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WO2006128800A1 - Electroluminescent device - Google Patents

Electroluminescent device Download PDF

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Publication number
WO2006128800A1
WO2006128800A1 PCT/EP2006/062483 EP2006062483W WO2006128800A1 WO 2006128800 A1 WO2006128800 A1 WO 2006128800A1 EP 2006062483 W EP2006062483 W EP 2006062483W WO 2006128800 A1 WO2006128800 A1 WO 2006128800A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
substituted
aryl
group
alkoxy
Prior art date
Application number
PCT/EP2006/062483
Other languages
French (fr)
Inventor
Junichi Tanabe
Hidetaka Oka
Hiroshi Yamamoto
Original Assignee
Ciba Specialty Chemicals Holding Inc.
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Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=36791677&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2006128800(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to DE602006011734T priority Critical patent/DE602006011734D1/en
Priority to KR1020137016703A priority patent/KR101425423B1/en
Priority to EP06777232.7A priority patent/EP1885818B2/en
Priority to CN200680019047.6A priority patent/CN101184822B/en
Priority to AT06777232T priority patent/ATE455162T1/en
Application filed by Ciba Specialty Chemicals Holding Inc. filed Critical Ciba Specialty Chemicals Holding Inc.
Priority to US11/921,050 priority patent/US7989644B2/en
Priority to JP2008514060A priority patent/JP5107237B2/en
Publication of WO2006128800A1 publication Critical patent/WO2006128800A1/en
Priority to KR1020077030813A priority patent/KR101345104B1/en
Priority to US13/164,016 priority patent/US8735610B2/en
Priority to US14/252,870 priority patent/US8946984B2/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/917—Electroluminescent

Definitions

  • the present invention relates to electroluminescent devices that comprise organic layers that contain dibenzofuran compounds.
  • the compounds are suitable components of, for example, blue-emitting, durable, organo-electroluminescent layers.
  • the electroluminescent devices may be employed for full color display panels in, for example, mobile phones, televisions and personal computer screens.
  • JP9151182 discloses dibenzofurandiamine derivatives, which are suitable as a positive hole transporting agent, etc., in electrophotographic photoreceptor, solar cell, electroluminescence element etc.
  • the dibenzofurandiamine derivatives are represented by the following formula wherein R 1 to R 5 are each a halogen, a (substituted)alkyl, a (substituted)alkoxy, a (substituted)aryl or (substituted)aralkyl; (a), (b), (c) and (d) are each 0-5; (e) is 0-6.
  • R 1 to R 5 are each a halogen, a (substituted)alkyl, a (substituted)alkoxy, a (substituted)aryl or (substituted)aralkyl; (a), (b), (c) and (d) are each 0-5; (e) is 0-6.
  • JP2004311404 discloses compounds having at least one biaryl part structure for use in OLED application.
  • the dimeric dibenzofuran compound shown below is explicitly mentioned.
  • WO03105538 relates to benzotriazole compounds and their use in OLED application.
  • the dimeric benzotriazole compound shown below is explicitly mentioned.
  • the present invention relates to compounds of the formula
  • R 96' and R 97' are independently of each other H, -OR 201 , -SR 202 and/or -NR 203 R 204 , Ci-C 24 alkyl; Ci-C 24 alkyl, which is substituted by E and/or interrupted by D; C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkenyl, which is substituted by E, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl, which is substituted by G, aryl, aryl, which is substituted by G, heteroaryl, or heteroaryl, which is substituted by G, silyl, - ⁇ - SiR 62 R 63 R 64 , -CN, cyclic ether, -B(OR 65 ) 2 and/or halogen, especially fluorine, or R 81 and R 82 , R 82 and R 83 , R 83 and R 84 , R 85 and R 86 , R 86
  • a 41 , A ⁇ A 4J , A 44 , A 4S , A 4b and A v 4 4 7' are independently of each other H 1 halogen, hydroxy, CrC 24 alkyl, CrC 24 alkyl which is substituted by E and/or interrupted by D, Ci-C 24 perfluoroalkyl, C 5 -Ci 2 cycloalkyl, C 5 -Ci 2 cycloalkyl which is substituted by G and/or interrupted by S-, -O-, or -NR 5 -, C 5 -C 12 cycloalkoxy, C 5 - Ci 2 cycloalkoxy which is substituted by E, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 - C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 24 alkenyl, C 2 -C 24 alkynyl, d- C 24 al
  • M is a bonding group, such as a single (direct) bond, -CO-, -COO-; -S-; -SO-; -SO 2 -; -0-; C 1 - Ci 2 alkylene, C 2 -Ci 2 alkenylene, or C 2 -Ci 2 alkinylene, which are optionally interrupted by one or more -0-, or -S-; or a group [M 1 J n , wherein n is an integer 1 to 20, M 1 is arylene, or heteroarylene, which is optionally substituted by G, especially naphthylene, biphenylene, styrylene, anthrylene, or pyrenylene, which are optionally substituted by C r Ci 2 alkyl, halogen, -OR 201 , -SR 202 and/or -NR 203 R 204 , wherein R 201 is hydrogen, Ci-C 24 alkyl, Ci-C 24 alkyl, which is substituted by E and
  • R 202 is Ci-C 24 alkyl, Ci-C 24 alkyl, which is substituted by E and/or interrupted by D; C 2 - Ci 2 alkenyl, CrC 8 alkanoyl, C 2 -Ci 2 alkenyl, C 3 -C 6 alkenoyl; C 3 -C 8 cycloalkyl, or benzoyl, each of which may optionally be substituted by one or more groups CrC 6 alkyl, halogen, -OH, C r C 4 alkoxy or CrC 4 alkylsulfanyl; C 6 -Ci 4 aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, each of which may optionally be substituted by halogen, C r Ci 2 alkyl, C r Ci 2 alkoxy, phenyl-CrC 3 alkyloxy, phenoxy, CrCi 2 alkylsulfanyl, pheny
  • R 205 is hydrogen, CrC 24 alkyl, CrC 24 alkyl, which is substituted by E and/or interrupted by D; C 2 -C 5 alkenyl, C 3 -C 8 cycloalkyl, phenyl-CrC 3 alkyl, CrC 8 alkanoyl, C 3 -Ci 2 alkenoyl, C 6 -Ci 4 aryl, especially benzoyl; phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, each of which is optionally substituted by CrCi 2 alkyl, benzoyl, or Ci-Ci 2 alkoxy;
  • E is halogen, C 6 -Ci 4 aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, which may be substituted by -OR 5 , -SR 5 , -NR 5 R 6 , ⁇ SiR 62 R 63 R 64 , wherein R 62 , R 63 and R 64 are independently of each other a Ci-C 8 alkyl group, a C 6 -C 24 aryl group or a C 7 - Ci 2 aralkylgroup, -CN, cyclic ether and/or -B(OR 65 J 2 , wherein R 65 is hydrogen, CrC 24 alkyl, C 3 - C 8 cycloalkyl, C 7 -C 24 aralkyl, C 2 -Ci 8 alkenyl, C 2- C 24 alkynyl, hydroxy, mercapto, CrC 24 alkoxy, CrC 24 alkylthio, C 6
  • G is E, or CrCi 8 alkyl, wherein R 5 and R 6 are independently of each other H, C 6 -Ci 8 aryl; C 6 - Ci 8 aryl which is substituted by CrCi 8 alkyl, C r Ci 8 alkoxy, or silyl; Ci-d 8 alkyl or C r Ci 8 alkyl which is interrupted by -O-; or
  • R 5 and R 6 together form a five or six membered ring, in particular or
  • R 7 is H, C 6 -Ci 8 aryl, C 7 -Ci 2 alkylaryl, which are optionally substituted by CrCi 8 alkyl, or d-
  • R 8 is C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by Ci-Ci 8 alkyl, or Ci-Ci 8 alkoxy; Ci-Ci 8 alkyl,
  • R 61 and R 62 are independently of each other C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by d-
  • R 63 and R 64 are independently of each other H, C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by
  • the compound or compounds of the present invention emit light below about 520 nm, in particular between about 380 nm and about 520 nm.
  • the compound or compounds of the present invention have especially a NTSC coordinate of between about (0.12, 0.05) and about (0.16, 0.10), very especially a NTSC coordinate of about (0.14, 0.08).
  • the compound or compounds of the present invention have a melting point above about 15O 0 C, preferably above about 200 0 C and most preferred above about 25O 0 C.
  • the present organic compounds have a glass transition temperature greater than about 100°C, for example greater than about 110°C, for example greater than about 120 0 C, for instance greater than about 130 0 C.
  • compounds of formula I, or Il are preferred, wherein at least one of the groups R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 , R 91 , R 92 , R 93 , R 94 , R 95 , R 96 , R 97 , R 91' , R 92' , R 93' , R 94' , R 95' , R 96' and R 97' is a C 7 -C 30 aryl group, especially a polycyclic C 8 -C 30 aryl group.
  • M is a single bond, -CO-, -COO-, -S-, -SO-, -SO 2 -, , especially
  • n1, n2, n3, n4, n5, n6 and n7 are integers of 1 to 10, in particular 1 to 3,
  • a 6 and A 7 are independently of each other H, Ci-Ci 8 alkyl, d-Ci 8 alkyl which is substituted by E' and/or interrupted by D', C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G', C 2 -C 2 oheteroaryl, C 2 -C 2 oheteroaryl which is substituted by G', C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, CrCi 8 alkoxy, d- Ci 8 alkoxy which is substituted by E' and/or interrupted by D', C 7 -C 25 aralkyl, or -CO-A 28 ,
  • a 8 is CrCi 8 alkyl, C r Ci 8 alkyl which is substituted by E' and/or interrupted by D
  • a 9 and A 10 are independently of each other CrCi 8 alkyl, C r Ci 8 alkyl which is substituted by E' and/or interrupted by D', C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G', C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G', C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, CrCi 8 alkoxy, d- Ci 8 alkoxy which is substituted by E' and/or interrupted by D', or C 7 -C 25 aralkyl, or A 9 and A 10 form a ring, especially a five- or six-membered ring, which can optionally be substituted by one or more C r Ci 8 alkyl groups;
  • a 14 and A 15 are independently of each other H, CrCi 8 alkyl, Ci-Ci 8 alkyl which is substituted by E' and/or interrupted by D', C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G', C 2 - C 20 heteroaryl, or C 2 -C 20 heteroaryl which is substituted by G',
  • E' is -OA 29 ; -SA 29 ; -NA 25 A 26 ; -COA 28 ; -COOA 27 ; -CONA 25 A 26 ; -CN; -OCOOA 27 ; or halogen;
  • G' is E', or Ci-Ci 8 alkyl; wherein A 23 , A 24 , A 25 and A 26 are independently of each other H; C 6 - Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by CrCi 8 alkyl, or Ci-Ci 8 alkoxy; CrCi 8 alkyl, or d- Ci 8 alkyl which is interrupted by -0-; or A 25 and A l together form a five or six membered ring,
  • a 27 and A 28 are independently of each other H; C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by
  • CrCi 8 alkyl or Ci-Ci 8 alkoxy; CrCi 8 alkyl, or Ci-Ci 8 alkyl which is interrupted by -0-,
  • a 29 is H; C 6 -Ci 8 aryl; C 6 -Ci 8 aryl, which is substituted by CrCi 8 alkyl, or C r Ci 8 alkoxy; d-
  • Ci 8 alkyl or Ci-Ci 8 alkyl which is interrupted by -O-,
  • a 30 and A 31 are independently of each other CrCi 8 alkyl, C 6 -Ci 8 aryl, or C 6 -Ci 8 aryl, which is substituted by Ci-d 8 alkyl, and A 32 is Ci-Ci 8 alkyl, C 6 -Ci 8 aryl, or C 6 -Ci 8 aryl, which is substituted by d-Ci 8 alkyl.
  • a 6 and A 7 are independently of each other H, Ci-Ci 8 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methyl butyl, n-pentyl, isopentyl, n- hexyl, 2-ethylhexyl, or n-heptyl, C r Ci 8 alkyl which is substituted by E' and/or interrupted by D', such as -CH 2 OCH 3 , -CH 2 OCH 2 CH 3 , -CH 2 OCH 2 CH 2 OCH 3 , or -CH 2 OCH 2 CH 2 OCH 2 CH 3 , C 6 - C 24 aryl, such as phenyl, naphthyl, or biphenyl, C 6 -C 24 aryl which is substituted by G', such as -C 6 H 4 O
  • a 8 is preferably H, CrCi 8 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methyl butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, or C 6 - C 24 aryl, such as phenyl, naphthyl, or biphenyl.
  • a 14 and A 15 are independently of each other H, C r Ci 8 alkyl, such as as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C 6 -C 24 aryl, such as phenyl, naphthyl, or biphenyl.
  • C r Ci 8 alkyl such as as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl
  • C 6 -C 24 aryl such as phenyl, naphthyl, or biphenyl.
  • D' is preferably -CO-, -COO-, -S-, -SO-, -SO 2 -, -0-, -NA 25 -, wherein A 25 is C r Ci 8 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C 6 -C 24 aryl, such as phenyl, naphthyl, or biphenyl.
  • E' is preferably -OA 29 ; -SA 29 ; -NA 25 A 25 ; -COA 28 ; -COOA 27 ; -CONA 25 A 25 ; or -CN; wherein A 25 , A 27 , A 28 and A 29 are independently of each other CrCi 8 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C 6 -C 24 aryl, such as phenyl, naphthyl, or biphenyl.
  • CrCi 8 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-he
  • a 8 and A 9 are independently of each other Ci-Ci 8 alkyl, or cyclohexan; wherein A 6 and A 7 are
  • Groups M having a polycyclic C 8 -C 30 arylen group, or a polycyclic C 4 -C 26 heteroarylen group, wherein
  • polycyclic ring system comprises at least 8 atoms, are preferred, and
  • R 95 and R 95 are independently of each other Ci-C 24 alkyl, or C 6 -Ci 4 aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, which may be substituted by one, or more Ci-C 8 alkyl, or C r C 8 alkoxy groups, such as a group of formula
  • R 41 , R 41 , R 42 and R 42 are independently of each other is hydrogen, Ci-C 8 alkyl, or Ci-C 8 alkoxy
  • R 45 is hydrogen, phenyl, or 1 -naphthyl, which can be substituted by one, or more CrC 8 alkyl, or Ci-C 8 alkoxy groups; or CrC 8 alkyl, or Ci-C 8 alkoxy.
  • compounds of formula Hb are preferred, wherein M is a single bond, R 96 and R 96' are a group . especially , and R 81 , R 92 , R 93 , R 94 ,
  • R 95 , R 96 , R 97 , R 91' , R 92' , R 93' , R 94' , R 95' , R 96' and R 97' are hydrogen.
  • R 95 , R 96 and R 97 are a group , wherein A 14 and A 15 are independently of each other H, CrCi 8 alkyl, CrCi 8 alkyl which is substituted by E and/or interrupted by D, C 6 - C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 2 oheteroaryl, or C 2 -C 2 oheteroaryl which is substituted by G, and A 16 is H, CrCi 8 alkyl, d-Ci 8 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, or C 2 - C 20 heteroaryl which is substituted by G; or a polycyclic aryl group, especially pentalenyl, indenyl, azulenyl, naphthyl, biphenylenyl,
  • R 300 is Ci-C 8 alkyl, phenyl, which can be substituted by one, or more Ci-C 8 alkyl, or d-C 8 alkoxy groups
  • R 14 is hydrogen, CrC 8 alkyl, phenyl, or 1-naphthyl, , which can be substituted by one, or more CrC 8 alkyl, or C r C 8 alkoxy groups; or CrC 8 alkoxy
  • R 18 and R 19 are independently of each other CrC 8 alkyl, or cyclohexan.
  • R 82 , R 87 , R 83 , R 86 , R 83' and R 86' are independently of each other one of the above groups.
  • R 82 and R 87 , R 83 and R 86 , R 83' and R 86' can be the same or different.
  • At least one, especially two of the groups R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 , R 91 , R 92 , R 93 , R 94 , R 95 , R 96 , R 97 , R 91' , R 92' , R 93' , R 94' , R 95' , R 96' and R 97' are independently of each other a group the formula -(W 1 ) a -(W 2 ) b -W 3 (Y 1 ), wherein a and b are 0, or 1 , W 1 and W 2 are independently of each other a group of formula
  • R 46 , R 46' , R 47 and R 47' are independently of each other H, E, silyl, such as tri(Ci-C 8 alkyl)silyl, C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by G; C r Ci 8 alkyl; C r Ci 8 alkyl which is substituted by E and/or interrupted by D; C r Ci 8 alkoxy; or C r Ci 8 alkoxy which is substituted by E and/or interrupted by D; C 7 -Ci 8 aralkyl; or C 7 -Ci 8 aralkyl which is substituted by G; R 14 is H, silyl, such as tri(Ci-C 8 alkyl)silyl, Ci-d 8 alkyl; or C r Ci 8 alkyl which is substituted by E and/or interrupted by D; Ci-Ci 8 alkoxy; or Ci-Ci 8 alkoxy which is substituted by E and/or
  • R 18 and R 19 are independently of each other C r Ci 8 alkyl; CrCi 8 alkoxy, C 6 -Ci 8 aryl; C 7 -
  • Ci 8 aralkyl or R 18 and R 19 together form a ring especially a five- or six-membered ring, which can optionally be substituted by C r C 8 alkyl,
  • R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 are independently of each other H, E, C r Ci 8 alkyl; C r
  • Ci 8 alkyl which is substituted by E and/or interrupted by D C 7 -Ci 8 aralkyl; C 7 -Ci 8 aralkyl which is substituted by G; or W 3 is a group of formula
  • R and R are independently of each other a hydrogen atom, a CrCi 8 alkyl group, a d-
  • Ci 8 alkoxy group a group of formula , or wherein R 318 , R 319 and R 320 independently from each other stand for hydrogen, Ci-C 8 -alkyl, Ci-C 8 -alkoxy, or phenyl, and R stands for is a hydrogen atom, a Ci-C 25 alkyl group, which might be interrupted by -O-, a cycloalkyl group, a C 7 -Ci 8 aralkyl group, a C 6 -Ci 8 aryl group, or a heterocyclic group, which may be substituted by G; wherein
  • E is -OR 5 , -SR 5 , -NR 5 R 6 , -COR 8 , -COOR 7 , -OCOOR 7 , -CONR 5 R 6 , -CN, or halogen;
  • G is E, or CrCi 8 alkyl; wherein R 5 and R 6 are independently of each other C 6 -Ci 8 aryl; C 6 -
  • Ci 8 aryl which is substituted by Ci-d 8 alkyl, or C r Ci 8 alkoxy; C r Ci 8 alkyl, or C r Ci 8 alkyl which is interrupted by -0-; or
  • R 5 and R 6 together form a five or six membered ring, in particular
  • R 7 is C 7 -Ci 2 alkylaryl; C r Ci 8 alkyl; or C r Ci 8 alkyl which is interrupted by -0-;
  • R 8 is C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by CrCi 8 alkyl, or Ci-Ci 8 alkoxy; Ci-Ci 8 alkyl;
  • R 61 and R 62 are independently of each other C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by d-
  • Ci 8 alkyl or C r Ci 8 alkoxy; or C r Ci 8 alkyl which is interrupted by -O-, and
  • R 63 and R 64 are independently of each other H, C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by
  • W 3 is derived from a heteroaromatic group, it is preferably a group of formula
  • Examples of preferred groups W 1 and W 2 are , and wherein R 11 is hydrogen, or d-C 8 alkyl.
  • R , R and R are hydrogen, phenyl, tri(Ci-C 8 alkyl)silyl, or C r
  • R and R are independently of each other CrC 8 alkyl, or cyclohexan.
  • R 83 , R 86 and R 87 are independently of each other a group the formula -(W 1 ) a -(W 2 ) b -W 3 .
  • R 82 , R 83 , R 86 and R 87 can be different, but are preferably the same; and R 81 and R 88 are as defined above.
  • W 2 is a group wherein R ⁇ and R are independently of each other C r
  • R 82 and at least R 83 are a group of formula wherein A 14 and A 15 are independently of each other H, CrCi 8 alkyl, C 6 -C 24 aryl, or phenyl, which is substituted by one, or more CrC 8 alkyl, or Ci-C 8 alkoxy groups and the other, and R 87
  • R 86 are a group of formula , or a group of formula -(W 1 ) a -(W 2 ) b -W 3 .
  • a further preferred embodiment of the present invention is directed to compounds of formula
  • R 14 is hydrogen, phenyl, tri(C r
  • C 8 alkyl)silyl, or CrC 8 alkyl, R 18 and R 19 are independently of each other CrC 8 alkyl, or cyclohexan.
  • Particularly suitable dibenzo-, dinaphthofurans are compounds A-1 , A-2, A-4, A-5, A-10, A-11 , A-16, A-19, B-1 and B-2.
  • At least one, preferably two of the substituents R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 , R 91 , R 92 , R 93 , R 94 , R 95 , R 96 , R 97 , R 91' , R 92' , R 93' , R 94' , R 95' , R 96' and R 97' are independently of each other a group of the formula -W 1 -(W 2 ) b -W 3 (Y 2 ), wherein b is 0, or, 1 , W 1 and W 2 are as defined above and are preferably independently of each other a group of
  • W 3 is a group of formula -NR 70 R 71 , wherein R 70 and R 71 are independently of each other a
  • R are independently of each other hydrogen, CrC 8 alkyl, a hydroxyl group, a mercapto group, CrC 8 alkoxy, CrC 8 alkylthio, halogen, halo-CrC 8 alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group or a siloxanyl group, or R 70 and R 71 together with the nitrogen atom to which they are bonded form a five or six membered heterocyclic ring, such as x 1
  • R 217 independently from each other stands for hydrogen, Ci-C 8 alkyl, Ci-C 8 alkoxy, or phenyl, and
  • X 1 stands for hydrogen, or d-C 8 alkyl
  • R 75 , R 76 , R 77 and R 78 are independently of each other H, E, C 6 -Ci 8 aryl; C 6 -Ci 8 aryl which is substituted by E; Ci-Ci 8 alkyl; Ci-Ci 8 alkyl which is substituted by G and/or interrupted by D;
  • R 16' , R 17 , R 17' , R 18 , R 19 , R 30 , R 31 , R 32 and R 33 are as defined above, and R 30' , R 31' , R 32' and R 33' independently of each other have the meaning of R 30 .
  • R 70 and R 71 are independently of each other a group of formula b is preferably 1.
  • W 1 and W 2 are independently of each other a group of formula
  • W 3 is a group of formula 0
  • R7 n 1 are independently of each other a group of formula or wherein R 72 is Ci_i 8 alkyl.
  • compounds of formula Ia and Ib are preferred, wherein R 82 and R 87 and R 83 and R 86 are independently of each other a group of formula - (W 2 ) b -W 3 .
  • the groups -(W 2 ) b -W 3 can be different, but are preferably the same.
  • the present invention is directed to compounds of formula I wherein at least one of R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 is a group Y 1 and at least one of R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 is a group Y 2 .
  • compounds of formula Ia are preferred, wherein R 81 is H, R 88 is Y 2 and R 83 and R 86 are Y 1 ; or R 81 and R 88 are H 1 R 83 is Y 2 and R 86 are Y 1 .
  • the present benzofuran compounds show a high solid state fluorescence in the desired wavelength range and can be prepared according to or analogous to known procedures (see, for example, WO99/47474, WO2004039786 and WO2004077885).
  • W 3 is as defined above, can, for example, be prepared according to a process, which comprises reacting a derivative of formula
  • R 100 stands for halogen such as chloro or bromo, preferably bromo, or E having the meaning of
  • a is 2 or 3, with boron ic acid derivative E-W 3 , or - in case R 100 is not halogen - HaI-W 3 , wherein Hal stands for halogen, preferably for bromo, in the presence of an allylpalladium catalyst of the ⁇ -halo(triisopropylphosphine)( ⁇ 3 -allyl)palladium(ll) type (see for example
  • the 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, Na 2 CO 3 , K 2 CO 3 , Cs 2 CO 3 and the like, preferably an aqueous K 2 CO 3 solution is chosen.
  • an aqueous K 2 CO 3 solution is chosen.
  • the molar ratio of the base to compound III is chosen in the range of from 0.5:1 to 50:1.
  • reaction temperature is chosen in the range of from 40 to 180°C, preferably under reflux conditions.
  • 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 catalyst such as known tetrakis(triarylphosphonium)- palladium, preferably (Ph 3 P) 4 Pd and derivatives thereof.
  • Pd-based catalyst such as known tetrakis(triarylphosphonium)- palladium, preferably (Ph 3 P) 4 Pd and derivatives thereof.
  • the catalyst is added in a molar ratio from inventive DPP polymer to the catalyst in the range of from 100:1 to 10:1, preferably from 50:1 to 30:1.
  • 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.
  • the obtained inventive polymer can be isolated by well-known methods. Preferably, after cooling down the reaction mixture to room temperature, it is poured into acetone and the obtained precipitation is filtered off, washed and dried.
  • Ci-CisAlkyl is a branched or unbranched radical such as for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1- methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3- tetramethylbutyl, 1 -methyl heptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl
  • Ci-Ci 8 AIkOXy radicals are straight-chain or branched alkoxy radicals, e.g. methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy.
  • alkoxy radicals e.g. methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-a
  • C 2 -Ci 8 Alkenyl radicals are straight-chain or branched alkenyl radicals, such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2- enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
  • alkenyl radicals such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2- enyl, n-oct-2-enyl, n-
  • C 2-24 Alkynyl is straight-chain or branched and preferably C 2-8 alkynyl, which may be unsubstituted or substituted, such as, for example, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1 -yl, trans-3-methyl-2-penten-4-yn-1 -yl, 1 ,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-tetracosyn-24-yl.
  • C 4 -Ci ⁇ cycloalkyl is preferably C 5 -Ci 2 cycloalkyl, such as, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclododecyl. Cyclohexyl and cyclododecyl are most preferred.
  • aryl group is typically C 6 -C 3 oaryl, such as phenyl, indenyl, azulenyl, naphthyl, biphenyl, terphenylyl or quadphenylyl, as-indacenyl, s-indacenyl, acenaphthylenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl, naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, or anthracenyl, preferably phenyl, 1 -naphthyl, 2-naphthyl, 9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may be unsubstituted or substituted.
  • C 6 -Ci 8 aryl examples include phenyl, 1 -naphthyl, 2-naphthyl, 3- or 4-biphenyl, 9-phenanthryl, 2- or 9-fluorenyl, which may be unsubstituted or substituted.
  • C 7 -C 24 aralkyl radicals are preferably C 7 -d 8 aralkyl radicals, which may be substituted, such as, for example, benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, ⁇ -phenyl-butyl, ⁇ , ⁇ -dimethyl- ⁇ -phenyl-butyl, ⁇ -phenyl-dodecyl, ⁇ -phenyl-octadecyl, ⁇ -phenyl-eicosyl or ⁇ -phenyl-docosyl, preferably C 7 -Ci 8 aralkyl such as benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, ⁇ -phenyl-butyl, ⁇ , ⁇ -dimethyl- ⁇ -phenyl-butyl, ⁇ -phen
  • C 7 -Ci 2 alkylaryl is, for example, a phenyl group substituted with one, two or three d-C 6 alkyl groups, such as, for example, 2-, 3-, or 4-methylphenyl, 2-, 3-, or 4-ethyl phenyl, 3-, or 4- isopropylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, or 3,4,5-trimethylphenyl.
  • heteroaryl group is a ring, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically an unsaturated heterocyclic radical with five to 18 atoms having at least six conjugated ⁇ -electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, 2H-chromenyl, xanthenyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, 1 H-pyrrolizinyl, isoindolyl, pyridazinyl, indoli
  • Halogen is fluorine, chlorine, bromine and iodine.
  • haloalkyl mean groups given by partially or wholly substituting the above-mentioned alkyl group, with halogen, such as trifluoromethyl etc.
  • aldehyde group, ketone group, ester group, carbamoyl group and amino group include those substituted by an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group, wherein the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the heterocyclic group may be unsubstituted or substituted.
  • sil group means a group of formula -SiR 62 R 63 R 64 , wherein R 62 , R 63 and R 64 are independently of each other a C r C 8 alkyl group, in particular a C r C 4 alkyl group, a C 6 -C 24 aryl group or a C 7 -Ci 2 aralkylgroup, such as a trimethylsilyl group.
  • siloxanyl group means a group of formula -0-SiR 62 R 63 R 64 , wherein R 62 , R 63 and R 64 are as defined above, such as a trimethylsiloxanyl group.
  • Possible substituents of the above-mentioned groups are Ci-C 8 alkyl, a hydroxyl group, a mercapto group, CrC 8 alkoxy, CrC 8 alkylthio, halogen, halo-CrC 8 alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group or a silyl group.
  • radicals may be substituted by E and/or, if desired, interrupted by D.
  • Interruptions are of course possible only in the case of radicals containing at least 2 carbon atoms connected to one another by single bonds; C 6 -Ci 8 aryl is not interrupted; interrupted arylalkyl or alkylaryl contains the unit D in the alkyl moiety, d- Ci 8 alkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (CH 2 CH 2 O) n -R", where n' is a number from the range 1-9 and R x is H or Ci-Ci O alkyl or C 2 -Ci 0 alkanoyl (e.g.
  • R y is C r Ci 8 alkyl, C 5 -Ci 2 cycloalkyl, phenyl, C 7 -Ci 5 phenylalkyl, and R yi embraces the same definitions as R y or is H; CrC 8 alkylene-COO-R z , e.g.
  • the electroluminescent devices may be employed for full color display panels in, for example, mobile phones, televisions and personal computer screens.
  • electroluminescent devices of the present invention are otherwise designed as is known in the art, for example as described in U.S. Pat. Nos. 5,518,824, 6,225,467, 6,280,859, 5,629,389, 5,486,406, 5,104,740, 5,116,708 and 6,057,048, the relevant disclosures of which are hereby incorporated by reference.
  • organic EL devices contain one or more layers such as: substrate; base electrode; hole-injecting layer; hole transporting layer; emitter layer; electron- transporting layer; electron-injecting layer; top electrode; contacts and encapsulation.
  • This structure is a general case and may have additional layers or may be simplified by omitting layers so that one layer performs a plurality of tasks.
  • the simplest organic EL device consists of two electrodes which sandwich an organic layer that performs all functions, including the function of light emission.
  • a preferred EL device comprises in this order:
  • the benzofuran compounds of the present invention can, in principal be used for any organic layer, such as, for example, hole transporting layer, light emitting layer, or electron transporting layer, but are preferably used as the light emitting material in the light emitting layer, optionally as a host or guest component, or electron transporting layer.
  • organic layer such as, for example, hole transporting layer, light emitting layer, or electron transporting layer, but are preferably used as the light emitting material in the light emitting layer, optionally as a host or guest component, or electron transporting layer.
  • the present organic compounds function as light emitters and are contained in the light emission layer or form the light-emitting layer.
  • the light emitting compounds of this invention exhibit intense fluorescence in the solid state and have excellent electric-field-applied light emission characteristics. Further, the light emitting compounds of this invention are excellent in the injection of holes from a metal electrode and the transportation of holes; as well as being excellent in the injection of electrons from a metal electrode and the transportation of electrons. They are effectively used as light emitting materials and may be used in combination with other hole transporting materials, other electron transporting materials or other dopants.
  • the organic compounds of the present invention form uniform thin films.
  • the light emitting layers may therefore be formed of the present organic compounds alone.
  • the light-emitting layer may contain a known light-emitting material, a known dopant, a known hole transporting material or a known electron transporting material as required.
  • a decrease in the brightness and life caused by quenching can be prevented by forming it as a multi-layered structure.
  • the light-emitting material, a dopant, a hole-injecting material and an electron-injecting material may be used in combination as required. Further, a dopant can improve the light emission brightness and the light emission efficiency, and can attain the red or blue light emission.
  • each of the hole transporting zone, the light-emitting layer and the electron transporting zone may have the layer structure of at least two layers.
  • a layer to which holes are injected from an electrode is called “hole-injecting layer”
  • a layer which receives holes from the hole-injecting layer and transport the holes to a light-emitting layer is called “hole transporting layer”.
  • a layer to which electrons are injected from an electrode is called “electron-injecting layer”
  • a layer which receives electrons from the electron-injecting layer and transports the electrons to a light-emitting layer is called “electron transporting layer”.
  • the light-emitting material or the dopant which may be used in the light-emitting layer together with the organic compounds of the present invention includes for example anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloper ⁇ lene, naphthaloper ⁇ lene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarine, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinyl anthracene
  • the compounds of the present invention with phosphorescent materials as a dopant in the light-emitting layer.
  • phosphorescent materials are, for example, metal complexes of Ir, Pt, Eu, Ru, Rh, Pd, Ag, Re, Os and Au and are described, for example, in JP2005-11804 and WO2004/034751.
  • the electroluminescent device may comprise in this order (a) an anode, such as, for example, ITO, (b1) a hole injecting layer, such as, for example, CuPc,
  • a hole transporting layer such as, for example, such as, for example, N 1 N'- Di(naphthalene-1-yl)-N,N'-diphenyl-benzidine (NPD), or TCTA,
  • a light-emitting layer comprising a phosphorescent compound and a dibenzofuran compound of the present invention, especially a compound A-1 to A-66, B-1 to B-18, C-1 and C-2.
  • a positive hole inhibiting layer such as, for example, BCP, or BAIq
  • an electron transporting layer such as, for example, AIq 3
  • an inorganic compound layer such as, for example, LiF
  • a cathode such as, for example, Al.
  • dibenzofuran compounds of the present invention are used as host together with guest compounds, such, as for example, 2,5,8,11-tetra-t-butylperylene (Jiaumin Shi Ching W. Tang, Appl. Phys. Lett. 80, 3201 (2002), or the compounds, described, for example, in
  • the electroluminescent device may comprise in this order
  • an anode such as, for example, ITO
  • a hole injecting layer such as, for example, CuPc
  • a hole transporting layer such as, for example, NPD, or TCTA
  • a light-emitting layer comprising a fluorescent guest compound and a dibenzofuran host compound of the present invention, especially a compound A-1 to A-66, B-1 to B-18, C-1 and C-2, optionally a positive hole inhibiting layer, such as, for example, BCP,
  • an electron transporting layer such as, for example, AIq 3 , or TPBI
  • an inorganic compound layer such as, for example, LiF
  • a cathode such as, for example, Al.
  • the weight ratio of compound of the formula I to the dopant in general 50:50 to 99.99:0.01, preferably 90:10 to 99.99:0.01 , more preferably 95:5 to 99.9:0.1. If the guest is a phosphorescent compound, its concentration is normally 5-10%.
  • the present invention also relates to compositions comprising a compound of the present invention.
  • the compounds of the present invention and the above compound or compounds that can be used in a light-emitting layer may be used in any mixing ratio for forming a light-emitting layer. That is, the organic compounds of the present invention may provide a main component for forming a light-emitting layer, or they may be a doping material in another main material, depending upon a combination of the above compounds with the organic compounds of the present invention.
  • the hole-injecting material is selected from compounds which are capable of transporting holes, are capable of receiving holes from the anode, have an excellent effect of injecting holes to a light-emitting layer or a light-emitting material, prevent the movement of excitons generated in a light-emitting layer to an electron-injecting zone or an electron-injecting material and have the excellent capability of forming a thin film.
  • Suitable hole-injecting materials include for example a phthalocyanine derivative, a naphthalocyanine derivative, a porphyrin derivative, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolthione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, polyarylalkane, stilbene, butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, derivatives of these, and polymer materials such as polyvinylcarbazole, polysilane and an electroconducting polymer.
  • the hole-injecting material which is more effective is an aromatic tertiary amine derivative or a phthalocyanine derivative.
  • the tertiary amine derivative include triphenylamine, tritolylamine, tolyldiphenylamine, N.N'-diphenyl-N.N'- ⁇ -methylphenylJ-i.i-biphenyl- ⁇ 1 - diamine, N,N,N l ,N l -tetra(4-methylphenyl)-1 ,1 l -phenyl-4,4 l -diamine, N,N,N',N 1 -tetra(4- methylphenylj-i .i'-biphenyl ⁇ '-diamine, N,N l -diphenyl-N,N l -di(1-naphthyl)-1 ,1'-biphenyl-
  • phthalocyanine (Pc) derivative examples include phthalocyanine derivatives or naphthalocyanine derivatives such as H 2 Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, CIAIPc, CIGaPc, CIInPc, CISnPc, CI 2 SiPc, (HO)AIPc, (HO)GaPc, VOPc, TiOPc, MoOPc, and GaPc-O-GaPc.
  • phthalocyanine (Pc) derivative examples include phthalocyanine derivatives or naphthalocyanine derivatives such as H 2 Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, CIAIPc, CIGaPc, CIInPc, CISnPc, CI 2 SiPc, (HO)AIPc, (HO)GaPc, VOPc,
  • the hole transporting layer can reduce the driving voltage of the device and improve the confinement of the injected charge recombination within the light emitting layer, comprising the compounds of the present invention.
  • Any conventional suitable aromatic amine hole transporting material described for the hole-injecting layer may be selected for forming this layer.
  • a preferred class of hole transporting materials is comprised of 4,4'-bis(9-carbazolyl)-1 ,1 1 - biphenyl compounds of the formula wherein R 61 and R 62 is a hydrogen atom or an d-C 3 alkyl group; R 63 through R 66 are substituents independently selected from the group consisting of hydrogen, a d-C 6 alkyl group, a C r C 6 alkoxy group, a halogen atom, a dialkylamino group, a C 6 -C 30 aryl group, and the like.
  • 4,4'-bis(9-carbazolyl)-1 ,1 l -biphenyl compounds include 4,4'- bis(9-carbazolyl)-1 ,1'-biphenyl and 4,4 l -bis(3-methyl-9-carbazolyl)-1 ,1 l -biphenyl J and the like; or 4,4',4"-tri-(N-carbazoyl)triphenylamine (TCTA).
  • polymeric material can be used as a hole injection material and a hole transporting material, such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4- styrenesulfonate), also called PEDOT/PSS.
  • PVK poly(N-vinylcarbazole)
  • polythiophenes polypyrrole
  • polyaniline polyaniline
  • copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4- styrenesulfonate), also called PEDOT/PSS.
  • the electron transporting layer is not necessarily required for the present device, but is optionally and preferably used for the primary purpose of improving the electron injection characteristics of the EL devices and the emission uniformity.
  • Illustrative examples of electron transporting compounds, which can be utilized in this layer include the metal chelates of 8-hydroxyquinoline as disclosed in U.S. Pat. Nos. 4,539,507, 5,151 ,629, and 5,150,006, the disclosures of which are totally incorporated herein by reference.
  • Suitable electron transporting materials are metal complex compounds and nitrogen-containing five-membered ring derivatives.
  • the metal complex compound examples include lithium 8-hydroxyquinolinate, zinc bis(8-hydroxyquinolinate), copper bis(8- hydroxyquinolinate), manganese bis(8-hydroxyquinolinate), aluminum tris(8- hydroxyquinolinate), aluminum tris(2-methyl-8-hydroxyquinolinate), gallium tris(8- hydroxyquinolinate), beryllium bis(10-hydroxybenzo[h]quinolinate), zinc bis(10- hydroxybenzo[h]quinolinate), chlorogallium bis(2-methyl-8-quinolinate), gallium bis(2-methyl- 8-quinolinate)(o-cresolate), aluminum bis(2-methyl-8-quinolinate)(1-naphtholate), gallium bis(2-methyl-8-quinolinate)(2-naphtholate), gallium bis(2-methyl-8-quinolinate)phenolate, zinc bis(o-(2-benzooxazolyl)phenolate), zinc bis(o-(2-benzothiazolyl)phenolate) and
  • the nitrogen-containing five-membered derivative is preferably an oxazole, thiazole, thiadiazole, or triazole derivative.
  • specific examples of the above nitrogen-containing five-membered derivative include 2,5-bis(1- phenyl)-1 ,3,4-oxazole, 1 ,4-bis(2-(4-methyl-5-phenyloxazolyl)benzene, 2,5-bis(1 -phenyl)- 1 J 3 J 4-thiazole J 2 J 5-bis(1-phenyl)-1 J 3 J 4-oxadiazole J 2-(4 l -tert-butylphenyl)-5-(4"-biphenyl)1,3 J 4- oxadiazole, 2,5-bis(1-naphthyl)-1 ,3,4-oxadiazole, 1 ,4-bis[2-(5-phenyloxadiazolyl)]benzene, 1 ,4-bis[2-(5-phenyloxadiazolyl
  • oxadiazole metal chelates such as bis[2-(2-hydroxyphenyl)-5-phenyl-1,3,4- oxadiazolato]zinc; bis[2-(2-hydroxyphenyl)-5-phenyl-1 ,3,4-oxadiazolato]beryllium; bis[2-(2- hydroxyphenyl)-5-(1 -naphthyl)-1 ,3,4-oxadiazolato]zinc; bis[2-(2-hydroxyphenyl)-5-(1 - naphthyl)-1 ,3,4-oxadiazolato]beryllium; bis[5-biphenyl-2-(2-hydroxyphenyl)-1 ,3,4- oxadiazolato]zinc; bis[5-biphenyl-2-(2-hydroxyphenyl)-1 ,3,4-oxadiazolato]beryllium; bis(2- hydroxyphenyl)-5-phenyl-1 ,3,4-oxadiazolato
  • hetero-cyclic compounds such as benzimidazole derivatives, benzoxazole derivatives, oxadiazole derivatives, thiadiazole derivative, triazole derivatives, pyrazine derivatives, phenanthroline derivatives, quinoxaline derivatives, quinoline derivatives, benzoquinoline derivatives, oligo-pyridine derivatives, e.g. bipyridine derivatives and terpyridine derivatives, naphthylidine derivatives, indole derivatives and naphthalimide derivatives; silole derivatives; and phosphineoxide derivatives.
  • hetero-cyclic compounds such as benzimidazole derivatives, benzoxazole derivatives, oxadiazole derivatives, thiadiazole derivative, triazole derivatives, pyrazine derivatives, phenanthroline derivatives, quinoxaline derivatives, quinoline derivatives, benzoquinoline derivatives, oligo-pyridine derivatives, e.g. bipyridine derivative
  • the property of charge injection can be improved by adding an electron-accepting compound to the hole injection layer and/or the hole transporting layer and electron-donating material to the electron transporting layer.
  • the reducing dopant is a material that can reduce the electron transporting material.
  • examples of the reducing dopant are alkaline metals, e.g. Na, K, Rb and Cs, and alkaline earth metals, e.g. Ca, Sr, and Ba.
  • the organic EL device of the present invention may comprise an inorganic compound layer between at least one of the electrodes and the above organic thin layer.
  • the inorganic compound used for the inorganic compound layer include various types of oxides, nitrides and oxide nitrides such as alkali metal oxides, alkaline earth metal oxides, rare earth oxides, alkali metal halides, alkaline earth metal halides, rare earth halides, SiO x , AIO x , SiN x , SiON, AION, GeO x , LiO x , LiON, TiO x , TiON, TaO x , TaON, TaN x and C.
  • SiO x , AIO x , SiN x , SiON, AION, GeO x and C are preferred since a suitable interface layer of injection is formed.
  • the light-emitting layer may contain, in addition to the light-emitting organic material of the present invention, at least one of other light-emitting material, other dopant, other hole-injecting material and other electron-injecting material.
  • a protective layer may be formed on the surface of the device, or the device as a whole may be sealed with a silicone oil, or the like.
  • the electrically conductive material used for the anode of the organic EL device is suitably selected from those materials having a work function of greater than 4 eV.
  • the electrically conductive material includes carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, alloys of these, metal oxides such as tin oxide and indium oxide used for ITO substrates or NESA substrates, and organic electroconducting polymers, such as polythiophene and poly pyrrole.
  • the electrically conductive material used for the cathode is suitably selected from those having a work function of smaller than 4 eV.
  • the electrically conductive material includes magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum and alloys of these, while the electrically conductive material shall not be limited to these.
  • the alloys include magnesium/silver, magnesium/indium and lithium/aluminum, while the alloys shall not be limited to these.
  • Each of the anode and the cathode may have a layer structure formed of two layers or more as required.
  • the electrodes are desirably sufficiently transparent in the light emission wavelength region of the device.
  • the substrate is desirably transparent as well.
  • the transparent electrode is produced from the above electrically conductive material by a deposition method or a sputtering method such that a predetermined light transmittance is secured.
  • the electrode on the light emission surface side has for instance a light transmittance of at least 10%.
  • the substrate is not specially limited so long as it has adequate mechanical and thermal strength and has transparency. For example, it is selected from glass substrates and substrates of transparent resins such as a polyethylene substrate, a polyethylene terephthalate substrate, a polyether sulfone substrate and a polypropylene substrate.
  • each layer can be formed by any one of dry film forming methods such as a vacuum deposition method, a sputtering method, a plasma method and an ion plating method and wet film forming methods such as a spin coating method, a dipping method and a flow coating method.
  • dry film forming methods such as a vacuum deposition method, a sputtering method, a plasma method and an ion plating method
  • wet film forming methods such as a spin coating method, a dipping method and a flow coating method.
  • the thickness of each layer is not specially limited, while each layer is required to have a proper thickness. When the layer thickness is too large, inefficiently, a high voltage is required to achieve predetermined emission of light. When the layer thickness is too small, the layer is liable to have a pinhole, etc., so that sufficient light emission brightness is hard to obtain when an electric field is applied.
  • the thickness of each layer is for example in the range of from about 5 nm to about 10 ⁇ m, for
  • a material for forming an intended layer is dissolved or dispersed in a proper solvent, such as toluene, ethanol, chloroform, tetrahydrofuran and dioxane, and a thin film is formed from the solution or dispersion.
  • a proper solvent such as toluene, ethanol, chloroform, tetrahydrofuran and dioxane
  • the solvent shall not be limited to the above solvents.
  • the above solution or dispersion for forming the layer may contain a proper resin and a proper additive.
  • the resin that can be used includes insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate and cellulose, copolymers of these, photoconductive resins such as poly-N-vinylcarbozole and polysilane, and electroconducting polymers such as polythiophene and polypyrrole.
  • the above additive includes an antioxidant, an ultraviolet absorbent and a plasticizer.
  • an organic EL device When the light-emitting organic material of the present invention is used in a light-emitting layer of an organic EL device, an organic EL device can be improved in organic EL device characteristics such as light emission efficiency and maximum light emission brightness. Further, the organic EL device of the present invention is remarkably stable against heat and electric current and gives a usable light emission brightness at a low actuation voltage. The problematic deterioration of conventional devices can be remarkably decreased.
  • the organic EL device of the present invention has significant industrial values since it can be adapted for a flat panel display of an on-wall television set, a flat light-emitting device, a light source for a copying machine or a printer, a light source for a liquid crystal display or counter, a display signboard, lighting application and a signal light.
  • the material of the present invention can be used in the fields of an organic EL device, an electrophotographic photoreceptor, a photoelectric converter, a solar cell, and an image sensor.
  • Tetrethylamine hydroxide (13.6 g, 18.4 mmol), tetrakis(triphenylphosphine)palladium(0) (142 mg) and trans-2-phenylvinylboronic acid (2.3 g, 15.3 mmol) are added to a solution of the product from example 1a) (2.00 g, 6.14 mmol) in N,N'-Dimethylacetamide (DMA) (30 ml). The mixture is then stirred at 110 0 C for 24 hours. The reaction mixture is cooled to room temperature and poured into H 2 O. A gray crude product is obtained after filtration and washing with n-hexane. The crude product is purified by silicagel column chromatography with CH 2 CI 2 , which result in a white solid (71% yield, mp.: 226°C).
  • Bromine (3.02 g, 18.9 mmol) is added at 0 0 C to a solution of 2,6-di-tert-butylanthracene (5.0 g, 17.2 mol) in carbontetrachloride (200 ml). The mixture is then stirred at 0°C for 15 hours.
  • step 15d) 4-(2, 6-Di-tert-butyl-10-naphthalen-2-yl-anthracen-9-yl)-dibenzofuran (A-35) is prepared in the same manner as described in example 2b) using the compound obtained in step 15c) and 2-(4, 4, 5, 5-tetramethyl-1 ,3,2-dioxaboran-2-yl) naphthalene as starting materials.
  • Example 15 is repeated except using 1-(4,4,5,5-tetramethyl-1 ,3,2-dioxaboran-2-yl) pyrene in the last step.
  • 6-Bromo-2-iodo-dibenzofuran is prepared in the same manner as described in example 11b), except using 4-bromodibenzofurane as a starting material.
  • 6-Bromo-2-pyren-1-yl-dibenzofuran is prepared in the same manner as described in example
  • A-58 is prepared in analogy to A-17 using the appropriate educts.
  • A-59 is prepared in analogy to A-58 using the appropriate educts.
  • A-60 is prepared in analogy to A-17 using the appropriate educts.
  • A-61 is prepared in analogy to A-58 using the appropriate educts.
  • Compounds A-1, B-1, C-1, C-2, A-9, A-10 and A-7, respectively are deposited under vacuum on a glass plate in a thickness of 60 nm. Fluorescence spectra of the deposited films are measured by fluorescence spectrophotometer (F-4500, HITACHI). The emission ⁇ max is shown below.
  • the following device structure is prepared: ITO/CuPCfTCTA/ Compound B-1 /TPBI/LiF/AI where ITO is indium tin oxide, CuPC is copper phthalocyanine, TCTA is 4,4',4"-tri-(N- carbazoyl)triphenylamine and TPBI is 1,3,5-tris-(N-phenyl-benzimidazol-2-yl)benzene.
  • ITO indium tin oxide
  • CuPC copper phthalocyanine
  • TCTA 4,4',4"-tri-(N- carbazoyl)triphenylamine
  • TPBI 1,3,5-tris-(N-phenyl-benzimidazol-2-yl)benzene.
  • a brightness of 50 cd/m 2 is observed at 100 mA/cm 2 .
  • the following device structure is prepared: ITO/CuPCfTCTA/ Compound B-1 + Compound G-1 (1.1 % by weight)/TPBI/LiF/AI. Using this device structure, a brightness of 500 cd/m 2 is observed at 100 mA/cm 2 .
  • the following device structure is prepared: ITO/CuPCfTCTA/ Compound C-2 /TPBI/LiF/AI. Using this device structure, a brightness of 120 cd/m 2 is observed at 100 mA/cm 2 .
  • Application Example 5
  • the following device structure is prepared: ITO/CuPCfTCTA/ Compound C-2 + Compound G-1 (1.9 % by weight)/TPBI/LiF/AI. Using this device structure, a brightness of 70 cd/m 2 is observed at 100 mA/cm 2 .
  • the following device structure is prepared: ITO/CuPC/NPD/ Compound B-1 /TPBI/LiF/AI where NPD is N,N'-Di(naphthalene-1-yl)-N,N'-diphenyl-benzidine. Using this device structure, a brightness of 370 cd/m 2 is observed at 100 mA/cm2.
  • the following device structure is prepared: ITO/CuPC/NPD/ Compound B-1 + TBPe (1.4%) /TPBI/LiF/AI where TPBe is 2,5,8,11-tetra-t-butylperylene. Using this device structure, a brightness of 680 cd/m 2 is observed at 88 mA/cm 2 .
  • the following device structure is prepared: ITO/CuPC/NPD/ Compound A-10 /TPBI/LiF/AI. Using this device structure, a brightness of 3,800 cd/m 2 is observed at 111 mA/cm2.
  • the following device structure is prepared: ITO/CuPC/NPD/ Compound A-10 + TBPe (1.5%) /TPBI/LiF/AI. Using this device structure, a brightness of 2,030 cd/m 2 is observed at 90 mA/cm 2 .
  • the following device structure is prepared: ITO / CuPC / NPD / Emitting layer (dibenzofuran of the present invention as a host + TBPe as a guest) / TPBI / LiF / Al. Using this device structure, bright blue EL emission is observed.
  • the EL properties of the devices are summarized in Table 1.
  • the following device structure is prepared: ITO / CuPC / NPD / Emitting layer (dibenzofuran of the present invention as a host + dibenzofuran of the present invention as a guest) / TPBI / LiF / Al. Using this device structure, bright blue EL emission is observed.
  • the EL properties of the device is summarized in Table 2.

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Abstract

Disclosed are electroluminescent devices that comprise organic layers that contain dibenzofuran compounds. The compounds are suitable components of, for example, blue-emitting, durable, organo-electroluminescent layers. The electroluminescent devices may be employed for full color display panels in, for example, mobile phones, televisions and personal computer screens.

Description

Electroluminescent Device
The present invention relates to electroluminescent devices that comprise organic layers that contain dibenzofuran compounds. The compounds are suitable components of, for example, blue-emitting, durable, organo-electroluminescent layers. The electroluminescent devices may be employed for full color display panels in, for example, mobile phones, televisions and personal computer screens.
H. O. Wirth et al., Die Makromolekulare Chemie 86 (1965) 139 - 167 describes the synthesis and properties of oxydo-p-oligophenylenes. The following two dibenzofuran compounds are described therein:
Figure imgf000002_0001
JP9151182 discloses dibenzofurandiamine derivatives, which are suitable as a positive hole transporting agent, etc., in electrophotographic photoreceptor, solar cell, electroluminescence element etc. The dibenzofurandiamine derivatives are represented by the following formula
Figure imgf000003_0001
wherein R1 to R5 are each a halogen, a (substituted)alkyl, a (substituted)alkoxy, a (substituted)aryl or (substituted)aralkyl; (a), (b), (c) and (d) are each 0-5; (e) is 0-6. The following compounds are explicitly disclosed in JP9151182:
Figure imgf000003_0002
JP2004311404 discloses compounds having at least one biaryl part structure for use in OLED application. The dimeric dibenzofuran compound shown below is explicitly mentioned.
Figure imgf000004_0001
WO03105538 relates to benzotriazole compounds and their use in OLED application. The dimeric benzotriazole compound shown below is explicitly mentioned.
Figure imgf000004_0002
The compounds shown below are also known:
Figure imgf000004_0003
(J. Chem. Soc. (1962) 5291, (J. Chem. Soc.
Figure imgf000004_0004
(1962) 5291, (J. Org. Chem. 46 (1981) 851-855),
Figure imgf000004_0005
(Bull. Chem. Soc. Japan 9 (1934) 55), and
Figure imgf000004_0006
(Bull. Chem. Soc. Japan 9 (1934) 55). Surprisingly, it was found that luminescent devices, which are high durability besides high in the efficiency of electrical energy utilisation and high in luminance, can be obtained if specific benzofuran compounds are used, especially as light emitting substances.
Accordingly, the present invention relates to compounds of the formula
Figure imgf000005_0001
(I), or (II), wherein
R 81 D82 r>83 D84 D85 D86 D87 D88 D91 D92 D93 D94 D95 D96 D97 D91' D92' D93' D94' D95'
R96' and R97' are independently of each other H, -OR201, -SR202 and/or -NR203R204, Ci-C24alkyl; Ci-C24alkyl, which is substituted by E and/or interrupted by D; C2-Ci 8alkenyl, C2-Ci8alkenyl, which is substituted by E, C3-C8cycloalkyl, C3-C8cycloalkyl, which is substituted by G, aryl, aryl, which is substituted by G, heteroaryl, or heteroaryl, which is substituted by G, silyl, -≡- SiR62R63R64, -CN, cyclic ether, -B(OR65)2 and/or halogen, especially fluorine, or R81 and R82, R82 and R83, R83 and R84, R85 and R86, R86 and R87, R87 and R88, R97 and R96, R96 and R95, R95 and R94, R97' and R96', R96' and R95', R95' and/or R94', and/or two of the groups R91, R92 and R93 or R91 , R92 and R93 , which are in neighbourhood to each other, together form a
group
Figure imgf000005_0002
, wherein A41, A~ A4J, A44, A4S, A4b and A v 447' are independently of each other H1 halogen, hydroxy, CrC24alkyl, CrC24alkyl which is substituted by E and/or interrupted by D, Ci-C24perfluoroalkyl, C5-Ci2cycloalkyl, C5-Ci2cycloalkyl which is substituted by G and/or interrupted by S-, -O-, or -NR5-, C5-C12cycloalkoxy, C5- Ci2cycloalkoxy which is substituted by E, C6-C24aryl, C6-C24aryl which is substituted by G, C2- C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2-C24alkenyl, C2-C24alkynyl, d- C24alkoxy, CrC24alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, C7- C25aralkyl, which is substituted by G, C7-C25aralkoxy, C7-C25aralkoxy which is substituted by E, or -CO-R8,
M is a bonding group, such as a single (direct) bond, -CO-, -COO-; -S-; -SO-; -SO2-; -0-; C1- Ci2alkylene, C2-Ci2alkenylene, or C2-Ci2alkinylene, which are optionally interrupted by one or more -0-, or -S-; or a group [M1Jn, wherein n is an integer 1 to 20, M1 is arylene, or heteroarylene, which is optionally substituted by G, especially naphthylene, biphenylene, styrylene, anthrylene, or pyrenylene, which are optionally substituted by CrCi2alkyl, halogen, -OR201, -SR202 and/or -NR203R204, wherein R201 is hydrogen, Ci-C24alkyl, Ci-C24alkyl, which is substituted by E and/or interrupted by D; C2-Ci2alkenyl, C3-C6alkenoyl, C3-C8cycloalkyl, or benzoyl, each of which may optionally be substituted by one or more groups Ci-C6alkyl, halogen, -OH and/or d-C4alkoxy; C6-Ci4aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, each of which may optionally be substituted by halogen, -OH, CrCi2alkyl, CrCi2alkoxy, phenoxy, CrCi2alkylsulfanyl, phenylsulfanyl, -N(Ci-Ci2alkyl)2 and/or diphenylamino;
R202 is Ci-C24alkyl, Ci-C24alkyl, which is substituted by E and/or interrupted by D; C2- Ci2alkenyl, CrC8alkanoyl, C2-Ci2alkenyl, C3-C6alkenoyl; C3-C8cycloalkyl, or benzoyl, each of which may optionally be substituted by one or more groups CrC6alkyl, halogen, -OH, Cr C4alkoxy or CrC4alkylsulfanyl; C6-Ci4aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, each of which may optionally be substituted by halogen, CrCi2alkyl, CrCi2alkoxy, phenyl-CrC3alkyloxy, phenoxy, CrCi2alkylsulfanyl, phenylsulfanyl, -N(Ci-Ci2alkyl)2, diphenylamino, -(CO)O(CrC8alkyl), -(CO)-Ci -C8alkyl, or (CO)N(CrC8alkyl)2; R203 and R204 are independently of each other hydrogen, CrC24alkyl, CrC24alkyl, which is substituted by E and/or interrupted by D; C2-C5alkenyl, C3-C8cycloalkyl, or benzoyl, each of which may optionally be substituted by one or more groups CrC6alkyl, halogen, -OH, or Cr C4alkoxy; phenyl-CrC3alkyl, CrC8alkanoyl, C3-Ci2alkenoyl, C6-Ci4aryl, especially phenyl naphthyl, phenanthryl anthranyl, or pyrenyl, each of which is optionally substituted by Cr Ci2alkyl, benzoyl or Ci-Ci2alkoxy; or R203 and R204 together are C2-C8alkylene, or branched C2-C8alkylene optionally interrupted by -0-, -S-, or -NR205- and/or optionally substituted by hydroxyl, CrC4alkoxy, C2-C4alkanoyloxy, or benzoyloxy, wherein the ring formed by R203 and R204 can optionally be condensed one or two times by phenyl which can be substituted one to three times with CrC8-alkyl, CrC8-alkoxy, halogen, or cyano;
R205 is hydrogen, CrC24alkyl, CrC24alkyl, which is substituted by E and/or interrupted by D; C2-C5alkenyl, C3-C8cycloalkyl, phenyl-CrC3alkyl, CrC8alkanoyl, C3-Ci2alkenoyl, C6-Ci4aryl, especially benzoyl; phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, each of which is optionally substituted by CrCi2alkyl, benzoyl, or Ci-Ci2alkoxy;
D is -CO-, -COO-, -OCOO-, -S-, -SO-, -SO2-, -0-, -NR5-, -SiR61R62-, -POR5-, -CR63=CR64-, or -C≡C-;
E is halogen, C6-Ci4aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, which may be substituted by -OR5, -SR5, -NR5R6, ^SiR62R63R64, wherein R62, R63 and R64 are independently of each other a Ci-C8alkyl group, a C6-C24aryl group or a C7- Ci2aralkylgroup, -CN, cyclic ether and/or -B(OR65J2, wherein R65 is hydrogen, CrC24alkyl, C3- C8cycloalkyl, C7-C24aralkyl, C2-Ci8alkenyl, C2-C24alkynyl, hydroxy, mercapto, CrC24alkoxy, CrC24alkylthio, C6-C30aryl, C2-C30heteroaryl, halogen, especially fluorine, haloalkane, silyl, siloxanyl, and an alicyclic ring formed with adjacent substituents R65; -OR5, -SR5, -NR5R6, -COR8, -COOR7, -CONR5R6, -CN, halogen, silyl, d-dβalkyl, or heteroaryl,
G is E, or CrCi8alkyl, wherein R5 and R6 are independently of each other H, C6-Ci8aryl; C6- Ci8aryl which is substituted by CrCi8alkyl, CrCi8alkoxy, or silyl; Ci-d8alkyl or CrCi8alkyl which is interrupted by -O-; or
R5 and R6 together form a five or six membered ring, in particular
Figure imgf000007_0001
or
Figure imgf000007_0002
R7 is H, C6-Ci8aryl, C7-Ci2alkylaryl, which are optionally substituted by CrCi8alkyl, or d-
Ci8alkoxy; d-Ci8alkyl; or CrCi8alkyl which is interrupted by -O-;
R8 is C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ci8alkyl, or Ci-Ci8alkoxy; Ci-Ci8alkyl,
C7-Ci2alkylaryl, or CrCi8alkyl which is interrupted by -O-;
R61 and R62 are independently of each other C6-Ci8aryl; C6-Ci8aryl which is substituted by d-
Ci8alkyl, Ci-Ci8alkoxy; or Ci-Ci8alkyl which is interrupted by -O-, and
R63 and R64 are independently of each other H, C6-Ci8aryl; C6-Ci8aryl which is substituted by
Ci-Ci8alkyl, Ci-Ci8alkoxy; or Ci-Ci8alkyl which is interrupted by -O-; with the proviso that at least one of R81, R82, R83, R84, R85, R86, R87 and R88 is different from H, -OR201, -SR202 and C1-
C24alkyl; and the further proviso that the following compounds are excluded:
Figure imgf000007_0003
Figure imgf000008_0001
Figure imgf000009_0001
Preferably, the compound or compounds of the present invention emit light below about 520 nm, in particular between about 380 nm and about 520 nm.
The compound or compounds of the present invention have especially a NTSC coordinate of between about (0.12, 0.05) and about (0.16, 0.10), very especially a NTSC coordinate of about (0.14, 0.08).
The compound or compounds of the present invention have a melting point above about 15O0C, preferably above about 2000C and most preferred above about 25O0C.
To obtain organic layers of this invention with the proper T9, or glass transition temperature, it is advantageous that the present organic compounds have a glass transition temperature greater than about 100°C, for example greater than about 110°C, for example greater than about 1200C, for instance greater than about 1300C. In one embodiment of the present invention compounds of formula I, or Il are preferred, wherein at least one of the groups R81, R82, R83, R84, R85, R86, R87, R88, R91, R92, R93, R94, R95, R96, R97, R91', R92', R93', R94', R95', R96' and R97' is a C7-C30aryl group, especially a polycyclic C8-C30aryl group. Compounds of formula I, or Il are even more preferred, wherein at least two of the groups R81, R82, R83, R84, R85, R86, R87, R88, R91, R92, R93, R94, R95, R96, R97, R91', R92', R93', R94', R95', R96' and R97' are a C7-C30aryl group, especially a polycyclic C8-C30aryl group.
In a further embodiment of the present invention compounds of formula are preferred,
wherein M is a single bond, -CO-, -COO-, -S-, -SO-, -SO2-, , especially
Figure imgf000010_0001
Figure imgf000010_0002
, especially
Figure imgf000010_0003
or
Figure imgf000010_0004
, especially
Figure imgf000010_0005
Figure imgf000011_0001
, especially
Figure imgf000011_0002
Figure imgf000012_0001
, or , wherein n1, n2, n3, n4, n5, n6 and n7 are integers of 1 to 10, in particular 1 to 3, A6 and A7 are independently of each other H, Ci-Ci8alkyl, d-Ci8alkyl which is substituted by E' and/or interrupted by D', C6-C24aryl, C6-C24aryl which is substituted by G', C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G', C2-Ci8alkenyl, C2-Ci 8alkynyl, CrCi8alkoxy, d- Ci8alkoxy which is substituted by E' and/or interrupted by D', C7-C25aralkyl, or -CO-A28, A8 is CrCi8alkyl, CrCi8alkyl which is substituted by E' and/or interrupted by D', C6-C24 aryl, or C7-C25aralkyl,
A9 and A10 are independently of each other CrCi8alkyl, CrCi8alkyl which is substituted by E' and/or interrupted by D', C6-C24aryl, C6-C24aryl which is substituted by G', C2-C20heteroaryl, C2-C20heteroaryl which is substituted by G', C2-Ci 8alkenyl, C2-Ci 8alkynyl, CrCi8alkoxy, d- Ci8alkoxy which is substituted by E' and/or interrupted by D', or C7-C25aralkyl, or A9 and A10 form a ring, especially a five- or six-membered ring, which can optionally be substituted by one or more CrCi8 alkyl groups;
A14 and A15 are independently of each other H, CrCi8alkyl, Ci-Ci8alkyl which is substituted by E' and/or interrupted by D', C6-C24aryl, C6-C24aryl which is substituted by G', C2- C20heteroaryl, or C2-C20heteroaryl which is substituted by G',
D' is -CO-; -COO-; -S-; -SO-; -SO2-; -0-; -NA25-; -SiA30A31-; -POA32-; -CA23=CA24-; or -C≡C-; and
E' is -OA29; -SA29; -NA25A26; -COA28; -COOA27; -CONA25A26; -CN; -OCOOA27; or halogen; G' is E', or Ci-Ci8alkyl; wherein A23, A24, A25 and A26 are independently of each other H; C6- Ci8aryl; C6-Ci 8aryl which is substituted by CrCi8alkyl, or Ci-Ci8alkoxy; CrCi8alkyl, or d- Ci8alkyl which is interrupted by -0-; or A25 and Altogether form a five or six membered ring,
in particular
Figure imgf000012_0002
A27 and A28 are independently of each other H; C6-Ci8aryl; C6-Ci8aryl which is substituted by
CrCi8alkyl, or Ci-Ci8alkoxy; CrCi8alkyl, or Ci-Ci8alkyl which is interrupted by -0-,
A29 is H; C6-Ci8aryl; C6-Ci8aryl, which is substituted by CrCi8alkyl, or CrCi8alkoxy; d-
Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -O-,
A30 and A31 are independently of each other CrCi8alkyl, C6-Ci8aryl, or C6-Ci8aryl, which is substituted by Ci-d8alkyl, and A32 is Ci-Ci8alkyl, C6-Ci8aryl, or C6-Ci8aryl, which is substituted by d-Ci8alkyl.
Preferably, A6 and A7 are independently of each other H, Ci-Ci8alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methyl butyl, n-pentyl, isopentyl, n- hexyl, 2-ethylhexyl, or n-heptyl, CrCi8alkyl which is substituted by E' and/or interrupted by D', such as -CH2OCH3, -CH2OCH2CH3, -CH2OCH2CH2OCH3, or -CH2OCH2CH2OCH2CH3 , C6- C24aryl, such as phenyl, naphthyl, or biphenyl, C6-C24aryl which is substituted by G', such as -C6H4OCH3, -C6H4OCH2CH3, -C6H3(OCH3J2, or -C6H3(OCH2CH3)2, -C6H4CH3, -C6H3(CH3J2, -C6H2(CH3J3, or -C6H4tBu. A8 is preferably H, CrCi8alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methyl butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, or C6- C24aryl, such as phenyl, naphthyl, or biphenyl.
Preferably, A9 and A10 are independently of each other H, CrCi8alkyl, such as n-butyl, sec- butyl, hexyl, octyl, or 2-ethyl-hexyl, Ci-d8alkyl which is substituted by E' and/or interrupted by D', such as -CH2(OCH2CH2)WOCH3, w = 1 , 2, 3, or 4, C6-C24aryl, such as phenyl, naphthyl, or biphenyl, C6-C24aryl which is substituted by G', such as -C6H4OCH3, -C6H4OCH2CH3, -C6H3(OCH3J2, -C6H3(OCH2CH3)2, -C6H4CH3, -C6H3(CH3J2, -C6H2(CH3J3, or -C6H4tBu, or A9 and A10 together form a 4 to 8 membered ring, especially a 5 or 6 membered ring, such as cyclohexyl, or cyclopentyl.
Preferably, A14 and A15 are independently of each other H, CrCi8alkyl, such as as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C6-C24aryl, such as phenyl, naphthyl, or biphenyl.
D' is preferably -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -NA25-, wherein A25 is CrCi8alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C6-C24aryl, such as phenyl, naphthyl, or biphenyl.
E' is preferably -OA29; -SA29; -NA25A25; -COA28; -COOA27; -CONA25A25; or -CN; wherein A25, A27, A28 and A29 are independently of each other CrCi8alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-C24 aryl, such as phenyl, naphthyl, or biphenyl.
Among the above-mentioned groups M the following groups are preferred:
Figure imgf000014_0001
and . Examples of especially preferred groups M are:
Figure imgf000014_0002
wherein A8 and A9 are independently of each other Ci-Ci8alkyl, or cyclohexan;
Figure imgf000015_0001
wherein A6 and A7 are
independently of each other H, or d-Ci8alkyl; or
Figure imgf000015_0002
. Groups M having a polycyclic C8-C30arylen group, or a polycyclic C4-C26heteroarylen group, wherein
polycyclic ring system comprises at least 8 atoms, are preferred,
Figure imgf000015_0003
and
Figure imgf000015_0004
are most preferred.
Among the compounds of formula Il compounds of formula
Figure imgf000015_0005
Compounds of formula
Figure imgf000016_0001
Figure imgf000016_0002
are even more preferred, wherein R95 and R95 are independently of each other Ci-C24alkyl, or C6-Ci4aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, which may be substituted by one, or more Ci-C8alkyl, or CrC8alkoxy groups, such as a group of formula
, especially
Figure imgf000016_0003
, or , wherein
R41, R41 , R42 and R42 are independently of each other is hydrogen, Ci-C8alkyl, or Ci-C8alkoxy, R45 is hydrogen, phenyl, or 1 -naphthyl, which can be substituted by one, or more CrC8alkyl, or Ci-C8alkoxy groups; or CrC8alkyl, or Ci-C8alkoxy.
In another embodiment compounds of formula Hb are preferred, wherein M is a single bond, R96 and R96' are a group
Figure imgf000017_0001
. especially , and R81, R92, R93, R94,
R95, R96, R97, R91', R92', R93', R94', R95', R96' and R97' are hydrogen.
Examples of especially preferred compounds are:
Figure imgf000017_0002
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
In further preferred embodiment of the present invention at least one, preferably two of the groups R81, R82, R83, R84, R85, R86, R87, R88, R91, R92, R93, R94, R95, R96, R97, R91', R92', R93', R94',
R95 , R96 and R97 are a group
Figure imgf000020_0002
, wherein A14 and A15 are independently of each other H, CrCi8alkyl, CrCi8alkyl which is substituted by E and/or interrupted by D, C6- C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G, and A16 is H, CrCi8alkyl, d-Ci8alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C20heteroaryl, or C2- C20heteroaryl which is substituted by G; or a polycyclic aryl group, especially pentalenyl, indenyl, azulenyl, naphthyl, biphenylenyl, as-indacenyl, s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl, anthracenyl, fluoranthenyl, acephenanthrylenyl, aceanthrylenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, picenyl, perylenyl, pentacenyl, pentaphenyl, hexacenyl, or hexaphenyl, which can optionally be substituted by G, wherein D, E and G are as defined above. Examples of particularly preferred groups are:
Figure imgf000020_0003
Figure imgf000021_0001
wherein R300 is Ci-C8alkyl, phenyl, which can be substituted by one, or more Ci-C8alkyl, or d-C8alkoxy groups, R14 is hydrogen, CrC8alkyl, phenyl, or 1-naphthyl, , which can be substituted by one, or more CrC8alkyl, or CrC8alkoxy groups; or CrC8alkoxy, and R18 and R19 are independently of each other CrC8alkyl, or cyclohexan. Compounds of formula Ia, Ib and Ic are preferred, wherein R82, R87, R83, R86, R83' and R86' are independently of each other one of the above groups. R82 and R87, R83 and R86, R83' and R86' can be the same or different.
In a further preferred embodiment of the present invention at least one, especially two of the groups R81, R82, R83, R84, R85, R86, R87, R88, R91, R92, R93, R94, R95, R96, R97, R91', R92', R93', R94', R95', R96' and R97' are independently of each other a group the formula -(W1)a-(W2)b-W3 (Y1), wherein a and b are 0, or 1 , W1 and W2 are independently of each other a group of formula
Figure imgf000021_0002
, especially or , and
Figure imgf000022_0001
R 11 π11' π12 D12' D13 D13' D15 D15' D16 D16' D17 D17' D41 D41' D42 D42' D44 D44' D45 D45'
R46, R46', R47 and R47' are independently of each other H, E, silyl, such as tri(Ci-C8alkyl)silyl, C6-Ci8aryl; C6-Ci8aryl which is substituted by G; CrCi8alkyl; CrCi8alkyl which is substituted by E and/or interrupted by D; CrCi8alkoxy; or CrCi8alkoxy which is substituted by E and/or interrupted by D; C7-Ci 8aralkyl; or C7-Ci8aralkyl which is substituted by G; R14 is H, silyl, such as tri(Ci-C8alkyl)silyl, Ci-d8alkyl; or CrCi8alkyl which is substituted by E and/or interrupted by D; Ci-Ci8alkoxy; or Ci-Ci8alkoxy which is substituted by E and/or
interrupted by D;
Figure imgf000022_0002
R18 and R19 are independently of each other CrCi8alkyl; CrCi8alkoxy, C6-Ci8aryl; C7-
Ci8aralkyl; or R18 and R19 together form a ring especially a five- or six-membered ring, which can optionally be substituted by CrC8alkyl,
R21, R22, R23, R24, R25, R26 and R27 are independently of each other H, E, CrCi8alkyl; Cr
Ci8alkyl which is substituted by E and/or interrupted by D; C7-Ci 8aralkyl; C7-Ci8aralkyl which is substituted by G; or W3 is a group of formula
Figure imgf000023_0001
Figure imgf000023_0002
Figure imgf000023_0003
wherein
R and R are independently of each other a hydrogen atom, a CrCi8alkyl group, a d-
Ci8alkoxy group, a group of formula
Figure imgf000023_0004
, or wherein R318, R319 and R320 independently from each other stand for hydrogen, Ci-C8-alkyl, Ci-C8-alkoxy, or phenyl, and R stands for is a hydrogen atom, a Ci-C25alkyl group, which might be interrupted by -O-, a cycloalkyl group, a C7-Ci8aralkyl group, a C6-Ci8aryl group, or a heterocyclic group, which may be substituted by G; wherein
D is -CO-, -COO-, -OCOO-, -S-, -SO-, -SO2-, -0-, -NR5-, SiR61R62-, -POR5-, -CR63=CR64-, or -
C≡C-;
E is -OR5, -SR5, -NR5R6, -COR8, -COOR7, -OCOOR7, -CONR5R6, -CN, or halogen;
G is E, or CrCi8alkyl; wherein R5 and R6 are independently of each other C6-Ci8aryl; C6-
Ci8aryl which is substituted by Ci-d8alkyl, or CrCi8alkoxy; CrCi8alkyl, or CrCi8alkyl which is interrupted by -0-; or
R5 and R6 together form a five or six membered ring, in particular
Figure imgf000024_0001
Figure imgf000024_0002
R7 is C7-Ci2alkylaryl; CrCi8alkyl; or CrCi8alkyl which is interrupted by -0-;
R8 is C6-Ci8aryl; C6-Ci8aryl which is substituted by CrCi8alkyl, or Ci-Ci8alkoxy; Ci-Ci8alkyl;
C7-Ci2alkylaryl, or CrCi8alkyl which is interrupted by -0-;
R61 and R62 are independently of each other C6-Ci8aryl; C6-Ci8aryl which is substituted by d-
Ci8alkyl, or CrCi8alkoxy; or CrCi8alkyl which is interrupted by -O-, and
R63 and R64 are independently of each other H, C6-Ci8aryl; C6-Ci8aryl which is substituted by
CrCi8alkyl, CrCi8alkoxy; or CrCi8alkyl which is interrupted by -O-.
If W3 is derived from a heteroaromatic group, it is preferably a group of formula
Figure imgf000024_0003
Figure imgf000025_0001
or wherein Fr1' is CrCi8alkyl.
Figure imgf000025_0002
Examples of preferred groups W1 and W2 are , and wherein R11 is hydrogen, or d-C8alkyl.
Examples of preferred groups W3 are
Figure imgf000025_0003
Figure imgf000025_0004
wherein R , R and R are hydrogen, phenyl, tri(Ci-C8alkyl)silyl, or Cr
C8alkyl, R and R are independently of each other CrC8alkyl, or cyclohexan.
\ // % /
Examples of preferred groups -(W )a-(W )b-W are
Figure imgf000026_0001
, or , wherein F »T11 , D R1144, D R1π8B an rdi D R1π9a are independently of each other hydrogen, or d-C8alkyl.
Among the compounds of formula I compounds of formula
Figure imgf000026_0002
Figure imgf000026_0003
(Ib), and (Ic), are more preferred, wherein R82,
R83, R86 and R87 are independently of each other a group the formula -(W1)a-(W2)b-W3. R82, R83, R86 and R87 can be different, but are preferably the same; and R81 and R88 are as defined above.
In a preferred embodiment of the present invention at least one, preferably two of the
Figure imgf000026_0005
substituents
Figure imgf000026_0004
RBB are , especially Compounds of formula Ia are even more preferred, wherein R and R are
Figure imgf000027_0001
, especially
In a further preferred embodiment of the present invention compounds of formula
(Id), (Id) and (Ie) are preferred, wherein R81, R83 and R83 a group the formula -(W2)-W3, wherein
W2 is a group
Figure imgf000027_0003
wherein R ό and R are independently of each other Cr
Ci8alkyl, or CrCi8alkoxy,
Figure imgf000027_0004
A further preferred embodiment of the present invention is directed to compounds of formula
Ia and Ib, wherein at least R82 and at least R83 are a group of formula
Figure imgf000027_0005
wherein A14 and A15 are independently of each other H, CrCi8alkyl, C6-C24aryl, or phenyl, which is substituted by one, or more CrC8alkyl, or Ci-C8alkoxy groups and the other, and R87
and R86 are a group of formula
Figure imgf000027_0006
, or a group of formula -(W1)a-(W2)b-W3. A further preferred embodiment of the present invention is directed to compounds of formula
Figure imgf000028_0001
(Ic), wherein R and R are independently of each other H,
Ci-Ci8alkyl,
Figure imgf000028_0002
Figure imgf000028_0003
or , wherein R14 is hydrogen, phenyl, tri(C r
C8alkyl)silyl, or CrC8alkyl, R18 and R19 are independently of each other CrC8alkyl, or cyclohexan.
Examples of especially preferred compounds are given below:
Figure imgf000028_0004
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Particularly suitable dibenzo-, dinaphthofurans are compounds A-1 , A-2, A-4, A-5, A-10, A-11 , A-16, A-19, B-1 and B-2.
In another preferred embodiment at least one, preferably two of the substituents R81, R82, R83, R84, R85, R86, R87, R88, R91, R92, R93, R94, R95, R96, R97, R91', R92', R93', R94', R95', R96' and R97' are independently of each other a group of the formula -W1 -(W2)b-W3 (Y2), wherein b is 0, or, 1 , W1 and W2 are as defined above and are preferably independently of each other a group of
formula
especiall
Figure imgf000037_0001
, or
W3 is a group of formula -NR70R71, wherein R70 and R71 are independently of each other a
group of formula
Figure imgf000037_0002
, wherein R 72 , D R7'3J and
R are independently of each other hydrogen, CrC8alkyl, a hydroxyl group, a mercapto group, CrC8alkoxy, CrC8alkylthio, halogen, halo-CrC8alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group or a siloxanyl group, or R70 and R71 together with the nitrogen atom to which they are bonded form a five or six membered heterocyclic ring, such as x1
216 - ,216
R21 R216 R >"
Figure imgf000037_0003
Figure imgf000038_0001
, which can be condensed by one or
two optionally substituted phenyl groups, such as
Figure imgf000038_0002
R κ , wherein R216 and
R217 independently from each other stands for hydrogen, Ci-C8alkyl, Ci-C8alkoxy, or phenyl, and
X1 stands for hydrogen, or d-C8alkyl;
R75, R76, R77 and R78 are independently of each other H, E, C6-Ci8aryl; C6-Ci8aryl which is substituted by E; Ci-Ci8alkyl; Ci-Ci8alkyl which is substituted by G and/or interrupted by D;
C7-Ci8aralkyl; or C7-Ci8aralkyl which is substituted by E; wherein D, E, G, R11, R11', R12', R16,
R16', R17, R17', R18, R19, R30, R31, R32 and R33 are as defined above, and R30', R31', R32' and R33' independently of each other have the meaning of R30.
If R70 and R71 are independently of each other a group of formula
Figure imgf000038_0003
b is preferably 1.
In said embodiment groups of the formula -W -(W )b-W are more preferred , wherein b is 0,
Figure imgf000038_0004
or 1 , W1 and W2 are independently of each other a group of formula
Figure imgf000038_0005
W3 is a group of formula 0
Figure imgf000038_0006
R 7'u an ^d D R7n1 are independently of each other a group of formula
Figure imgf000039_0001
or wherein R72 is Ci_i8alkyl.
In said embodiment of the present invention compounds of formula Ia and Ib are preferred, wherein R82 and R87 and R83 and R86 are independently of each other a group of formula - (W2)b-W3. The groups -(W2)b-W3 can be different, but are preferably the same.
Examples of preferred compounds are given below:
Figure imgf000039_0002
Figure imgf000039_0003
In another preferred embodiment the present invention is directed to compounds of formula I wherein at least one of R81, R82, R83, R84, R85, R86, R87 and R88 is a group Y1 and at least one of R81, R82, R83, R84, R85, R86, R87 and R88 is a group Y2.
In said embodiment compounds of formula Ia are preferred, wherein R81 is H, R88 is Y2 and R83 and R86 are Y1; or R81 and R88 are H1 R83 is Y2 and R86 are Y1.
Figure imgf000039_0004
Examples of preferred compounds are given below:
Figure imgf000040_0001
Figure imgf000040_0002
The present benzofuran compounds show a high solid state fluorescence in the desired wavelength range and can be prepared according to or analogous to known procedures (see, for example, WO99/47474, WO2004039786 and WO2004077885).
The benzofuran compounds of the present invention of the formula:
Figure imgf000040_0003
, wherein W3 is as defined above, can, for example, be prepared according to a process, which comprises reacting a derivative of formula
Figure imgf000040_0004
wherein R100 stands for halogen such as chloro or bromo, preferably bromo, or E having the meaning of
Figure imgf000040_0005
wherein a is 2 or 3, with boron ic acid derivative E-W3, or - in case R100 is not halogen - HaI-W3, wherein Hal stands for halogen, preferably for bromo, in the presence of an allylpalladium catalyst of the μ-halo(triisopropylphosphine)(η3-allyl)palladium(ll) type (see for example
WO99/47474).
Preferably, the 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. Usually, the amount of the solvent is chosen in the range of from 1 to 10 I per mol of boronic acid derivative. Also preferred, the reaction is carried out under an inert atmosphere such as nitrogen, or argon.
Further, it is preferred to carry out the reaction in the presence of an aqueous base, such as an alkali metal hydroxide or carbonate such as NaOH, KOH, Na2CO3, K2CO3, Cs2CO3 and the like, preferably an aqueous K2CO3 solution is chosen. Usually, the molar ratio of the base to compound III is chosen in the range of from 0.5:1 to 50:1.
Generally, the reaction temperature is chosen in the range of from 40 to 180°C, preferably under reflux conditions.
Preferred, the reaction time is chosen in the range of from 1 to 80 hours, more preferably from 20 to 72 hours.
In a preferred embodiment a usual catalyst for coupling reactions or for polycondensation reactions is used, preferably Pd-based catalyst such as known tetrakis(triarylphosphonium)- palladium, preferably (Ph3P)4Pd and derivatives thereof. Usually, the catalyst is added in a molar ratio from inventive DPP polymer to the catalyst in the range of from 100:1 to 10:1, preferably from 50:1 to 30:1.
Also preferred, the catalyst is added as in solution or suspension. Preferably, 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.
The obtained inventive polymer can be isolated by well-known methods. Preferably, after cooling down the reaction mixture to room temperature, it is poured into acetone and the obtained precipitation is filtered off, washed and dried.
Ci-CisAlkyl is a branched or unbranched radical such as for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1- methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3- tetramethylbutyl, 1 -methyl heptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1 ,3,3,5,5- hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or octadecyl.
Ci-Ci8AIkOXy radicals are straight-chain or branched alkoxy radicals, e.g. methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy.
C2-Ci8Alkenyl radicals are straight-chain or branched alkenyl radicals, such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2- enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
C2-24Alkynyl is straight-chain or branched and preferably C2-8alkynyl, which may be unsubstituted or substituted, such as, for example, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1 -yl, trans-3-methyl-2-penten-4-yn-1 -yl, 1 ,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-tetracosyn-24-yl.
C4-Ci βcycloalkyl is preferably C5-Ci2cycloalkyl, such as, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclododecyl. Cyclohexyl and cyclododecyl are most preferred.
The term "aryl group" is typically C6-C3oaryl, such as phenyl, indenyl, azulenyl, naphthyl, biphenyl, terphenylyl or quadphenylyl, as-indacenyl, s-indacenyl, acenaphthylenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl, naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, or anthracenyl, preferably phenyl, 1 -naphthyl, 2-naphthyl, 9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may be unsubstituted or substituted. Examples of C6-Ci8aryl are phenyl, 1 -naphthyl, 2-naphthyl, 3- or 4-biphenyl, 9-phenanthryl, 2- or 9-fluorenyl, which may be unsubstituted or substituted.
C7-C24aralkyl radicals are preferably C7-d8aralkyl radicals, which may be substituted, such as, for example, benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C7-Ci8aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, and particularly preferred C7-Ci2aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, or ω,ω-dimethyl-ω-phenyl-butyl, in which both the aliphatic hydrocarbon group and aromatic hydrocarbon group may be unsubstituted or substituted.
C7-Ci2alkylaryl is, for example, a phenyl group substituted with one, two or three d-C6alkyl groups, such as, for example, 2-, 3-, or 4-methylphenyl, 2-, 3-, or 4-ethyl phenyl, 3-, or 4- isopropylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, or 3,4,5-trimethylphenyl.
The term "heteroaryl group", especially C2-C3oheteroaryl, is a ring, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically an unsaturated heterocyclic radical with five to 18 atoms having at least six conjugated π-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, 2H-chromenyl, xanthenyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, 1 H-pyrrolizinyl, isoindolyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, 3H- indolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl, 4aH- carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, preferably the above-mentioned mono- or bicyclic heterocyclic radicals, which may be unsubstituted or substituted.
Halogen is fluorine, chlorine, bromine and iodine.
The terms "haloalkyl" mean groups given by partially or wholly substituting the above-mentioned alkyl group, with halogen, such as trifluoromethyl etc. The "aldehyde group, ketone group, ester group, carbamoyl group and amino group" include those substituted by an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group, wherein the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the heterocyclic group may be unsubstituted or substituted. The term "silyl group" means a group of formula -SiR62R63R64, wherein R62, R63 and R64 are independently of each other a Cr C8alkyl group, in particular a CrC4alkyl group, a C6-C24aryl group or a C7-Ci2aralkylgroup, such as a trimethylsilyl group. The term "siloxanyl group" means a group of formula -0-SiR62R63R64, wherein R62, R63 and R64 are as defined above, such as a trimethylsiloxanyl group. Possible substituents of the above-mentioned groups are Ci-C8alkyl, a hydroxyl group, a mercapto group, CrC8alkoxy, CrC8alkylthio, halogen, halo-CrC8alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group or a silyl group.
As described above, the aforementioned radicals may be substituted by E and/or, if desired, interrupted by D. Interruptions are of course possible only in the case of radicals containing at least 2 carbon atoms connected to one another by single bonds; C6-Ci 8aryl is not interrupted; interrupted arylalkyl or alkylaryl contains the unit D in the alkyl moiety, d- Ci8alkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (CH2CH2O)n-R", where n' is a number from the range 1-9 and Rx is H or Ci-CiOalkyl or C2-Ci0alkanoyl (e.g. CO-CH(C2H5)C4H9), CH2-CH(ORyi)-CH2-O-Ry, where Ry is CrCi8alkyl, C5-Ci2cycloalkyl, phenyl, C7-Ci5phenylalkyl, and Ryi embraces the same definitions as Ry or is H; CrC8alkylene-COO-Rz, e.g. CH2COOR2 CH(CH3)COOR2, C(CH3)2COORZ, where Rz is H, CrCi8alkyl, (CH2CH2O)i-9-Rx, and Rx embraces the definitions indicated above; CH2CH2-O-CO-CH=CH2; CH2CH(OH)CH2-O-CO-C(CH3)=CH2.
The electroluminescent devices may be employed for full color display panels in, for example, mobile phones, televisions and personal computer screens.
The electroluminescent devices of the present invention are otherwise designed as is known in the art, for example as described in U.S. Pat. Nos. 5,518,824, 6,225,467, 6,280,859, 5,629,389, 5,486,406, 5,104,740, 5,116,708 and 6,057,048, the relevant disclosures of which are hereby incorporated by reference.
For example, organic EL devices contain one or more layers such as: substrate; base electrode; hole-injecting layer; hole transporting layer; emitter layer; electron- transporting layer; electron-injecting layer; top electrode; contacts and encapsulation. This structure is a general case and may have additional layers or may be simplified by omitting layers so that one layer performs a plurality of tasks. For instance, the simplest organic EL device consists of two electrodes which sandwich an organic layer that performs all functions, including the function of light emission. A preferred EL device comprises in this order:
(a) an anode,
(b) a hole injecting layer and/or a hole transporting layer,
(c) a light-emitting layer,
(d) optionally an electron transporting layer and (e) a cathode.
The benzofuran compounds of the present invention can, in principal be used for any organic layer, such as, for example, hole transporting layer, light emitting layer, or electron transporting layer, but are preferably used as the light emitting material in the light emitting layer, optionally as a host or guest component, or electron transporting layer.
In particular, the present organic compounds function as light emitters and are contained in the light emission layer or form the light-emitting layer.
The light emitting compounds of this invention exhibit intense fluorescence in the solid state and have excellent electric-field-applied light emission characteristics. Further, the light emitting compounds of this invention are excellent in the injection of holes from a metal electrode and the transportation of holes; as well as being excellent in the injection of electrons from a metal electrode and the transportation of electrons. They are effectively used as light emitting materials and may be used in combination with other hole transporting materials, other electron transporting materials or other dopants.
The organic compounds of the present invention form uniform thin films. The light emitting layers may therefore be formed of the present organic compounds alone. Alternatively, the light-emitting layer may contain a known light-emitting material, a known dopant, a known hole transporting material or a known electron transporting material as required. In the organic EL device, a decrease in the brightness and life caused by quenching can be prevented by forming it as a multi-layered structure. The light-emitting material, a dopant, a hole-injecting material and an electron-injecting material may be used in combination as required. Further, a dopant can improve the light emission brightness and the light emission efficiency, and can attain the red or blue light emission. Further, each of the hole transporting zone, the light-emitting layer and the electron transporting zone may have the layer structure of at least two layers. In the hole transporting zone in this case, a layer to which holes are injected from an electrode is called "hole-injecting layer", and a layer which receives holes from the hole-injecting layer and transport the holes to a light-emitting layer is called "hole transporting layer". In the electron transporting zone, a layer to which electrons are injected from an electrode is called "electron-injecting layer", and a layer which receives electrons from the electron-injecting layer and transports the electrons to a light-emitting layer is called "electron transporting layer". These layers are selected and used depending upon factors such as the energy level and heat resistance of materials and adhesion to an organic layer or metal electrode. The light-emitting material or the dopant which may be used in the light-emitting layer together with the organic compounds of the present invention includes for example anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperγlene, naphthaloperγlene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarine, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinyl anthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, an imidazole- chelated oxynoid compound, quinacridone, rubrene, and fluorescent dyestuffs for a dyestuff laser or for brightening.
It is also possible to use the compounds of the present invention with phosphorescent materials as a dopant in the light-emitting layer. Examples of the phosphorescent materials are, for example, metal complexes of Ir, Pt, Eu, Ru, Rh, Pd, Ag, Re, Os and Au and are described, for example, in JP2005-11804 and WO2004/034751.
Examples of typical structures of the metal complex are shown below:
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
In that case the electroluminescent device may comprise in this order (a) an anode, such as, for example, ITO, (b1) a hole injecting layer, such as, for example, CuPc,
(b2) a hole transporting layer, such as, for example, such as, for example, N1N'- Di(naphthalene-1-yl)-N,N'-diphenyl-benzidine (NPD), or TCTA,
(c) a light-emitting layer, comprising a phosphorescent compound and a dibenzofuran compound of the present invention, especially a compound A-1 to A-66, B-1 to B-18, C-1 and C-2. a positive hole inhibiting layer, such as, for example, BCP, or BAIq, (d) an electron transporting layer, such as, for example, AIq3, and an inorganic compound layer, such as, for example, LiF,
(e) a cathode, such as, for example, Al.
If the dibenzofuran compounds of the present invention are used as host together with guest compounds, such, as for example, 2,5,8,11-tetra-t-butylperylene (Jiaumin Shi Ching W. Tang, Appl. Phys. Lett. 80, 3201 (2002), or the compounds, described, for example, in
Figure imgf000050_0001
WO03/105538, such as, for example, (G-1), the electroluminescent device may comprise in this order
(a) an anode, such as, for example, ITO,
(b1) a hole injecting layer, such as, for example, CuPc,
(b2) a hole transporting layer, such as, for example, NPD, or TCTA,
(c) a light-emitting layer, comprising a fluorescent guest compound and a dibenzofuran host compound of the present invention, especially a compound A-1 to A-66, B-1 to B-18, C-1 and C-2, optionally a positive hole inhibiting layer, such as, for example, BCP,
(d) an electron transporting layer, such as, for example, AIq3, or TPBI and an inorganic compound layer, such as, for example, LiF,
(e) a cathode, such as, for example, Al.
The weight ratio of compound of the formula I to the dopant in general 50:50 to 99.99:0.01, preferably 90:10 to 99.99:0.01 , more preferably 95:5 to 99.9:0.1. If the guest is a phosphorescent compound, its concentration is normally 5-10%.
Accordingly, the present invention also relates to compositions comprising a compound of the present invention.
The compounds of the present invention and the above compound or compounds that can be used in a light-emitting layer may be used in any mixing ratio for forming a light-emitting layer. That is, the organic compounds of the present invention may provide a main component for forming a light-emitting layer, or they may be a doping material in another main material, depending upon a combination of the above compounds with the organic compounds of the present invention. The hole-injecting material is selected from compounds which are capable of transporting holes, are capable of receiving holes from the anode, have an excellent effect of injecting holes to a light-emitting layer or a light-emitting material, prevent the movement of excitons generated in a light-emitting layer to an electron-injecting zone or an electron-injecting material and have the excellent capability of forming a thin film. Suitable hole-injecting materials include for example a phthalocyanine derivative, a naphthalocyanine derivative, a porphyrin derivative, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolthione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, polyarylalkane, stilbene, butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, derivatives of these, and polymer materials such as polyvinylcarbazole, polysilane and an electroconducting polymer.
In the organic EL device of the present invention, the hole-injecting material which is more effective is an aromatic tertiary amine derivative or a phthalocyanine derivative. Although not specially limited, specific examples of the tertiary amine derivative include triphenylamine, tritolylamine, tolyldiphenylamine, N.N'-diphenyl-N.N'-β-methylphenylJ-i.i-biphenyl-^1- diamine, N,N,Nl,Nl-tetra(4-methylphenyl)-1 ,1l-phenyl-4,4l-diamine, N,N,N',N1-tetra(4- methylphenylj-i .i'-biphenyl^^'-diamine, N,Nl-diphenyl-N,Nl-di(1-naphthyl)-1 ,1'-biphenyl- 4,4'-diamine, N, N'-di(methylphenyl)-N,N1-di(4-n-butylphenyl)-phenanthrene-9, 10- diamine, 4,4", 4"-tris(3-methylphenyl)-N-phenylamino)triphenylamine, 1 , 1 -bis(4-di-p- tolylaminophenyl)cyclohexane, and oligomers or polymers having aromatic tertiary amine structures of these.
Although not specially limited, specific examples of the phthalocyanine (Pc) derivative include phthalocyanine derivatives or naphthalocyanine derivatives such as H2Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, CIAIPc, CIGaPc, CIInPc, CISnPc, CI2SiPc, (HO)AIPc, (HO)GaPc, VOPc, TiOPc, MoOPc, and GaPc-O-GaPc.
The hole transporting layer can reduce the driving voltage of the device and improve the confinement of the injected charge recombination within the light emitting layer, comprising the compounds of the present invention. Any conventional suitable aromatic amine hole transporting material described for the hole-injecting layer may be selected for forming this layer.
A preferred class of hole transporting materials is comprised of 4,4'-bis(9-carbazolyl)-1 ,11- biphenyl compounds of the formula
Figure imgf000052_0001
wherein R61 and R62 is a hydrogen atom or an d-C3alkyl group; R63 through R66 are substituents independently selected from the group consisting of hydrogen, a d-C6alkyl group, a CrC6alkoxy group, a halogen atom, a dialkylamino group, a C6-C30aryl group, and the like. Illustrative examples of 4,4'-bis(9-carbazolyl)-1 ,1l-biphenyl compounds include 4,4'- bis(9-carbazolyl)-1 ,1'-biphenyl and 4,4l-bis(3-methyl-9-carbazolyl)-1 ,1l-biphenylJ and the like; or 4,4',4"-tri-(N-carbazoyl)triphenylamine (TCTA).
In addition, polymeric material can be used as a hole injection material and a hole transporting material, such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4- styrenesulfonate), also called PEDOT/PSS.
The electron transporting layer is not necessarily required for the present device, but is optionally and preferably used for the primary purpose of improving the electron injection characteristics of the EL devices and the emission uniformity. Illustrative examples of electron transporting compounds, which can be utilized in this layer, include the metal chelates of 8-hydroxyquinoline as disclosed in U.S. Pat. Nos. 4,539,507, 5,151 ,629, and 5,150,006, the disclosures of which are totally incorporated herein by reference.
Examples of suitable electron transporting materials are metal complex compounds and nitrogen-containing five-membered ring derivatives.
Although not specially limited, specific examples of the metal complex compound include lithium 8-hydroxyquinolinate, zinc bis(8-hydroxyquinolinate), copper bis(8- hydroxyquinolinate), manganese bis(8-hydroxyquinolinate), aluminum tris(8- hydroxyquinolinate), aluminum tris(2-methyl-8-hydroxyquinolinate), gallium tris(8- hydroxyquinolinate), beryllium bis(10-hydroxybenzo[h]quinolinate), zinc bis(10- hydroxybenzo[h]quinolinate), chlorogallium bis(2-methyl-8-quinolinate), gallium bis(2-methyl- 8-quinolinate)(o-cresolate), aluminum bis(2-methyl-8-quinolinate)(1-naphtholate), gallium bis(2-methyl-8-quinolinate)(2-naphtholate), gallium bis(2-methyl-8-quinolinate)phenolate, zinc bis(o-(2-benzooxazolyl)phenolate), zinc bis(o-(2-benzothiazolyl)phenolate) and zinc bis(o-(2- benzotrizolyl)phenolate). The nitrogen-containing five-membered derivative is preferably an oxazole, thiazole, thiadiazole, or triazole derivative. Although not specially limited, specific examples of the above nitrogen-containing five-membered derivative include 2,5-bis(1- phenyl)-1 ,3,4-oxazole, 1 ,4-bis(2-(4-methyl-5-phenyloxazolyl)benzene, 2,5-bis(1 -phenyl)- 1 J3J4-thiazoleJ 2J5-bis(1-phenyl)-1 J3J4-oxadiazoleJ 2-(4l-tert-butylphenyl)-5-(4"-biphenyl)1,3J4- oxadiazole, 2,5-bis(1-naphthyl)-1 ,3,4-oxadiazole, 1 ,4-bis[2-(5-phenyloxadiazolyl)]benzene, 1 ,4-bis[2-(5-phenyloxadiazolyl)-4-tert-butylbenzene], 2-(4'-tert-butylphenyl)-5-(4"-biphenyl)- 1 ,3,4-thiadiazole, 2,5-bis(1 -naphthyl)-1 ,3,4-thiadiazole, 1 ,4-bis[2-(5-phenylthiazolyl)]benzene, 2-(4'-tert-butylphenyl)-5-(4"-biphenyl)-1 ,3,4-triazole, 2,5-bis(1 -naphthyl)-1 ,3,4-triazole and 1 ,4-bis[2-(5-phenyltriazolyl)]benzene. Another class of electron transport materials are oxadiazole metal chelates, such as bis[2-(2-hydroxyphenyl)-5-phenyl-1,3,4- oxadiazolato]zinc; bis[2-(2-hydroxyphenyl)-5-phenyl-1 ,3,4-oxadiazolato]beryllium; bis[2-(2- hydroxyphenyl)-5-(1 -naphthyl)-1 ,3,4-oxadiazolato]zinc; bis[2-(2-hydroxyphenyl)-5-(1 - naphthyl)-1 ,3,4-oxadiazolato]beryllium; bis[5-biphenyl-2-(2-hydroxyphenyl)-1 ,3,4- oxadiazolato]zinc; bis[5-biphenyl-2-(2-hydroxyphenyl)-1 ,3,4-oxadiazolato]beryllium; bis(2- hydroxyphenyl)-5-phenyl-1 ,3,4-oxadiazolato]lithium; bis[2-(2-hydroxyphenyl)-5-p-tolyl-1 ,3,4- oxadiazolato]zinc; bis 2-(2-hydroxyphenyl)-5-p-tolyl-1 ,3,4-oxadiazolato]beryllium; bis[5-(p- tert-butylphenyl)-2-(2-hydroxyphenyl)-1 ,3,4-oxadiazolato]zinc; bis[5-(p-tert-butylphenyl)-2-(2- hydroxyphenyl)-1 ,3,4-oxadiazolato]berylliu m; bis[2-(2-hydroxyphenyl)-5-(3-fluorophenyl)- 1 ,3,4-oxadiazolato]zinc; bis[2-(2-hydroxyphenyl)-5-(4-fluorophenyl)-1 ,3,4-oxadiazolato]zinc; bis[2-(2-hydroxyphenyl)-5-(4-fluorophenyl)-1 ,3,4-oxadiazolato]beryllium; bis[5-(4- chlorophenyl)-2-(2-hydroxyphenyl)-1 ,3,4-oxadiazolato]zinc; bis[2-(2-hydroxy phenyl)-5-(4- methoxyphenyl)-1 ,3,4-oxadiazolato]zinc; bis[2-(2-hydroxy-4-methylphenyl)-5-phenyl-1 ,3,4- oxadiazolatojzinc; bis[2-. alpha. -(2-hydroxynaphthyl)-5-phenyl-1 ,3,4-oxadiazolato]zinc; bis[2- (2-hydroxyphenyl)-5-p-pyridyl-1,3,4-oxadiazolato]zinc; bis[2-(2-hydroxyphenyl)-5-p-pyridyl- 1 ,3,4-oxadiazolato]beryllium; bis[2-(2-hydroxyphenyl)-5-(2-thiophenyl)-1 ,3,4- oxadiazolato]zinc; bis[2-(2-hydroxyphenyl)-5-phenyl-1 ,3,4-thiadiazolato]zinc; bis[2-(2- hydroxyphenyl)-5-phenyl-1 ,3,4-thiadiazolato]beryllium; bis[2-(2-hydroxyphenyl)-5-(1 - naphthyl)-1 ,3,4-thiadiazolato]zinc; and bis[2-(2-hydroxyphenyl)-5-(1-naphthyl)-1 ,3,4- thiadiazolato]beryllium, and the like.
Other suitable compounds for the electron transporting material are hetero-cyclic compounds such as benzimidazole derivatives, benzoxazole derivatives, oxadiazole derivatives, thiadiazole derivative, triazole derivatives, pyrazine derivatives, phenanthroline derivatives, quinoxaline derivatives, quinoline derivatives, benzoquinoline derivatives, oligo-pyridine derivatives, e.g. bipyridine derivatives and terpyridine derivatives, naphthylidine derivatives, indole derivatives and naphthalimide derivatives; silole derivatives; and phosphineoxide derivatives.
The property of charge injection can be improved by adding an electron-accepting compound to the hole injection layer and/or the hole transporting layer and electron-donating material to the electron transporting layer.
It is possible to add reducing dopant to the electron transporting layer to improve the EL device property. The reducing dopant is a material that can reduce the electron transporting material. Examples of the reducing dopant are alkaline metals, e.g. Na, K, Rb and Cs, and alkaline earth metals, e.g. Ca, Sr, and Ba.
The organic EL device of the present invention may comprise an inorganic compound layer between at least one of the electrodes and the above organic thin layer. Examples of the inorganic compound used for the inorganic compound layer include various types of oxides, nitrides and oxide nitrides such as alkali metal oxides, alkaline earth metal oxides, rare earth oxides, alkali metal halides, alkaline earth metal halides, rare earth halides, SiOx, AIOx, SiNx, SiON, AION, GeOx, LiOx, LiON, TiOx, TiON, TaOx, TaON, TaNx and C. In particular, as the component contacting the anode, SiOx, AIOx, SiNx, SiON, AION, GeOx and C are preferred since a suitable interface layer of injection is formed. As the component contacting the cathode LiF, MgF2, CaF2 and NaF are preferred.
In the organic EL device of the present invention, the light-emitting layer may contain, in addition to the light-emitting organic material of the present invention, at least one of other light-emitting material, other dopant, other hole-injecting material and other electron-injecting material. For improving the organic EL device of the present invention in the stability against temperature, humidity and ambient atmosphere, a protective layer may be formed on the surface of the device, or the device as a whole may be sealed with a silicone oil, or the like.
The electrically conductive material used for the anode of the organic EL device is suitably selected from those materials having a work function of greater than 4 eV. The electrically conductive material includes carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, alloys of these, metal oxides such as tin oxide and indium oxide used for ITO substrates or NESA substrates, and organic electroconducting polymers, such as polythiophene and poly pyrrole. The electrically conductive material used for the cathode is suitably selected from those having a work function of smaller than 4 eV. The electrically conductive material includes magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum and alloys of these, while the electrically conductive material shall not be limited to these. Examples of the alloys include magnesium/silver, magnesium/indium and lithium/aluminum, while the alloys shall not be limited to these. Each of the anode and the cathode may have a layer structure formed of two layers or more as required.
For the effective light emission of the organic EL device, at least one of the electrodes is desirably sufficiently transparent in the light emission wavelength region of the device. Further, the substrate is desirably transparent as well. The transparent electrode is produced from the above electrically conductive material by a deposition method or a sputtering method such that a predetermined light transmittance is secured. The electrode on the light emission surface side has for instance a light transmittance of at least 10%. The substrate is not specially limited so long as it has adequate mechanical and thermal strength and has transparency. For example, it is selected from glass substrates and substrates of transparent resins such as a polyethylene substrate, a polyethylene terephthalate substrate, a polyether sulfone substrate and a polypropylene substrate.
In the organic EL device of the present invention, each layer can be formed by any one of dry film forming methods such as a vacuum deposition method, a sputtering method, a plasma method and an ion plating method and wet film forming methods such as a spin coating method, a dipping method and a flow coating method. The thickness of each layer is not specially limited, while each layer is required to have a proper thickness. When the layer thickness is too large, inefficiently, a high voltage is required to achieve predetermined emission of light. When the layer thickness is too small, the layer is liable to have a pinhole, etc., so that sufficient light emission brightness is hard to obtain when an electric field is applied. The thickness of each layer is for example in the range of from about 5 nm to about 10 μm, for instance about 10 nm to about 0.2 μm.
In the wet film forming method, a material for forming an intended layer is dissolved or dispersed in a proper solvent, such as toluene, ethanol, chloroform, tetrahydrofuran and dioxane, and a thin film is formed from the solution or dispersion. The solvent shall not be limited to the above solvents. For improving the film formability and preventing the occurrence of pinholes in any layer, the above solution or dispersion for forming the layer may contain a proper resin and a proper additive. The resin that can be used includes insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate and cellulose, copolymers of these, photoconductive resins such as poly-N-vinylcarbozole and polysilane, and electroconducting polymers such as polythiophene and polypyrrole. The above additive includes an antioxidant, an ultraviolet absorbent and a plasticizer.
When the light-emitting organic material of the present invention is used in a light-emitting layer of an organic EL device, an organic EL device can be improved in organic EL device characteristics such as light emission efficiency and maximum light emission brightness. Further, the organic EL device of the present invention is remarkably stable against heat and electric current and gives a usable light emission brightness at a low actuation voltage. The problematic deterioration of conventional devices can be remarkably decreased.
The organic EL device of the present invention has significant industrial values since it can be adapted for a flat panel display of an on-wall television set, a flat light-emitting device, a light source for a copying machine or a printer, a light source for a liquid crystal display or counter, a display signboard, lighting application and a signal light.
The material of the present invention can be used in the fields of an organic EL device, an electrophotographic photoreceptor, a photoelectric converter, a solar cell, and an image sensor.
Various features and aspects of the present invention are illustrated further in the examples that follow. While these examples are presented to show one skilled in the art how to operate within the scope of this invention, they are not to serve as a limitation on the scope of the invention where such scope is only defined in the claims. Unless otherwise indicated in the following examples and elsewhere in the specification and claims, all parts and percentages are by weight.
Examples Example 1 Synthesis of 2,8-Bis-((E)-styryl)-dibenzofuran
Figure imgf000056_0001
1a) 2,8-Dibromodibenzofuran
Bromine (92.6 g, 0.58 mol) in acetic acid (54 g) is added at 75°C to a solution of dibenzofuran (23.2 g, 0.14 mol) in acetic acid (232 g). The mixture is then stirred at 75°C for 3 hours. The reaction mixture is cooled to room temperature and poured into H2O. The orange solid is washed with Na2S2O3 aq. and H2O. The crude product is then purified by recrystallization from n-hexane, wherein the pure product is obtained as a white solid (38% yield; mp.: 226°C). 1H-NMR (CDCI3, ppm): 7.65 (d, 2H), 7.59 (dd, 2H), 8.03 (d, 2H).
1 b) 2,8-Bis-((E)-styryl)-dibenzofuran
Tetrethylamine hydroxide (13.6 g, 18.4 mmol), tetrakis(triphenylphosphine)palladium(0) (142 mg) and trans-2-phenylvinylboronic acid (2.3 g, 15.3 mmol) are added to a solution of the product from example 1a) (2.00 g, 6.14 mmol) in N,N'-Dimethylacetamide (DMA) (30 ml). The mixture is then stirred at 1100C for 24 hours. The reaction mixture is cooled to room temperature and poured into H2O. A gray crude product is obtained after filtration and washing with n-hexane. The crude product is purified by silicagel column chromatography with CH2CI2, which result in a white solid (71% yield, mp.: 226°C).
1H-NMR (CDCI3, ppm): 7.26-7.30 (m, 6H), 7.39 (t, 4H), 7.54-7.58 (m, 6H), 7.65 (dd, 2H), 8.12 (d, 2H)
Example 2
Synthesis of 1,5-dibenzofuranyl-3,7-di-tert-butylnaphthalene
Figure imgf000057_0001
2a) 1 ,5-dibromo-3,7-di-tert-butylnaphthalene
Fe (212 mg) and bromine (18.3 g, 0.11 mol) in carbontetrachloride (75 ml) are added at 0°C to a solution of 2,6-di-tert-butylnaphthalene (25 g, 0.1 mol) in carbontetrachloride (300 ml). The mixture is then stirred at 0°C for 3.5 hours. The reaction mixture is poured into H2O and then the organic layer is washed with Na2S2O3 aq. and H2O. The organic layer is dried over MgSO4 and concentrated by evaporation. The crude product is then purified by silicagel column chromatography with n-hexane, which result in a white solid (31% yield; mp.: 226°C). 1H-NMR (CDCI3, ppm): 1.41 (s, 18H), 7.88 (d, 2H), 8.11 (d, 2H).
2b) 1,5-Dibenzofuranyl-3,7-di-tert-butylnaphthalene Tetrethylaminehydroxide (3.5 g, 14.2 nnnnol), tetrakis(triphenylphosphine)palladiunn(0) (100 mg) and 4-denzofuranboronic acid (3 g, 14.0 nnnnol) are added to a solution of the product from example 2a) (1.88 g, 4.72 mmol) in DMA (30 ml). The mixture is stirred at 1100C for 1 hour, then cooled to room temperature, whereby a yellow solid product is obtained which is isolated by filtration and washed with H2O. The yellow solid is then dissolved in CH2CI2 and dried over MgSO4. Concentration by evaporation and silicagel column chromatography with ethylacetate/hexane=1/30 as eluent afforded a pure yellow solid product (65% yield; mp.: 226°C).
1H-NMR (CDCI3, ppm): 1.98 (s, 18H), 7.38-7.58 (m, 8H), 7.67 (d, 2H), 7.77 (d, 2H), 7.82 (d, 2H), 8.08 (dd, 2H), 8.11 (dd, 2H).
The compounds shown below (examples 3-10) are prepared in analogues manner using the appropriate educts.
Figure imgf000058_0001
Figure imgf000059_0001
Example 11
Synthesis of 2-Phenanthren-9-yl-8-pyren-1-yl-dibenzofuran
11a) 2-Bromodibenzofuran
Bromine (23.8 g, 0.156 mol) in acetic acid (5g) is added at 50°C to a solution of dibenzofuran (25 g, 0.149 mol) in acetic acid (230 g). The mixture is then stirred at 500C for 4 hours. The reaction mixture is cooled to room temperature and poured into H2O. The orange solid is washed with Na2S2O3 aq. and H2O. The crude product is then purified by recrystallization from toluene/CH2CI2, wherein the pure product is obtained as a white solid (13% yield). 1H-NMR (CDCI3, ppm): 7.59-7.73 (m, 5H), 7.90 (d, 1H), 8.70 (d, 1 H)
11b) 2-Bromo-8-iododibenzofuran
2-Bromodibenzofuran (2.5 g, 10.1 mmol), orthoperiodic acid (0.49 g, 2.15 mmol), iodine (1.02 g, 4.02 mmol), sulfuric acid, H2O (2 ml) and acetic acid (10 ml) are put into a reaction vessel and the mixture is stirred at 70°C for 3 hours. After cooling to room temperature the reaction mixture is poured into water and filtered. The white solid is washed by methanol and the desired product is obtained (1.92 g, 51%).
1H-NMR (CDCI3, ppm): 7.34 (d, 1H), 7.44 (d, 1H), 7.57(dd, 1 H), 7,75(dd, 1H), 8.01 (d, 1 H), 8.22 (d, 1 H)
11c) 2-Bromo-8-pyren-1 -yl-dibenzofuran
Figure imgf000060_0001
20% aq. solution of tetraethylammoninm hydroxide (5.33 g, 7.24 mmol), tetrakis- (triphenylphosphine)palladium(O) (200 mg) and 1-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) pyrene (1.74 g, 5.3 mmol) are added to a solution of the product of example 11 b) (1.81 g, 4.83 mmol) in N,N'-dimethylacetamide (DMA) (70 ml). The mixture is then stirred at 1200C for 3 hours. The reaction mixture is cooled down to room temperature and poured into H2O. A gray crude product is obtained after filtration and washing with n-hexane. The crude product is purified by silicagel column chromatography with hexane/CH2CI2-, which result in a white solid (71% yield). 1H-NMR (CDCI3, ppm): 7.53 (d, 1H), 7.61(dd, 1 H), 7.75(d, 2H), 8.01-8.28(m, 12H)
Figure imgf000060_0002
(A-17) 11d) 2-Phenanthren-9-yl-8-pyren-1-yl-dibenzofuran (A-17) is prepared in analogy to example 2b) using the compound obtained in step 11c) and 9-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2- yl) phenanthrene.
1H-NMR (CDCI3, ppm): 7.53-7.57 (m, 1 H), 7.60-7.70 (m, 4H), 7.74-7.83(m, 4H), 7.90-8.00 (m, 2H), 8.01-8.09(m, 3H), 8.15(d, 2H), 8.15-8.26(m, 6H), 8.74(d, 1 H), 8.80 (d, 1 H)
The compounds of examples 12 and 13, which are shown below, are prepared in analogues manner to example 11 using the appropriate educts.
Example 12 Diphenyl-[4-(8-pyren-1-yl-dibenzofuran-2-yl)-phenyl]-amine
Figure imgf000061_0001
1H-NMR (CDCI3, ppm): 7.00-7.06 (m, 2H), 7.12-7.18 (m, 6H), 7.24-7.28 (m, 3H), 7.54-7.58 (d, 2H), 7.64-7.78 (m, 4H), 8.01-8.28 (m, 12H)
Example 13 2-Naphthalen-2-yl-8-pyren-1-yl-dibenzofuran
Figure imgf000061_0002
1H-NMR (CDCI3, ppm): 7.46-7.53 (m, 2H), 7.73-7.96(m, 8H), 8.01-8.15 (m, 6H), 8.17-8.29 (m, 5H), 8.32 (d, 1 H)
Example 14 9,10-Bis-dibenzofuran-4-yl-2,6-di-tert-butyl-anthracen
Figure imgf000062_0001
Compound B-14 is prepared in analogues manner to example 2 using the appropriate educts. 1H-NMR (CDCI3, ppm): 1.15 (s, 18H), 7.35-7.43 (m, 8H), 7.58-7.67(m, 8H), 8.08-8.12(m, 2H), 8.18 (dd, 2H)
Example 15
Synthesis of 4-(2,6-Di-tert-butyl-10-naphthalen-2-yl-anthracen-9-yl)-dibenzofu ran
15a) 9-Bromo-2,6-di-tert-butyl-anthracene
Bromine (3.02 g, 18.9 mmol) is added at 00C to a solution of 2,6-di-tert-butylanthracene (5.0 g, 17.2 mol) in carbontetrachloride (200 ml). The mixture is then stirred at 0°C for 15 hours.
After allowing to heat up to room temperature, half the amount of solvent is evaporated and the resulting mixture is poured into methanol. The precipitate is collected by filtration, recrystallized from n-hexane/methanol and the desired product is obtained as a white solid
(1.13 g).
1H-NMR (CDCI3, ppm): 1.47 (s, 9H), 1.48 (s, 9H), 7.58 (dd, 1 H), 7.67 (dd, 1H), 7.85 (d, 1H),
7.91 (d, 1 H), 8.33 (s, 1H), 8.38 (d, 1 H), 8.43 (d, 1 H)
15b) 9-Bromo-2,6-di-tert-butyl-10-iodo-anthracene lodination is done in the same manner as described in example 11b) using the compound obtained in example 15a) as starting material.
1H-NMR (CDCI3, ppm): 1.48 (2s, 18H), 7.65-7.72 (m, 2H), 8.42-8.52 (m, 4H)
15c) 4-(10-Bromo-2,6-di-tert-butyl-anthracen-9-yl)-dibenzofuran
Figure imgf000062_0002
The compound shown above is prepared in the same manner as described in example 11c) using the compound obtained in example 15b) and 1-dibenzofuranylboronic acid as starting materials.
1H-NMR (CDCI3, ppm): 1.18 (s, 9H), 1.46 (s, 9H), 7.29-7.33 (m, 1 H), 7.35-7.42 (m, 3H), 7.48-7.59 (m, 4H), 7.68 (dd, 1H), 8.07 (m, 1H), 8.15 (dd, 1H), 8.53 (d, 1 H), 8.58 (d, 1H)
Figure imgf000063_0001
15d) 4-(2, 6-Di-tert-butyl-10-naphthalen-2-yl-anthracen-9-yl)-dibenzofuran (A-35) is prepared in the same manner as described in example 2b) using the compound obtained in step 15c) and 2-(4, 4, 5, 5-tetramethyl-1 ,3,2-dioxaboran-2-yl) naphthalene as starting materials. 1H-NMR (CDCI3, ppm): 1.16 (s, 9H), 1.21 (s, 9H), 7.35-7.42 (m, 5H), 7.55-7.73 (m, 9H), 7.92-7.97 (m, 1H), 8.01-8.11 (m, 4H), 8.16-8.19 (m, 1 H)
Example 16 4-(2,6-Di-tert-butyl-10-pyren-1-yl-anthracen-9-yl)-dibenzofuran
Figure imgf000063_0002
Example 15 is repeated except using 1-(4,4,5,5-tetramethyl-1 ,3,2-dioxaboran-2-yl) pyrene in the last step. 1H-NMR (CDCI3, ppm): 1.05 (s, 9H), 1.14 (s, 9H), 7.24-8.44 (m, 22H)
Example 17
2, 6-Di-pyren-1-yl-dibenzofuran
17a) 6-Bromo-2-iodo-dibenzofuran
Figure imgf000063_0003
6-Bromo-2-iodo-dibenzofuran is prepared in the same manner as described in example 11b), except using 4-bromodibenzofurane as a starting material.
1H-NMR (CDCI3, ppm): 7.22-7.27 (t, 1 H), 7.42-7.45 (d, 1 H), 7.62-7.66 (dd, 1 H), 7.75-7.79 (dd,1H), 7.82-7.85 (dd, 1H), 8.26 (d, 1 H)
17b) 6-Bromo-2-pyren-1-yl-dibenzofuran
Figure imgf000064_0001
6-Bromo-2-pyren-1-yl-dibenzofuran is prepared in the same manner as described in example
11c), except using 6-Bromo-2-iodo-dibenzofuran as a starting material.
1H-NMR (CDCI3, ppm):7.24-7.28 (t, 1H), 7.65-7.68 (dd,1H), 7.74-7.77(dd,1 H), 7.82-7.85 (d,
1H), 7.91-7.94(dd, 1 H), 8.01-8.06(m, 3H), 8.12-8.27 (m, 7H)
17c) 2,6-Di-pyren-1-yl-dibenzofuran (A-58)
Figure imgf000064_0002
A-58 is prepared in analogy to A-17 using the appropriate educts.
1H-NMR (CDCI3, ppm):7.58-7.62 (m, 2H), 7.67-7.74(m, 2H), 8.02-8.10 (m, 6H), 8.13-8.30(m, 13H), 8.35-8.38(d, 1 H)
Example 18 6-Phenanthren-9-yl-2-pyren-1-yl-dibenzofuran
Figure imgf000065_0001
A-59 is prepared in analogy to A-58 using the appropriate educts.
1H-NMR (CDCI3, ppm):7.52-7.61 (m, 3H), 7.63-7.80 (m,6H), 7.95-8.28 (m, 13H), 8.80-8.83 (d,
1H), 8.84-8.88 (d, 1 H)
Example 19
Figure imgf000065_0002
A-60 is prepared in analogy to A-17 using the appropriate educts. 1H-NMR (CDCI3, ppm):6.64-6.89 (m,5H), 7.04-7.46 (m,11H), 8.0-8.26 (m, 14H)
Example 20
Figure imgf000065_0003
A-61 is prepared in analogy to A-58 using the appropriate educts.
1H-NMR (CDCI3, ppm): 6.62-6.86(m, 5H), 7.02-7.14(m, 5H), 7.30-7.40(m, 5H), 7.58(s, 1 H), 7.66-8.26(m, 14H) Application Examples
Application Example 1
Compounds A-1, B-1, C-1, C-2, A-9, A-10 and A-7, respectively are deposited under vacuum on a glass plate in a thickness of 60 nm. Fluorescence spectra of the deposited films are measured by fluorescence spectrophotometer (F-4500, HITACHI). The emission λmax is shown below.
Figure imgf000066_0002
Application Example 2
The following device structure is prepared: ITO/CuPCfTCTA/ Compound B-1 /TPBI/LiF/AI where ITO is indium tin oxide, CuPC is copper phthalocyanine, TCTA is 4,4',4"-tri-(N- carbazoyl)triphenylamine and TPBI is 1,3,5-tris-(N-phenyl-benzimidazol-2-yl)benzene. Using this device structure, a brightness of 50 cd/m2 is observed at 100 mA/cm2.
Application Example 3
The following device structure is prepared: ITO/CuPCfTCTA/ Compound B-1 + Compound G-1 (1.1 % by weight)/TPBI/LiF/AI. Using this device structure, a brightness of 500 cd/m2 is observed at 100 mA/cm2.
Figure imgf000066_0001
Compound G-1 (WO03105538)
Application Example 4
The following device structure is prepared: ITO/CuPCfTCTA/ Compound C-2 /TPBI/LiF/AI. Using this device structure, a brightness of 120 cd/m2 is observed at 100 mA/cm2. Application Example 5
The following device structure is prepared: ITO/CuPCfTCTA/ Compound C-2 + Compound G-1 (1.9 % by weight)/TPBI/LiF/AI. Using this device structure, a brightness of 70 cd/m2 is observed at 100 mA/cm2.
Application Example 6
The following device structure is prepared: ITO/CuPC/NPD/ Compound B-1 /TPBI/LiF/AI where NPD is N,N'-Di(naphthalene-1-yl)-N,N'-diphenyl-benzidine. Using this device structure, a brightness of 370 cd/m2 is observed at 100 mA/cm2.
Application Example 7
The following device structure is prepared: ITO/CuPC/NPD/ Compound B-1 + TBPe (1.4%) /TPBI/LiF/AI where TPBe is 2,5,8,11-tetra-t-butylperylene. Using this device structure, a brightness of 680 cd/m2 is observed at 88 mA/cm2.
Application Example 8
The following device structure is prepared: ITO/CuPC/NPD/ Compound A-10 /TPBI/LiF/AI. Using this device structure, a brightness of 3,800 cd/m2 is observed at 111 mA/cm2.
Application Example 9
The following device structure is prepared: ITO/CuPC/NPD/ Compound A-10 + TBPe (1.5%) /TPBI/LiF/AI. Using this device structure, a brightness of 2,030 cd/m2 is observed at 90 mA/cm2.
Application Examples 10 to 21
The following device structure is prepared: ITO / CuPC / NPD / Emitting layer (dibenzofuran of the present invention as a host + TBPe as a guest) / TPBI / LiF / Al. Using this device structure, bright blue EL emission is observed. The EL properties of the devices are summarized in Table 1.
Table 1 - EL properties obtained in application examples 10 TO 21
Figure imgf000067_0001
Figure imgf000068_0001
Application Example 26
The following device structure is prepared: ITO / CuPC / NPD / Emitting layer (dibenzofuran of the present invention as a host + dibenzofuran of the present invention as a guest) / TPBI / LiF / Al. Using this device structure, bright blue EL emission is observed. The EL properties of the device is summarized in Table 2.
Table 2 - EL properties obtained in application example 26
Figure imgf000068_0002

Claims

Claims
1. A compound of the formula
Figure imgf000069_0001
wherein R81, R82, R83, R84, R85, R86, R87, R88, R91, R92, R93, R94, R95, R96, R97, R91', R92', R93', R94', R95', R96' and R97' are independently of each other H, -OR201, -SR202 and/or - NR203R204, Ci-C24alkyl; Ci-C24alkyl, which is substituted by E and/or interrupted by D; C2-Ci8alkenyl, C2-Ci 8alkenyl, which is substituted by E, C3-C8cycloalkyl, C3-C8cycloalkyl, which is substituted by G, aryl, aryl, which is substituted by G, heteroaryl, or heteroaryl, which is substituted by G, silyl, -^SiR62R63R64, -CN, cyclic ether, -B(OR65J2 and/or halogen, especially fluorine, or
R81 and R82, R82 and R83, R83 and R84, R85 and R86, R86 and R87, R87 and R88, R97 and R96, R96 and R95, R95 and R94, R97' and R96', R96' and R95', R95' and/or R94', and/or two of the groups R91, R92 and R93 or R91', R92' and R93', which are in neighbourhood to each
other, together form a group
Figure imgf000069_0002
, wherein A41, A42, A43, A44,
A45, A46 and A47 are independently of each other H, halogen, hydroxy, CrC24alkyl, Cr C24alkyl which is substituted by E and/or interrupted by D, Ci-C24perfluoroalkyl, C5- Ci2cycloalkyl, C5-d2cycloalkyl which is substituted by G and/or interrupted by S-, -O-, or -NR5-, C5-Ci2cycloalkoxy, C5-Ci2cycloalkoxy which is substituted by E, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2-C24alkenyl, C2-C24alkynyl, CrC24alkoxy, CrC24alkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, C7-C25aralkyl, which is substituted by G, C7-C25aralkoxy, C7-C25aralkoxy which is substituted by E, or -CO-R8, M is a bonding group, such as a single (direct) bond, -CO-, -COO-; -S-; -SO-; -SO2-; -O- ; CrCi2alkylene, C2-Ci2alkenylene, or C2-Ci2alkinylene, which are optionally interrupted by one or more -0-, or -S-; or a group [M1Jn, wherein n is an integer 1 to 20, M1 is arylene, or heteroarylene, which is optionally substituted by G, especially naphthylene, biphenylene, styrylene, anthrylene, or pyrenylene, which are optionally substituted by CrCi2alkyl, halogen, -OR201, -SR202 and/or -NR203R204, wherein R201 is hydrogen, Ci-C24alkyl, Ci-C24alkyl, which is substituted by E and/or interrupted by D; C2-Ci2alkenyl, C3-C6alkenoyl, C3-C8cycloalkyl, or benzoyl, each of which may optionally be substituted by one or more groups Ci-C6alkyl, halogen, -OH and/or Cr C4alkoxy; C6-Ci4aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, each of which may optionally be substituted by halogen, -OH, CrCi2alkyl, CrCi2alkoxy, phenoxy, CrCi2alkylsulfanyl, phenylsulfanyl, -N(Ci-Ci2alkyl)2 and/or diphenylamino; R202 is Ci-C24alkyl, Ci-C24alkyl, which is substituted by E and/or interrupted by D; C2- Ci2alkenyl, CrC8alkanoyl, C2-Ci2alkenyl, C3-C6alkenoyl; C3-C8cycloalkyl, or benzoyl, each of which may optionally be substituted by one or more groups CrC6alkyl, halogen, -OH, CrC4alkoxy or d-C4alkylsulfanyl; C6-Ci4aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, each of which may optionally be substituted by halogen, CrCi2alkyl, CrCi2alkoxy, phenyl-CrC3alkyloxy, phenoxy, CrCi2alkylsulfanyl, phenylsulfanyl, -N(CrCi2alkyl)2, diphenylamino, -(CO)O(CrC8alkyl), -(CO)-Ci -C8alkyl, or (CO)N(CrC8alkyl)2;
R203 and R204 are independently of each other hydrogen, CrC24alkyl, CrC24alkyl, which is substituted by E and/or interrupted by D; C2-C5alkenyl, C3-C8cycloalkyl, or benzoyl, each of which may optionally be substituted by one or more groups d-C6alkyl, halogen, -OH, or CrC4alkoxy; phenyl-CrC3alkyl, CrC8alkanoyl, C3-Ci2alkenoyl, C6-Ci4aryl, especially phenyl naphthyl, phenanthryl, anthranyl, or pyrenyl, each of which is optionally substituted by CrCi2alkyl, benzoyl or CrCi2alkoxy; or R203 and R204 together are C2-C8alkylene, or branched C2-C8alkylene optionally interrupted by -0-, -S-, or - NR205- and/or optionally substituted by hydroxyl, CrC4alkoxy, C2-C4alkanoyloxy, or benzoyloxy, wherein the ring formed by R203 and R204 can optionally be condensed one or two times by phenyl which can be substituted one to three times with CrC8-alkyl, Cr C8-alkoxy, halogen, or cyano;
R205 is hydrogen, CrC24alkyl, CrC24alkyl, which is substituted by E and/or interrupted by D; C2-C5alkenyl, C3-C8cycloalkyl, phenyl-CrC3alkyl, CrC8alkanoyl, C3-Ci2alkenoyl, C6-Ci4aryl, especially benzoyl; phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, each of which is optionally substituted by CrCi2alkyl, benzoyl, or Ci-Ci2alkoxy; D is -CO-, -COO-, -OCOO-, -S-, -SO-, -SO2-, -0-, -NR5-, -SiR61R62-, -POR5- , -CR63=CR64-, or -C≡C-;
E is halogen, C6-Ci4aryl, especially phenyl, naphthyl, phenanthryl, anthranyl, or pyrenyl, which may be substituted by -OR5, -SR5, -NR5R6, ^SiR62R63R64, wherein R62, R63 and R64 are independently of each other a Ci-C8alkyl group, a C6-C24aryl group or a C7- Ci2aralkylgroup, -CN, cyclic ether and/or -B(OR65J2, wherein R65 is hydrogen, d- C24alkyl, C3-C8cycloalkyl, C7-C24aralkyl, C2-Ci 8alkenyl, C2-C24alkynyl, hydroxy, mercapto, Ci-C24alkoxy, Ci-C24alkylthio, C6-C3OaPyI, C2-C3oheterc>arylJ halogen, especially fluorine, haloalkane, silyl, siloxanyl, and an alicyclic ring formed with adjacent substituents R65; -OR5, -SR5, -NR5R6, -COR8, -COOR7, -CONR5R6, -CN, halogen, silyl, d-dβalkyl, or heteroaryl,
G is E, or CrCi8alkyl, wherein R5 and R6 are independently of each other H, C6-Ci8aryl; C6-Ci8aryl which is substituted by CrCi8alkyl, Ci-Ci8alkoxy, or silyl; Ci-Ci8alkyl or d- Ci8alkyl which is interrupted by -O-; or
R5 and R6 together form a five or six membered ring, in particular
Figure imgf000071_0001
or
Figure imgf000071_0002
R7 is H, C6-Ci8aryl, C7-Ci2alkylaryl, which are optionally substituted by Ci-d8alkyl, or
Ci-Ci8alkoxy; Ci-Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -O-;
R8 is C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-d8alkyl, or CrCi8alkoxy; d-
Ci8alkyl, C7-Ci2alkylaryl, or Ci-Ci8alkyl which is interrupted by -O-;
R61 and R62 are independently of each other C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ci8alkyl, CrCi8alkoxy; or Ci-Ci8alkyl which is interrupted by -O-, and
R63 and R64 are independently of each other H, C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-d8alkyl, Ci-Ci8alkoxy; or Ci-Ci8alkyl which is interrupted by -O-; with the proviso that at least one of R81, R82, R83, R84, R85, R86, R87 and R88 is different from
H, -OR201, -SR202 and Ci-C24alkyl; and the further proviso that the following compounds are excluded:
Figure imgf000071_0003
Figure imgf000072_0001
Figure imgf000073_0001
2. The compound of formula Il according to claim 1, wherein M is a single
bond, -CO-, -COO-, -S-, -SO-, -SO2-, -O-,
Figure imgf000073_0002
, especially
Figure imgf000074_0001
, especially
Figure imgf000074_0002
especially
Figure imgf000074_0003
Figure imgf000074_0004
, especially or
Figure imgf000074_0005
, especially
Figure imgf000075_0001
, or , wherein n1, n2, n3, n4, n5, n6 and n7 are integers of 1 to 10, in particular 1 to 3, A6 and A7 are independently of each other H, CrCi8alkyl, d-Ci8alkyl which is substituted by E' and/or interrupted by D', C6-C24aryl, C6-C24aryl which is substituted by G', C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G', C2-Ci8alkenyl, C2- Ci8alkynyl, CrCi8alkoxy, Ci-Ci8alkoxy which is substituted by E' and/or interrupted by D', C7-C25aralkyl, or -CO-A28,
A8 is CrCi8alkyl, CrCi8alkyl which is substituted by E' and/or interrupted by D', C6-C24 aryl, or C7-C25aralkyl, A9 and A10 are independently of each other Ci-Ci8alkyl, d-Ci8alkyl which is substituted by E' and/or interrupted by D', C6-C24aryl, C6-C24aryl which is substituted by G', C2- C20heteroaryl, C2-C20heteroaryl which is substituted by G', C2-Ci 8alkenyl, C2-Ci 8alkynyl, CrCi8alkoxy, Ci-Ci8alkoxy which is substituted by E' and/or interrupted by D', or C7- C25aralkyl, or
A9 and A10 form a ring, especially a five- or six-membered ring, which can optionally be substituted by one or more CrCi8 alkyl groups;
A14 and A15 are independently of each other H, CrCi8alkyl, Ci-Ci8alkyl which is substituted by E' and/or interrupted by D', C6-C24aryl, C6-C24aryl which is substituted by G', C2-C20heteroaryl, or C2-C20heteroaryl which is substituted by G', D' is -CO-; -COO-; -S-; -SO-; -SO2-; -0-; -NA25-; -SiA30A31-; -POA32-; -CA23=CA24-; or - C≡C-; and
E' is -OA29; -SA29; -NA25A26; -COA28; -COOA27; -CONA25A26; -CN; -OCOOA27; or halogen; G' is E', or Ci-Ci8alkyl; wherein A23, A24, A25 and A26 are independently of each other H; C6-Ci8aryl; C6-Ci8aryl which is substituted by CrCi8alkyl, or Cr Ci8alkoxy; CrCi8alkyl, or Ci-Ci8alkyl which is interrupted by -O-; or A25 and A26
together form a five or six membered ring, in particular
Figure imgf000076_0001
Figure imgf000076_0002
A27 and A28 are independently of each other H; C6-Ci8aryl; C6-Ci8aryl which is substituted by CrCi8alkyl, or CrCi8alkoxy; CrCi8alkyl, or CrCi8alkyl which is interrupted by -O-,
A29 is H; C6-Ci8aryl; C6-Ci8aryl, which is substituted by CrCi8alkyl, or CrCi8alkoxy; Cr
Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -O-,
A30 and A31 are independently of each other CrCi8alkyl, C6-Ci8aryl, or C6-Ci8aryl, which is substituted by Ci-d8alkyl, and
A32 is CrCi8alkyl, C6-Ci8aryl, or C6-Ci8aryl, which is substituted by CrCi8alkyl.
3. The compound of formula I according to claim 1 , wherein at least one of the groups R81,
□82 R83 R84 R85 R86 R87 R88 R91 R92 R93 R94 R95 R96 R97 R91' R92' R93' R94' R95' R96 and R97 is a group
Figure imgf000077_0001
, wherein A14 and A15 are independently of each other H, CrCi8alkyl, CrCi8alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G, and A16 is H, CrCi8alkyl, CrCi8alkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, C2- C20heteroaryl, or C2-C20heteroaryl which is substituted by G; or a polycyclic aryl group, especially pentalenyl, indenyl, azulenyl, naphthyl, biphenylenyl, as-indacenyl, s- indacenyl, acenaphthylenyl, fluorenyl, phenanthryl, anthracenyl, fluoranthenyl, acephenanthrylenyl, aceanthrylenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, picenyl, perylenyl, pentacenyl, pentaphenyl, hexacenyl, or hexaphenyl, which can optionally be substituted by G, wherein D, E and G are as defined in claim 1.
4. The compound of formula I according to claim 1 , wherein at least one of the groups R81,
□82 R83 R84 R85 R86 R87 R88 R91 R92 R93 R94 R95 R96 R97 R91' R92' R93' R94' R95'
R96' and R97' is a group of the formula -(W1)a-(W2)b-W3, wherein a and b are 0, or 1 ,
W1 and W2 are independently of each other a group of formula
W
Figure imgf000077_0002
3 is a group of formula
Figure imgf000078_0001
R >1m1 D n1n1' D n1K2 D ni1z2' D nu13 D nu13' D ni155 D n1i5a' D n1i6o D n1i6b' D n1i7l D n1i7/' D n4il1 D n44Vi D n«42 D n«42' D n4444 D nM44' n 34w5 , r\ , r\ , , , , ,
R45', R46, R46', R47 and R47' are independently of each other H, E, silyl, such as tri(Cr C8alkyl)silyl, C6-Ci8aryl; C6-Ci8aryl which is substituted by G; CrCi8alkyl; Ci-Ci8alkyl which is substituted by E and/or interrupted by D; CrCi8alkoxy; or CrCi8alkoxy which is substituted by E and/or interrupted by D; C7-Ci 8aralkyl; or C7-Ci8aralkyl which is substituted by G;
R14 is H, Ci-Ci8alkyl; silyl, such as tri(Ci-C8alkyl)silyl, or Ci-Ci8alkyl which is substituted by E and/or interrupted by D; CrCi8alkoxy; or CrCi8alkoxy which is substituted by E
and/or interrupted by D;
Figure imgf000078_0002
Figure imgf000078_0003
R18 and R19 are independently of each other CrCi8alkyl; CrCi8alkoxy, C6-Ci8aryl; C7- Ci8aralkyl; or R18 and R19 together form a ring especially a five- or six-membered ring, which can optionally be substituted by CrC8alkyl,
R21, R22, R23, R24, R25, R26 and R27 are independently of each other H, E, CrCi8alkyl; Ci-Ci8alkyl which is substituted by E and/or interrupted by D; C7-Ci 8aralkyl; C7- Ci8aralkyl which is substituted by G; or W3 is a group of formula
Figure imgf000079_0001
Figure imgf000079_0002
, wherein R315 and R316 are independently of each other a hydrogen atom, a d-Ci8alkyl group, a
CrCi8alkoxy group, a group of formula
Figure imgf000080_0001
, or
Figure imgf000080_0002
, wherein R318, R319 and R320 independently from each other stand for hydrogen, Ci-C8-alkyl, Ci-C8-alkoxy, or phenyl, and
R317 stands for is a hydrogen atom, a Ci-C25alkyl group, which might be interrupted by - O-, a cycloalkyl group, a C7-Ci8aralkyl group, a C6-Ci8aryl group, or a heterocyclic group, which may be substituted by G; wherein
D is -CO-, -COO-, -OCOO-, -S-, -SO-, -SO2-, -0-, -NR5-, SiR61R62-, -POR5- , -CR63=CR64-, or -C≡C-;
E is -OR5, -SR5, -NR5R6, -COR8, -COOR7, -OCOOR7, -CONR5R6, -CN, or halogen; G is E, or Ci-Ci8alkyl; wherein R5 and R6 are independently of each other C6-Ci8aryl; C6-Ci8aryl which is substituted by CrCi8alkyl, or CrCi8alkoxy; CrCi8alkyl, or Cr Ci8alkyl which is interrupted by -O-; or
R5 and R6 together form a five or six membered ring, in particular
Figure imgf000080_0003
O
— N
O
R7 is C7-Ci2alkylaryl; Ci-Ci8alkyl; or Ci-Ci8alkyl which is interrupted by -0-;
R8 is C6-Ci8aryl; C6-Ci8aryl which is substituted by CrCi8alkyl, or CrCi8alkoxy; Cr
Ci8alkyl; C7-Ci2alkylaryl, or Ci-Ci8alkyl which is interrupted by -O-;
R61 and R62 are independently of each other C6-Ci8aryl; C6-Ci8aryl which is substituted by CrCi8alkyl, or CrCi8alkoxy; or CrCi8alkyl which is interrupted by -O-, and
R63 and R64 are independently of each other H, C6-Ci8aryl; C6-Ci8aryl which is substituted by CrCi8alkyl, CrCi8alkoxy; or CrCi8alkyl which is interrupted by -0-; or V\r is a group of formula -NR υR , wherein R υ and R are independently of each
other a group of formula
Figure imgf000081_0001
, wherein
R72, R73 and R74 are independently of each other hydrogen, d-C8alkyl, a hydroxyl group, a mercapto group, Ci-C8alkoxy, Ci-C8alkylthio, halogen, halo-Ci-C8alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group or a siloxanyl group, or R70 and R71 together with the nitrogen atom to which they are bonded form a five or six membered
heterocyclic ring, such as
Figure imgf000081_0002
Figure imgf000081_0003
, which can be condensed by one or two optionally substituted phenyl
groups, such as
Figure imgf000081_0004
, wherein R216 and R217 independently from each other stands for hydrogen, CrC8alkyl, CrC8alkoxy, or phenyl, and
X1 stands for hydrogen, or CrC8alkyl;
R75, R76, R77 and R78 are independently of each other H, E, C6-Ci8aryl; C6-Ci8aryl which is substituted by E; CrCi8alkyl; CrCi8alkyl which is substituted by G and/or interrupted by D; C7-Ci 8aralkyl; or C7-Ci8aralkyl which is substituted by E; wherein D, E and G are as defined above.
5. The compound according to claim 1 , 3, or 4:
Figure imgf000081_0005
(A-1),
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
(B-8),
Figure imgf000092_0001
(B-11), (B-12),
Figure imgf000093_0001
6. The compound of formula I according to claim 1 , wherein at least one, preferably two of the substituents R81, R82, R83, R84, R85, R86, R87, R88, R91, R92, R93, R94, R95, R96, R97, R91', R92', R93', R94', R95', R96' and R97' are independently of each other a group of the formula -W1 -(W2)b-W3, wherein b is 0, or, 1 , W1 and W2 are independently of each other a group of formula
Figure imgf000094_0001
,
Figure imgf000094_0002
, especially , or
W3 is a group of formula -NR70R71, wherein R70 and R71 are independently of each
other a group of formula
Figure imgf000094_0003
, especially or wherein R72, R73 and R74 are independently of each other hydrogen, d-C8alkyl, a hydroxyl group, a mercapto group, Ci-C8alkoxy, Ci-C8alkylthio, halogen, halo-Ci- C8alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group or a siloxanyl group, or R70 and R71 together with the nitrogen atom to which they are bonded form a
Figure imgf000094_0004
five or six membered heterocyclic ring, such as
Figure imgf000094_0005
, which can be condensed by one or two optionally substituted phenyl groups, such as
Figure imgf000095_0001
, wherein R216 and R217 independently from each other stands for hydrogen, d-C8alkyl, CrC8alkoxy, or phenyl, and X1 stands for hydrogen, or CrC8alkyl;
R75, R76, R77 and R78 are independently of each other H, E, C6-Ci8aryl; C6-Ci8aryl which is substituted by E; CrCi8alkyl; CrCi8alkyl which is substituted by G and/or interrupted by D; C7-Ci 8aralkyl; or C7-Ci8aralkyl which is substituted by E; wherein D, E, G, R11, R11', R12', R16, R16', R17, R17', R18, R19, R30, R31, R32 and R33 are as defined in claim 5, and R30', R31', R32' and R33' independently of each other have the meaning of R30.
7. The compound according to claim 6:
Figure imgf000095_0002
8. A composition comprising a compound according to any of claims 1 to 7.
9. An electroluminescent device, comprising a compound according to any of claims 1 to 7, or a composition according to claim 8.
10. Use of the compounds according to any of claims 1 to 7, or the composition according to claim 8 for electrophotographic photoreceptors, photoelectric converters, solar cells, image sensors, dye lasers and electroluminescent devices.
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