-hydroxyquinolate ligand or an 8-hydroxyquinolate derivative.
  • the electron-transport layer comprises at least one compound of the formul
  • R 34 , R 35 , R 36 , R 37 , R 34' , R 3 5', 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-C2 4 -aryl, C6-C2 4 -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;
  • E is -OR 44 ; -SR 44 ; -NR 4 0R 4 i ; -COR 43 ; -COOR 42 ; -CONR 4 0R 4 i ; -CN; or F;
  • G is E, Ci-Ci8-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,
  • 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 C1-C18- 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-Cie-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cie-alkyl,
  • R 47 is Ci-Cis-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cie-alkyl.
  • Preferred compounds of the formula (VIII) are compounds of the formula (Villa)
  • R 48 is H or Ci-Cis-alkyl
  • R 48 ' is H , Ci-Cis-alkyl or or
  • the electron-transport layer comprises a compound Liq and a compound ETM-2.
  • 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 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.
  • the electron-transport layer comprises at least one phenanthro- line derivative and/or pyridine derivative.
  • the electron-transport layer comprises at least one phe- nanthroline derivative and/or pyridine derivative and at least one alkali metal hydroxyquinolate complex.
  • 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.
  • the electron-transport layer comprises a compound described in WO2012/11 1462, WO2012/147397, WO2012014621 , such as, for example, a
  • 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.
  • 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.
  • the different layers if present, have the following thicknesses:
  • anode 500 to 5000 A (angstrom), preferably 1000 to 2000 A;
  • Suitable materials for the individual layers are known to those skilled in the art and are disclosed, for example, in WO 00/70655.
  • 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.
  • the inventive OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate.
  • Suitable substrates are, for example, glass, inorganic semi- conductors or polymer films.
  • vapor deposition it is possible to use customary techniques, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others.
  • 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.
  • 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.
  • 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.
  • 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 dis- play units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains.
  • inventive OLEDs are, for example, keyboards; items of clothing; furniture; wallpaper.
  • 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.
  • Example 1a) is repeated, except that instead of 6H-benzimidazolo[1 ,2-a]benzimidazole 9H-carabazole is used.
  • Example 1a) is repeated, except that instead of the product of Example 1 a) the product of Example 2a) is used.
  • N-iodosuccinimide N-iodosuccinimide
  • 2- bromobenzimidazolo[2,1-b][1 ,3]benzothiazole 175 ml acetic acid and 9 ml trifluoroacetic acid at 100 °C under nitrogen.
  • the product is stirred for 2.5 g at 100 °C and the precipitated product is filtered off.
  • the product is washed with a 10 % sodium dithionite solution, water and methanol.
  • the product is soxhlet extracted with 300 ml methyl ethyl ketone and the product is filtered off (yield: 15.1 g (82 %)).
  • the reaction mixture is stirred at 100 °C under nitrogen for 75 h and then filtered on Hyflo Super Cel (CAS number 91053-39-3) with dichloromethane.
  • the di- chloromethane is distilled off and the solution is poured into methanol.
  • the product is filtered off, filtered on silica gel with dichloromethane and then dichloromethane/ethanol 95/5.
  • the solvent is concentrated to a volume of 10 ml ethanol. 100 ml methanol are added and the product is filtered off (yield: 6.38 g (49 %)).
  • 2,9-di(dibenzofuran-4-yl)benzimidazolo[2,1-b][1 ,3]benzothiazole is prepared in analogy to Example 6 starting from 2-bromo-9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole and dibenzofuran-4-ylboronic acid.
  • 2,9-di(dibenzofuran-4-yl)benzimidazolo[2,1-b][1 ,3]benzothiazole is prepared in analogy to Example 6 starting from 9-iodo-benzimidazolo[2,1-b][1 ,3]benzothiazole and 9-[8-(4,4,5,5- tetramethyl-1 ,3,2-dioxaborolan-2-yl)dibenzofuran-2-yl]carbazole.
  • 9-[8-(4,4,5,5-tetramethyl- 1 ,3,2-dioxaborolan-2-yl)dibenzofuran-2-yl]carbazole is prepared as described in
  • the triplet energies of the materials are directly determined from the onsets of the ured phosphorescence spectra of the thin films of neat materials.
  • the 2% in PMMA films are prepared by dissolving 1 mg of the respective material in 370 ⁇ of a dichloromethane solution containing 10 wt% PMMA.
  • Compound (B-1 ) is deposited by vapor deposition to the quartz substrates at a rate of approx. 0.5-5 nm/min at about 10- 6 mbar until approx. 60 nm thick film is formed.
  • the resulting thin film samples are inserted into a liquid-helium cryostat Optistat CF (Oxford Instruments) and cooled to a temperature of 4-5K.
  • the phosphorescence spectra are measured with a fluorescence/phosphorescence spectrometer FLS- 920P (Edinburgh Instruments).
  • the samples are excited with an electrically pulsed LED model UVTOP 315-HL-T039 (Fa. Roithner, Vienna) with a center wavelength of 320 nm and a pulse width of 5 ⁇ .
  • the emission spectra are detected via time-gated spectroscopy with a delay-time of 260 ⁇ is.
  • the triplet energies (Ti) are determined from the onset of the phosphorescence spectra, the results are shown in the table below.
  • Compound F-12 has a higher triplet energy than comparative compound CC-1 . That is, compound F-12 is, in principal, a better host for deep blue phosphorescent emitters.
  • Cyclic voltammetry and differential pulsed voltammetry are performed using a computer- controlled Metrohm Autolab PGSTAT12 potentiostat in a three-electrode single- compartment cell with a platinum or glassy carbon working electrode, a platinum wire counter electrode and an Ag/AgCI or Ag/Ag + reference electrode.
  • Anhydrous DMF (distilled over P2O5) is used as the solvent under an inert atmosphere, and 0.1 M tetra-n-butylammonium hexafluorophosphate (TBAPF6) is used as the supporting electrolyte.
  • TAPF6 tetra-n-butylammonium hexafluorophosphate
  • the samples are measured at a concentration of 1 mM. All potentials are internally referenced to the ferro- cene/ferrocenium (Fc/Fc + ) couple.
  • IP ionization potential
  • EA electron affinity
  • IP [eV] 1.4x(1.0xE 0 nset - Fc/Fc + E 0 nset) + 4.6 ⁇ Org. El. 2005, 6, 1 1-20) and
  • the electron affinity of the benzimidazolo[2,1-b][1 ,3]benzothiazole derivatives, such as, for example, compound B-2, of the present invention is higher than the electron affinity of corresponding 6H-benzimidazolo[1 ,2-a]benzimidazole derivatives, such as, for example, comparative compound CC-2.
  • the ionization potential of the benzimidazolo[2,1- b][1 ,3]benzothiazole derivatives of the present invention is also lower (higher absolute value) than the ionization potential of corresponding 6H-benzimidazolo[1 ,2-a]benzimidazole derivatives.
  • the benzimidazolo[2,1-b][1 ,3]benzothiazoles of the present application are in general superior electron injection, hole blocking and electron transporting units in comparison with benzimidazolo[1 ,2-a]benzimidazoles of the prior art.
  • the ITO substrate used as the anode is first cleaned with an isopropanol in an ultrasonic bath. To eliminate any possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for further 30 minutes. This treatment also improves the hole injection properties of the ITO. Then Plexcore® OC AJ20-1000 (commercially available from Plextronics Inc.) is spin-coated and dried to form a hole injection layer (-40 nm). Thereafter, the organic materials specified below are applied by vapor deposition to the Plexcore® coated substrate at a rate of approx. 0.5-5 nm/min at about 10- 7 -10- 9 mbar. As a
  • hole transport material compound (HTM-1 ; for preparation, see Ir com- plex (7) in the application WO2005/019373) is applied by vapor deposition in a thickness of 10 nm doped with MoOx (-10%) to improve the conductivity.
  • EQE External quantum efficiency

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Abstract

La présente invention concerne des composés de formule (I), un procédé permettant de les préparer et leur utilisation dans des dispositifs électroniques, en particulier des dispositifs électroluminescents. Lorsqu'ils sont utilisés comme matière de transport d'électrons et/ou matière hôte pour des émetteurs phosphorescents dans des dispositifs électroluminescents, les composés de formule (I) peuvent permettre d'obtenir un rendement accru, une stabilité accrue, une aptitude accrue à la fabrication et/ou des caractéristiques spectrales accrues de dispositifs électroluminescents.
PCT/EP2014/066174 2013-07-30 2014-07-28 Benzimidazolo[2,1-b][1,3]benzothiazoles pour des applications électroniques WO2015014791A1 (fr)

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PCT/IB2015/055667 WO2016016791A1 (fr) 2014-07-28 2015-07-27 Benzimidazolo[1,2-a] benzimidazoles 2,9-fonctionnalisé utilisés comme hôtes pour diodes électroluminescentes organiques (oled)

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KR20170025809A (ko) * 2015-08-31 2017-03-08 희성소재 (주) 헤테로고리 화합물 및 이를 이용한 유기 발광 소자
CN106543205A (zh) * 2016-11-08 2017-03-29 江苏三月光电科技有限公司 一种含有苯并咪唑的化合物及其在oled上的应用
EP3150606A1 (fr) 2015-10-01 2017-04-05 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazoles avec des groupements benzofurane ou benzothiophène pour des diodes émittant de la lumière
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KR20180047313A (ko) * 2016-10-31 2018-05-10 엘지디스플레이 주식회사 유기 화합물과 이를 이용한 발광다이오드 및 유기발광다이오드 표시장치
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