WO2016079667A1 - Indole derivatives for electronic applications - Google Patents

Indole derivatives for electronic applications Download PDF

Info

Publication number
WO2016079667A1
WO2016079667A1 PCT/IB2015/058877 IB2015058877W WO2016079667A1 WO 2016079667 A1 WO2016079667 A1 WO 2016079667A1 IB 2015058877 W IB2015058877 W IB 2015058877W WO 2016079667 A1 WO2016079667 A1 WO 2016079667A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituted
optionally
cisalkyl
interrupted
Prior art date
Application number
PCT/IB2015/058877
Other languages
French (fr)
Inventor
Yuki Nakano
Takushi Shiomi
Original Assignee
Idemitsu Kosan Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Co., Ltd. filed Critical Idemitsu Kosan Co., Ltd.
Publication of WO2016079667A1 publication Critical patent/WO2016079667A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • 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
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • 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
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • 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
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
    • 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
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • 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
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • 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
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • 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
    • 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]
    • H10K50/18—Carrier blocking layers
    • 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

Definitions

  • the present invention relates to compounds of formula I, a process for their production and their use in electronic devices, especially electroluminescent devices.
  • the compounds of formula I may provide improved efficiency and reduced driving voltage of electroluminescent devices.
  • US2002117662 discloses a light-emitting device comprising: a pair of electrodes formed on a substrate; and at least one organic compound layer containing a light-emitting layer provided between the electrodes, wherein the at least one organic compound layer comprises a host material, a layer of the host material has an energy gap of not less than 3.6 eV and an ionization potential of the host material is from 5.4 eV to 6.3 eV.
  • the host material compri prising a partial structure repre-
  • L 12 represents one of a from 2- to 6-valent connecting group having a heteroaryl group and a from 2- to 6-valent connecting group comprising a non-conjugate connecting group having an arylene group; n represents an integer of from 2 to 6; R represents one of an alkyl group having from 1 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, a heteroaryl group having from 2 to 20 carbon atoms and a silyl group having from 3 to 20 carbon atoms; and m represents an integer of from 0 to 6.
  • WO08066196 is directed to an organic electroluminescent device comprising: a pair of electrodes; and at least one organic layer between the pair of electrodes, the at least one organic layer including a light-emitting layer containing a light-emitting material, wherein the at least one organic layer includes at least one layer containing an indole derivative represented by formula (1):
  • Rios e ach independently represents a hydrogen atom or a substituent
  • R 106 represents an alkyl group having a tertiary or quaternary carbon atom
  • R 101 and R 106 may be bonded to each other to form a ring
  • L 101 represents a linking group
  • n 101 represents an integer of 2 or higher.
  • JP2003277744 relates to a material for an organic electroluminescent element which comprises a compound comprising a group bearing an indole skeleton and, bonded thereto, a group bearing a cycloalkane skeleton or a meta-aromatic ring group.
  • the organic electroluminescent element comprises a monolayered or multi-layered organic thin film layers sandwiched between a cathode and an anode, where at least one layer of the organic thin film layers contains the material for the organic electroluminescent element.
  • JP2009049318 relates to an electroluminescent device which comprises an indole deriva
  • R 106 denotes a silyl substituent.
  • JP2012089777 relates to an electroluminescence element which is characterized in that at least one of the organic compound layers contains a compound represented by following
  • KR20140087805A discloses compounds for organic optoelectronic devices, including or
  • n is an integer of 1 to 3 and, R 1 is hydrogen, deuterium, halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1-C20 amine group, a nitro group, a carboxyl group, a ferrocenyl group, a substituted or unsubstituted C1- C20alkyl group, a substituted or unsubstituted C6-C30arylgroup, a substituted or unsubstituted C2 to C30heteroaryl group ...
  • L may be a group of formula (X is O, or S), which is bonded to the indole skeleton by a C-C bond.
  • KR20140103842 discloses an organic light emitting device including a compound repre-
  • the present invention provides further materials suitable for use in OLEDs and further applications in organic electronics. More particularly, it should be possible to provide charge transport materials, charge/exciton blocker materials and matrix materials for use in OLEDs.
  • the materials should be suitable especially for OLEDs which comprise at least one phosphorescence emitter, especially at least one green emitter or at least one blue emitter.
  • the materials should be suitable for providing OLEDs which ensure good efficiencies, good operative lifetimes and a high stability to thermal stress, and a low use and operating voltage of the OLEDs.
  • indole derivatives are found to be suitable for use in organo-electroluminescent devices.
  • said derivatives are suitable charge transport materials, or host materials for phosphorescent emitters with low driving voltage, good efficiency and good operative lifetimes.
  • Ar 1 and Ar 2 are independently of each other a C6-C24arylen group, which can optionally be substituted by G, a C2-C3oheteroarylen group, which can optionally be substituted by G, Bi is N, or CR 3 ,
  • B3 is N, or CRs
  • B 4 is N, or CR 6 ,
  • Bii is N, or CRsi
  • Bi6 is N, or CRse
  • Bi 8 is N, or CRss
  • R 1 and R 2 are independently of each other -H, -F, CN, a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24aryloxy group, which can optionally be substituted by G;
  • X i is O, S, Se or NR 7 ,
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is -CN, then A is -NR 10 R 11 , or -Si(R 1 )(R 13 )(R 14 ), a C 6 -C 2 4aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
  • R58 are independently of each other -H, -F, CN, a C2-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24 aryloxy group, which can optionally be substituted by G;
  • R 7 is a Ci-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C25cycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G;
  • R 10 and R 11 are independently of each other H, a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
  • R 12 , R 13 and R 14 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by L;
  • a C6-C24aryl group which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G; with the proviso that, if all of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are different from -CN, then
  • A is a C6-C24arylen group, which can optionally be substituted by G, a Ci3-C3oheteroarylen group, which can optionally be substituted by G, an azacarbazolyl, which can optionally be substituted by G, an azaindolyl, which can optionally be substituted by G, a dibenzofuranyl, which can optionally be substituted by G, a dibenzothiophenyl, which can optionally be substituted by G, a benzofuranyl, which can optionally be substituted by G, a benzothio- phenyl, which can optionally be substituted by G, a pyridyl, which can optionally be substituted by G, a pynmidinyl, which can optionally be substituted by G, a pyrazinyl, which can optionally be substituted by G, a triazinyl, which can optionally be substituted by G, a naph- , or
  • B 19 is N or CR 61 , preferably CR 61 ,
  • B 20 is N or CR 62 , preferably CR 62 ,
  • B 2i is N or CR6 3 , preferably CR6 3 ,
  • B 22 is N or CR 64 , preferably CR 64 ,
  • B 23 is N or CR 65 , preferably CR 65 ,
  • B 24 is N or CR 66 , preferably CR 66 ,
  • B 2 5 is N or CR6 7 , preferably CR6 7 ,
  • B 26 is N or CR 68 , preferably CR 68 ,
  • B 27 is N or CR 69 , preferably CR 69 ,
  • B 28 is N or CR 70 , preferably CR 70
  • B 29 is N or CR 71 , preferably CR 71 ,
  • B 30 is N or CR 72 , preferably CR 72 ,
  • B3 i is N or CR 7 3, preferably CR 7 3,
  • B 32 is N or CR 74 , preferably CR 74 ,
  • N in the groups of formula (III) and (IV) chemically binds to one of B 15 , B 16 , B 17 , or B 18 , or Ar 1 , or Ar 2 , if present;
  • R74 are independently of each other -H, -F, -C ⁇ N, a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2- C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24aryloxy group, which can optionally be substituted by G;
  • E is -ORS1 , -SR 31 , -NR 32 R 33 , -COR 34 , -COOR 34 , -CONR 32 R 33 , -C ⁇ N, or -F,
  • L is D, or -SiR 22 R 23 -,
  • G is E, or a Ci-Cisalkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by -F, Ci-Cisalkyl, or Ci-Cisalkyl which is interrupted by -0-; a C2-C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by -F, Ci-Cisalkyl, or Ci-Cisalkyl which is inter- rupted by O;
  • R 21 , R 32 and R 33 are independently of each other a C6-Cisaryl group; a C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O-; or R 32 and R 33 together form a five or six membered ring, R 22 and R 23 are independently of each other a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl,
  • R 24 is a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl,
  • R 25 and R 26 are independently of each other H, C6-Cisaryl; C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; Ci-Cisalkyl; or Ci-Cisalkyl which is interrupted by -0-, R 31 is a C6-Cisaryl; a C6-Cisaryl, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci- Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O- and
  • R 34 is a C6-Cisaryl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, or Ci- Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-.
  • the combination of the hole transporting indole group with the dibenzofuranyl group gives rise to materials that are highly suitable in devices that emit green, or blue light.
  • the improved amipolar characteristics give rise to more balanced charge transport in devices resulting in lower voltages and higher external quantum efficiencies (EQE's).
  • the compounds of the present invention may be used for electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaics), switching elements, such as organic transistors, for example, organic FETs and organic TFTs, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers and electroluminescent devices, such as, for example, organic light-emitting diodes (OLEDs).
  • a further subject of the present invention is directed to an electronic device, comprising a compound according to the present invention.
  • the electronic device is preferably an electroluminescent device.
  • the compounds of formula I can in principal be used in any layer of an EL device, but are preferably used as host, charge transport and/or charge/exciton blocking material. Particularly, the compounds of formula I are used as host material for green, especially blue light emitting phosphorescent emitters.
  • a further subject of the present invention is directed to a charge transport layer, comprising a compound of formula I according to the present invention.
  • a further subject of the present invention is directed to an emitting layer, comprising a compound of formula I according to the present invention.
  • a compound of formula I is preferably used as host material in combination with a phosphorescent emitter.
  • a further subject of the present invention is directed to a charge/exciton blocking layer, comprising a compound of formula I according to the present invention.
  • D is preferably -CO-, -COO-, -S-, -SO-, -S0 2 -, -0-, -NR21-, wherein R21 is Ci-Ci 8 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or Ce-C aryl, such as phenyl, tolyl, naphthyl, or biphenylyl, or C2-C3oheteroaryl, such as, for example, benzimid-
  • E is preferably -OR31 ; -SR3i ; -NR32R33; -COR34; -COOR34; -CONR32R33; 0 r -CN; wherein R3i , R32, R33 anc
  • R34 are independently of each other Ci-Cisalkyl, such as methyl, ethyl, n- propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or Ce-C aryl, such as phenyl, tolyl, naphthyl, or biphenylyl.
  • Ci-Cisalkyl such as methyl, ethyl, n- propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-eth
  • G is preferably -OR 31 ; -SR3 i ; -NR32R33; a Ci-Ci 8 alkyl group, a C 6 -Ci 4 aryl group, a Ce- C aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Ci3heteroaryl group, or a C2- Ci 3 heteroaryl group, which is substituted by F, or Ci-Cisalkyl; wherein R 31 , R 3 2, R33 and R 3 4 are independently of each other Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n- butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-Ci 4 aryl, such as phenyl, tolyl, naphthyl, or biphenylyl.
  • benzim- idazolo[2,1-b][1 ,3]benzothiazolyl carbazolyl, dibenzofuranyl, or dibenzotihophenyl, which can be unsubstituted or substituted, especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl ; or C2-Ci3heteroaryl.
  • (la) are more pi ferred, wherein R 1 , R 2 , R 3 , R 4 , R5, R6, en, B 12 , B 13 , B 14 , B 15 , B 16 , B 17 , B 1 8, ⁇ , Ar 1 , Ar 2 , A, and n are defined above and below.
  • X i is NR 7 , O, or S,
  • R 1 , R 2 , R 3 , R 4 , Rs, Re, R7, Ar 1 and A are defined above and below, and
  • n 0.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other -H, or -CN.
  • Ar 1 and Ar 2 are independently of each other a C6-C24arylen group, which can optionally be substituted by G, a C2-C3oheteroarylen group, which can optionally be substituted by G,
  • the C6-C24arylen groups Ar 1 and Ar 2 which optionally can be substituted by G, are typically phenylene, 4-methylphenylene, 4-methoxyphenylene, naphthylene, especially 1- naphthylene, or 2-naphthylene, biphenylylene, terphenylylene, pyrenylene, 2- or 9- fluorenylene, phenanthrylene, or anthrylene, which may be unsubstituted or substituted.
  • the C2-C3oheteroarylen groups Ar 1 and Ar 2 which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms havi ated-electrons such as, for example, benzofu-
  • R 24' is a C6-C24aryl group, or a C2-C3oheteroaryl group, which can optionally be substituted by G, wherein G is as defined in above.
  • a further example for a C2-C3oheteroarylen group Ar 1 and Ar 2 is 2-phenyl pyrimidinylene.
  • C6-C24arylen groups are 1 ,3-phenylene, 1 ,4-phenylene, 3,3'-biphenylylene, 3,3'- m-te ⁇ henylene, 2- or 9-fluorenylene, phenanthrylene, which may be unsubstituted or substituted, especially by C6-Cioaryl , C6-Cioaryl which is substituted by Ci-C4alkyl ; or C2- C heteroaryl.
  • Preferred C2-C3oheteroarylen groups are pyridylene, triazinylene, pyrimidinylene, benzofu- ro[2,3-b]pyridylene, benzothiopheno[2,3-b]pyridylene , pyrido[2,3-b]indolylene , benzofu- ro[2,3-c]pyridylene, benzothiopheno[2,3-c]pyridylene , pyrido[2,3-c]indolylene, furo[3,2- b:4,5-b']dipyridylene, thieno[3,2-b:4,5-b']dipyridylene, pyrrolo[3,2-b:4,5-b']dipyridylene, dibenzofuranylene, dibenzothiophenylene , carbazolylene and benzimidazo[1 ,2- a] benzimidazo-2,5-ylene,
  • G is preferably Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, -CF3, a C6-Ci4aryl group, a Ce-C aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Ci3heteroaryl group, or a C2-Ci3heteroaryl group, which is substituted by F, or Ci-Cisalkyl.
  • Ci-Cisalkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, -CF3, a C6
  • Benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimidazo[1 ,2-a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are examples of a C2-Ci3heteroaryl group.
  • Phenyl, 1-naphthyl and 2- naphthyl are examples of a Ce-C aryl group.
  • Ar 1 and Ar 2 are independently of each other a group of formula
  • Ar 1 and Ar 2 are:
  • Ri, R2, R3, R4, R5 and R6 is -CN
  • A is -NRi°Rii, or -Si(Ri2)(Ri3)(Ri4), a C6-C24ar l group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G.
  • the C6-C24aryl group A which optionally can be substituted by G, is typically phenyl, 4- methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, or anthryl, or triphenylenyl (especially triphenylen-2-yl), which may be unsubstituted or substituted.
  • the C2-C3oheteroaryl group A which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated ⁇ -electrons such as 9H-pyrido[2,3-b]indolyl, benzofuro[2,3- b]pyridyl, benzothiopheno[2,3-b]pyridyl, 9H-pyrido[2,3-c]indolyl, benzofuro[2,3-c]pyridyl, benzothiopheno[2,3-c]pyridyl, furo[3,2-b:4,5-b']dipyridyl, pyrrolo[3,2-b:4,5-b']dipyridyl, thieno[3,2-b:4,5-b']dipyrid
  • the C6-C24aryl and C2-C3oheteroaryl groups may be substituted by G.
  • G is preferably Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl; -CF3, a C6-Ci4aryl group, a Ce-C aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Ci3heteroaryl group, or a C2-Ci3heteroaryl group, which is substituted by F, or Ci-Cisalkyl.
  • Prefered C2-C3oheteroaryl groups are pyridyl, triazinyl, pyrimidinyl, especially 9H-pyrido[2,3- b]indolyl, benzofuro[2,3-b]pyridyl, benzothiopheno[2,3-b]pyridyl, 9H-pyrido[2,3-c]indolyl, benzofuro[2,3-c]pyridyl, benzothiopheno[2,3-c]pyridyl, furo[3,2-b:4,5-b']dipyridyl, pyr- rolo[3,2-b:4,5-b']dipyridyl, thieno[3,2-b:4,5-b']dipyridyl, benzimidazo[1 ,2-a]benzimidazo-5-yl
  • azolo[2,1-b][1 ,3]benzothiazolyl ( , or ), carba- zolyl, dibenzofuranyl, or dibenzothiophenyl, which can be unsubstituted or substituted especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl .
  • R 41 are independently of each other -H, -CN, or a phenyl group.
  • A is a C 6 -C 2 4aryl group, which can optionally be substituted by G, a Ci3-C3oheteroaryl group, which can optionally be sub- stituted by G, an azacarbazolyl, which can optionally be substituted by G, an azaindolyl, which can optionally be substituted by G, a dibenzofuranyl, which can optionally be substituted by G, a dibenzothiophenyl, which can optionally be substituted by G, a benzofuranyl, which can optionally be substituted by G, a benzothiophenyl, which can optionally be substituted by G, a pyridyl, which can optionally be substituted by G, a pyrimidinyl, which can optionally be substituted by G, a pyrazinyl, which can optionally be substituted by
  • the group of formula (III) is preferably a group of formula
  • R 41 are independently of each other -H, -CN, or a phenyl group.
  • the present invention relates to compounds of formula (I), wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are H.
  • compounds of formula (I) wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are H.
  • the present invention relates to compounds of formula (I), wherein at least one of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is -CN.
  • R 1 , R2, R3, R5, or R 6 is -CN are shown below.
  • Examples of preferred compounds of formula I are compounds (D-33), (D-34), (D-35), (D- 36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) shown above.
  • compounds (D74) to (D131) shown above are compounds (D-33), (D-34), (D-35), (D- 36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57
  • Ci-C25alkyl (Ci-Cisalkyl) is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.
  • n-butyl isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3- pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1 -methyl hexyl, 1,1 ,3,3,5,5- hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyl- heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, oroctadecyl.
  • Ci-Csalkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2- ethylhexyl.
  • Ci-C4alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, iso- butyl, tert.-butyl.
  • Ci-C25alkoxy groups are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, un- decyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy.
  • Ci-Csalkoxy examples are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2- dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1,1,3,3-tetramethylbutoxy and 2- ethylhexyloxy, preferably Ci-C4alkoxy such as typically methoxy, ethoxy, n-propoxy, iso- propoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy.
  • cycloalkyl group is typically C5-Ci2cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted.
  • C6-C24aryl (C6-Cisaryl), which optionally can be substituted, is typically phenyl, 4- methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, oranthryl, which may be unsubstituted or substituted.
  • Phenyl, 1-naphthyl and 2-naphthyl are examples of a C6-Cioaryl group.
  • C6-C24aryloxy which optionally can be substituted, is typically C6-Cioaryloxy, which optionally can be substituted by one, or more Ci-Csalkyl and/or Ci-Csalkoxy groups, such as, for example, phenoxy, 1-naphthoxy, or 2-naphthoxy.
  • C 7 -C25aralkyl is typically benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, ⁇ -phenyl-butyl, ⁇ , ⁇ -dimethyl-co-phenyl-butyl, ⁇ -phenyl-dodecyl, ⁇ -phenyl-octadecyl, co-phenyl-eicosyl or ⁇ -phenyl-docosyl, preferably C 7 -Cisaralkyl such as benzyl, 2-benzyl-2- propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, ⁇ -phenyl-butyl, ⁇ , ⁇ -dimethyl-co-phenyl-butyl, ⁇ -phenyl-dodecyl or ⁇ -phenyl-octadecyl, and particularly preferred C 7 -
  • C2-C3oheteroaryl represents a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen , oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated ⁇ -electrons such as thienyl , benzothiophenyl , dibenzothiophenyl, thianthrenyl , furyl , furfuryl , 2H-pyranyl, benzo- furanyl , isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl , pyrazolyl , pyridyl , bipyridyl, triazinyl, pyrimidinyl
  • Benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimidazo[1 ,2- a]benzimidazo-2-yl , carbazolyl and dibenzofuranyl are examples of a C2-Ci4heteroaryl group.
  • C6-C24arylen groups which optionally can be substituted by G, are typically phenylene, 4- methylphenylene, 4-methoxyphenylene, naphthylene, especially 1-naphthylene, or 2- naphthylene, biphenylylene, terphenylylene, pyrenylene, 2- or 9-fluorenylene, phenan- thrylene, or anthrylene, which may be unsubstituted or substituted.
  • Preferred C6-C24arylen groups are 1 ,3-phenylene, 3,3'-biphenylylene, 3,3'-m-terphenylene, 2- or 9-fluorenylene, phenanthrylene, which may be unsubstituted or substituted.
  • C2-C3oheteroarylen groups which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen , oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated -electrons such as thienylene, benzothiophenylene, dibenzothio- phenylene, thianthrenylene, furylene, furfurylene, 2H-pyranylene, benzofuranylene, isoben- zofuranylene, dibenzofuranylene, phenoxythienylene, pyrrolylene, imidazolylene, pyrazol- ylene, pyridylene, bipyridylene, triazinylene, pyrimidinylene, pyrazinylene, pyridazinylene, indolizinylene, isoindolylene, indo
  • C2-C3oheteroarylen groups are pyridylene, triazinylene, pyrimidinylene, carbazolyl ene and benzimidazo[1 ,2-a]benzimidazo-2,5-ylene
  • C6-Cioaryl which is substituted by Ci-C4alkyl ; or C2-Ci4heteroaryl.
  • Possible substituents of the above-mentioned groups are Ci-Csalkyl, a hydroxyl group, a mercapto group, Ci-Csalkoxy, Ci-Csalkylthio, halogen, halo-Ci-Csalkyl, or a cyano group.
  • the C6-C24aryl (C6-Cisaryl) and C2-C3oheteroaryl groups are preferably substituted by one, or more Ci-Csalkyl groups.
  • a substituent occurs more than one time in a group, it can be different in each occurrence.
  • Halo-Ci-Csalkyl is an alkyl group where at least one of the hydrogen atoms is replaced by a halogen atom. Examples are -CF 3 , -CF2CF3, -CF2CF2CF3, -CF(CF 3 ) 2 , -(CF 2 ) 3 CF 3 , and -C(CF 3 ) 3 .
  • substituted by G means that one, or more, especially one to three substituents G might be present.
  • Ci-Cisalkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (Ch Ch OJi-g- R x , where R* is H or Ci-Cioalkyl or C 2 -Ci 0 alkanoyl (e.g.
  • R y is Ci-Cisalkyl, C5-Ci2cycloalkyl, phenyl, Cz-Cisphenylalkyl, and R y ' embraces the same definitions as R y or is H;
  • Ci-C 8 alkylene-COO-R z e.g. CH 2 COOR z , CH(CH 3 )COOR z , C(CH 3 ) 2 COOR z , where R ⁇ is H, Ci-Cisalkyl, (Ch Ch OJi-g-R*, and R x embraces the definitions indicated above;
  • An alkyl group substituted by E is, for example, an alkyl group where at least one of the hydrogen atoms is replaced by F.
  • Examples are -CF 3 , -CF2CF 3 ,
  • Suitable base skeletons of the formula are either commercially available
  • the halogenation can be performed by methods known to those skilled in the art. Preference is given to brominating or iodinating in the 3 and 6 positions (dibromination) or in the 3 or 6 positions (monobromination) of the base skeleton of the formula 2,8 positions (diben- zofuran and dibenzothiophene) or 3,6 positions (carbazole).
  • Optionally substituted dibenzofurans, dibenzothiophenes and carbazoles can be dibromin- ated in the 2,8 positions (dibenzofuran and dibenzothiophene) or 3,6 positions (carbazole) with bromine or NBS in glacial acetic acid or in chloroform.
  • the bromination with Br2 can be effected in glacial acetic acid or chloroform at low temperatures, e.g. 0°C.
  • 3,6-dibromocarbazole, 3,6-dibromo-9-phenylcarbazole, 2,8- dibromodibenzothiophene, 2,8-dibromodibenzofuran, 2-bromocarbazole, 3- bromodibenzothiophene, 3-bromodibenzofuran, 3-bromocarbazole, 2- bromodibenzothiophene and 2-bromodibenzofuran are commercially available.
  • Dibenzofuran (diben- zothiophene) can be monobrominated in the 3 position by a sequence known to those skilled in the art, comprising a nitration, reduction and subsequent Sandmeyer reaction.
  • the introduction of the group 3 ⁇ 4 is performed in the presence of a base.
  • Suitable bases are known to those skilled in the art and are preferably selected from the group consisting of alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca(OH)2, alkali metal hydrides such as NaH, KH, alkali metal amides such as NaNH2, alkali metal or alkaline earth metal carbonates such as K2CO3 or CS2CO3, and alkali metal alkox- ides such as NaOMe, NaOEt.
  • alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca(OH)2
  • alkali metal hydrides such as NaH, KH
  • alkali metal amides such as NaNH2
  • alkali metal or alkaline earth metal carbonates such as K2CO3 or CS2CO3
  • alkali metal alkox- ides such as NaOMe, NaOEt.
  • mixtures of the aforementioned bases are suitable. Particular preference is given to NaOH, KOH, NaH
  • the N-arylation is, for example, disclosed in H. Gilman and D. A. Shirley, J. Am. Chem. Soc. 66 (1944) 888; D. Li et al., Dyes and Pigments 49 (2001) 181 - 186 and Eur. J. Org. Chem. (2007) 2147-2151.
  • the reaction can be performed in solvent or in a melt.
  • Suitable solvents are, for example, (polar) aprotic solvents such as dimethyl sulfoxide, dimethylfor- mamide, N-methyl-2-pyrrolidone (NMP), tridecane or alcohols.
  • Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and car- apeloles can be readily prepared by an increasing number of routes.
  • An overview of the synthetic routes is, for example, given in Angew. Chem. Int. Ed. 48 (2009) 9240 - 9261.
  • diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes, and carbazoles can be obtained by reacting halogenated dibenzofurans, dibenzothiophenes and carbazoles with (Y 1 0)2B-B(OY 1 )2,
  • a catalyst such as, for example, [1 ,1'- bis(diphenylphosphino)ferrocene]dichloropalladium(ll), complex (Pd(CI)2(dppf)), and a base, such as, for example, potassium acetate, in a solvent, such as, for example, dimethyl formamide, dimethyl sulfoxide, dioxane and/or toluene (cf.
  • a solvent such as, for example, dimethyl formamide, dimethyl sulfoxide, dioxane and/or toluene (cf.
  • Y 1 is independently in each occurrence a C1-C1 sal kylg roup and Y 2 is independently in each occurrence a C2-Cioalkylene group, such as -CY 3 Y 4 -CY 5 Y 6 -, or -CY7Y8-CY9Y10- CY11Y12-, wherein Y3, Y 4 , Y3 ⁇ 4, ⁇ ⁇ , ⁇ , ⁇ ⁇ _ ⁇ 9 ⁇ _ ⁇ and Y ⁇ are independently of each other hydrogen, or a Ci-Cisalkylgroup, especially -C(CH3)2C(CH3)2-, - C(CH 3 )2CH 2 C(CH3)2-, or -CH 2 C(CH 3 )2CH2-, and Y « and Y ⁇ are independently of each other hydrogen, or a Ci-Cisalkylgroup.
  • Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting halogenated dibenzofurans, dibenzothiophenes and carbazoles with alkyl lithium reagents, such as, for example, n-butyl lithium, or t-buthyl lithium, followed nic esters, such as, for example, B(isopropoxy)3,
  • Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting dibenzofurans, dibenzothiophenes and carbazoles with lithium amides, such as, for example, lithium diisopropylamide (LDA) followed by reaction with boronic esters such as, for example, B(isopropoxy)3, B(methoxy)3, or
  • lithium amides such as, for example, lithium diisopropylamide (LDA) followed by reaction with boronic esters such as, for example, B(isopropoxy)3, B(methoxy)3, or
  • (ID are starting materials in the synthesis of the compounds of formula (I) and form a further subject of the present invention.
  • A is CI, Br, or I.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X 1 , Ar 1 , Ar 2 , m and n are defined above.
  • X i is NR 7 , O, or S,
  • A' is CI, Br, or I
  • Ari are defined above, and
  • the compounds of the formula I are particularly suitable for use in applications in which charge carrier conductivity is required, especially for use in organic electronics applications, for example selected from switching elements such as organic transistors, e.g. organic FETs and organic TFTs, organic solar cells and organic light- emitting diodes (OLEDs), the compounds of the formula I being particularly suitable in OLEDs for use as matrix material in a light-emitting layer and/or as electron and/or exciton blocker material and/or as hole and/or exciton blocker material, especially in combination with a phosphorescence emitter.
  • switching elements such as organic transistors, e.g. organic FETs and organic TFTs, organic solar cells and organic light- emitting diodes (OLEDs)
  • OLEDs organic light- emitting diodes
  • inventive compounds of the formula I In the case of use of the inventive compounds of the formula I in OLEDs, OLEDs which have good efficiencies and a long lifetime and which can be operated especially at a low use and operating voltage are obtained.
  • inventive compounds of the formula I are suitable especially for use as matrix and/or charge/exciton blocker materials for blue and green emitters, for example light blue or deep blue emitters, these being especially phosphorescence emitters.
  • the compounds of the formula I can be used as conductor/complementary materials in organic electronics applica- tions selected from switching elements and organic solar cells.
  • the compounds of the formula I can be used as matrix material and/or charge/exciton blocker material and/or charge transport material (charge conductor material).
  • the inventive compounds of the formula I are preferably used as matrix materials in organic elec- tronics applications, especially in OLEDs.
  • an emitter material In the emission layer or one of the emission layers of an OLED, it is also possible to combine an emitter material with a matrix material of the compound of the formula I and a further matrix material. This may achieve a high quantum efficiency of this emission layer.
  • a compound of the formula I is used as matrix (host) material in an emission layer and additionally as charge/exciton blocker material, owing to the chemical identity or similarity of the materials, an improved interface between the emission layer and the adjacent charge/exciton blocker material, which can lead to a decrease in the voltage with equal luminance and to an extension of the lifetime of the OLED.
  • the use of the same material for charge/exciton blocker material and for the matrix of an emission layer allows the production process of an OLED to be simplified, since the same source can be used for the vapor deposition process of the material of one of the compounds of the formula I.
  • Suitable structures of organic electronic devices are known to those skilled in the art and are specified below.
  • the organic transistor generally includes a semiconductor layer formed from an organic layer with charge transport capacity; a gate electrode formed from a conductive layer; and an insulat- ing layer introduced between the semiconductor layer and the conductive layer. A source electrode and a drain electrode are mounted on this arrangement in order thus to produce the transistor element. In addition, further layers known to those skilled in the art may be present in the organic transistor.
  • the organic solar cell photoelectric conversion element
  • the organic layer generally comprises an organic layer present between two plate-type electrodes arranged in parallel.
  • the organic layer may be configured on a comb-type electrode. There is no particular restriction regarding the site of the organic layer and there is no particular restriction regarding the material of the electrodes.
  • At least one electrode is preferably formed from a transparent electrode, for example an ITO electrode or a fluorine-doped tin oxide electrode.
  • the organic layer is formed from two sublayers, i.e. a layer with p-type semiconductor properties or hole transport capacity, and a layer formed with n-type semiconductor properties or charge transport capacity.
  • the layers with charge transport capacity may com- prise the compounds of formula I. It is likewise possible that the compounds of the formula I are present both in the light- emitting layer (preferably as matrix material) and in the blocking layers (as charge/exciton blockers).
  • the present invention further provides an organic light-emitting diode comprising an anode (a) and a cathode (i) and a light-emitting layer (e) arranged between the anode (a) and the cathode (i), and if appropriate at least one further layer selected from the group consisting of at least one blocking layer for holes/excitons, at least one blocking layer for elec- trons/excitons, at least one hole injection layer, at least one hole transport layer, at least one electron injection layer and at least one electron transport layer, wherein the at least one compound of the formula I is present in the light-emitting layer (e) and/or in at least one of the further layers.
  • the at least one compound of the formula I is preferably present in the light-emitting layer and/or the charge/exciton blocking layers.
  • At least one compound of the formula I is used as charge transport material.
  • Examples of preferred compounds of formula I are compounds (D-33), (D-34), (D-35), (D-36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) shown above.
  • compounds (D74) to (D131) shown above are compounds (D-33), (D-34), (D-35), (D-36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57
  • At least one compound of the formula I is used as charge/exciton blocker mate- rial.
  • Examples of preferred compounds of formula I are compounds (D-33), (D-34), (D-35), (D-36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) shown above.
  • compounds (D74) to (D131) shown above are compounds (D-33), (D-34), (D-35), (D-36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57
  • the present application further relates to a light-emitting layer comprising at least one compound of the formula I.
  • the inventive organic light-emitting diode thus generally has the following structure: an anode (a) and a cathode (i) and a light-emitting layer (e) arranged between the anode (a) and the cathode (i).
  • the inventive OLED may, for example - in a preferred embodiment - be formed from the following layers:
  • Layer sequences different than the aforementioned structure are also possible, and are known to those skilled in the art.
  • the OLED does not have all of the layers mentioned; for example, an OLED with layers (a) (anode), (e) (light-emitting layer) and (i) (cathode) is likewise suitable, in which case the functions of the layers (c) (hole transport layer) and (f) (blocking layer for holes/excitons) and (g) (electron transport layer) are assumed by the adjacent layers.
  • OLEDs which have layers (a), (c), (e) and (i), or layers (a), (e), (f), (g) and (i), are likewise suitable.
  • the OLEDs may have a blocking layer for electrons/excitons (d) between the hole transport layer (c) and the Light- emitting layer (e).
  • a plurality of the aforementioned functions are combined in one layer and are assumed, for example, by a single material present in this layer.
  • a material used in the hole transport layer, in one em- bodiment may simultaneously block excitons and/or electrons.
  • the individual layers of the OLED among those specified above may in turn be formed from two or more layers.
  • the hole transport layer may be formed from a layer into which holes are injected from the electrode, and a layer which transports the holes away from the hole-injecting layer into the light-emitting layer.
  • the electron conduction layer may likewise consist of a plurality of layers, for example a layer in which electrons are injected by the electrode, and a layer which receives electrons from the electron injection layer and transports them into the light-emitting layer.
  • These layers mentioned are each selected according to factors such as energy level, thermal resistance and charge carrier mobility, and also energy difference of the layers specified with the organic layers or the metal electrodes.
  • the person skilled in the art is capable of selecting the structure of the OLEDs such that it is matched optimally to the organic compounds used in accordance with the invention.
  • the OLED according to the present invention comprises in this order:
  • the anode is an electrode which provides positive charge carriers. It may be composed, for example, of materials which comprise a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides. Alternatively, the anode may be a conductive polymer. Suitable metals comprise the metals of groups 1 1 , 4, 5 and 6 of the Periodic Table of the Elements, and also the transition metals of groups 8 to 10. When the anode is to be transparent, mixed metal oxides of groups 12, 13 and 14 of the Periodic Table of the Elements are generally used, for example indium tin oxide (ITO). It is likewise possible that the anode (a) comprises an organic material, for example polyaniline, as described, for example, in Nature, Vol.
  • Preferred anode materials include conductive metal oxides, such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AlZnO), and metals.
  • Anode (and substrate) may be sufficiently transparent to create a bottom-emitting device.
  • a preferred transparent substrate and anode combination is commercially available ITO (anode) deposited on glass or plastic (substrate).
  • a reflective anode may be preferred for some top-emitting devices, to increase the amount of light emitted from the top of the device. At least either the anode or the cathode should be at least partly transparent in order to be able to emit the light formed. Other anode materials and structures may be used.
  • injection layers are comprised of a material that may improve the injection of charge carriers from one layer, such as an electrode or a charge generating layer, into an adjacent organic layer. Injection layers may also perform a charge transport function.
  • the hole injection layer may be any layer that improves the injection of holes from anode into an adjacent organic layer.
  • a hole injection layer may comprise a solution deposited material, such as a spin-coated polymer, or it may be a vapor deposited small molecule material, such as, for example, CuPc or MTDATA.
  • Polymeric hole-injection materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers, such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]- 2,5-diyl) (Plexcore ® OC Conducting Inks commercially available from Plextronics), and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PEDOT/PSS.
  • PVK poly(N-vinylcarbazole)
  • polythiophenes polypyrrole
  • polyaniline polyaniline
  • self-doping polymers such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]- 2,5-di
  • hole transport material Either hole-transporting molecules or polymers may be used as the hole transport material.
  • Suitable hole transport materials for layer (c) of the inventive OLED are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996, US20070278938, US2008/0106190, US2011/0163302 (triarylamines with (di)benzothiophen/(di)benzofuran; Nan-Xing Hu et al. Synth. Met. 111 (2000) 421 (in- dolocarbazoles), WO2010002850 (substituted phenylamine compounds) and
  • WO2012/16601 (in particular the hole transport materials mentioned on pages 16 and 17 of WO2012/16601 ). Combination of different hole transport material may be used.
  • polymeric hole-injection materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers, such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]-2,5- diyl) (Plexcore® OC Conducting Inks commercially available from Plextronics), and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PE- DOT/PSS.
  • PVK poly(N-vinylcarbazole)
  • polythiophenes polypyrrole
  • polyaniline polyaniline
  • self-doping polymers such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]-2,5- diyl)
  • Preferred examples of a material of the hole injecting layer are a porphyrin compound, an aromatic tertiary amine compound, or a styrylamine compound. Particularly preferable examples include an aromatic tertiary amine compound such as hexacyanohex- aazatriphenylene (HAT).
  • HAT hexacyanohex- aazatriphenylene
  • metal carbene complexes as hole transport materials.
  • Suitable carbene complexes are, for example, carbene complexes as described in WO2005/019373A2, WO2006/056418 A2, WO2005/113704, WO2007/115970,
  • carbene complex is lr(DPBIC)3 with the formula: (HTM-1).
  • Another exa ne complex is lr(ABIC)3 with the formu-
  • the hole-transporting layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device.
  • Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, 2003, 359 (p-doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No.
  • mixtures may, for example, be the following mixtures: mixtures of the abovementioned hole transport materials with at least one metal oxide, for example M0O2, M0O3, WO x , Re03 and/or V2O5, preferably M0O3 and/or Re03, more pref- erably M0O3, or mixtures comprising the aforementioned hole transport materials and one or more compounds selected from 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6- tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), 2,5-bis(2-hydroxyethoxy)-7,7,8,8- tetracyanoquinodimethane, bis(tetra-n-butylammonium)tetracyanodiphenoquinodimethane, 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene, 1 1 ,11
  • Preferred mixtures comprise the aforementioned carbene complexes, such as, for example, the carbene complexes HTM-1 and HTM-2, and M0O3 and/or ReC>3, especially M0O3.
  • the hole transport layer comprises from 0.1 to 10 wt % of M0O3 and 90 to 99.9 wt % carbene complex, especially of the carbene complex HTM-1 and HTM-2, wherein the total amount of the M0O3 and the carbene complex is 100 wt %.
  • Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer.
  • An electron/exciton blocking layer (d) may be disposed between the first emitting layer (e) and the hole transport layer (c), to block electrons from emitting layer (e) in the direction of hole transport layer (c). Blocking layers may also be used to block excitons from diffusing out of the emissive layer.
  • Suitable metal com- plexes for use as electron/exciton blocker material are, for example, carbene complexes as described in WO2005/019373A2, WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981 , WO2008/000727 and PCT/EP2014/055520. Explicit reference is made here to the disclosure of the WO applications cited, and these disclosures shall be considered to be incorporated into the content of the present application.
  • One example of a suita- ble carbene complex is compound HTM-1 and HTM-2.
  • the light-emitting layer (e) comprises at least one emitter material.
  • it may be a fluorescence or phosphorescence emitter, suitable emitter materials being known to those skilled in the art.
  • the at least one emitter material is preferably a phosphorescence emitter.
  • the phosphorescence emitter compounds used with preference are based on metal complexes, and especially the complexes of the metals Ru, Rh, Ir, Pd and Pt, in particular the complexes of Ir, have gained significance.
  • the compounds of the formula I can be used as the matrix in the light-emitting layer.
  • Suitable metal complexes for use in the inventive OLEDs are described, for example, in documents WO 02/60910 A1 , US 2001/0015432 A1 , US 2001/0019782 A1 ,
  • WO 2005/113704 A2 WO 2006/115301 A1 , WO 2006/067074 A1 , WO 2006/056418, WO 200612181 1 A1 , WO 2007095118 A2, WO 2007/115970, WO 2007/1 15981 ,
  • metal complexes are the commercially available metal complexes tris(2- phenylpyridine)iridium(lll), iridium(lll) tris(2-(4-tolyl)pyridinato-N,C 2 '), bis(2- phenylpyridine)(acetylacetonato)iridium(lll), iridium(lll) tris(l-phenylisoquinoline), iridium(lll) bis(2,2'-benzothienyl)pyridinato-N,C 3 ')(acetylacetonate), tris(2-phenylquinoline)iridium(lll), iridium(lll) bis(2-(4,6-difluorophenyl)pyridinato-N,C 2 )picolinate, iridium(lll) bis(1- phenylisoquinoline)(acetylacetonate), bis(2-phenylquinoline)(acett
  • Preferred phosphorescence emitters are carbene complexes. Suitable phosphorescent blue emitters are specified in the following publications: WO2006/056418A2,
  • the light emitting layer (e) comprises at least one carbine complex as phosphorescence emitter.
  • Suitable carbine complexes are, for example, compounds of the
  • M is a metal atom selected from the group consisting of Co, Rh, Ir, Nb, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re, Cu, Ag and Au in any oxidation state possible for the respective metal atom;
  • Carbene is a carbene ligand which may be uncharged or monoanionic and monodentate, bidentate or tridentate, with the carbene ligand also being able to be a biscarbene or triscarbene ligand;
  • L is a monoanionic or dianionic ligand, which may be monodentate or bidentate;
  • K is an uncharged monodentate or bidentate ligand selected from the group consisting of phosphines; phosphonates and derivatives thereof, arsenates and derivatives thereof; phosphites; CO; pyridines; nitriles and conjugated dienes which form a ⁇ complex with M 1 ; n1 is the number of carbene ligands, where n1 is at least 1 and when n1 > 1 the carbene ligands in the complex of the formula I can be identical or different;
  • nl is the number of ligands L, where ml can be 0 or ⁇ 1 and when ml > 1 the ligands L can be identical or different;
  • o is the number of ligands K, where o can be 0 or ⁇ 1 and when o > 1 the ligands K can be identical or different;
  • n1 + ml + o is dependent on the oxidation state and coordination number of the metal atom and on the denticity of the ligands carbene, L and K and also on the charge on the ligands, carbene and L, with the proviso that n1 is at least 1.
  • n1 is an integer selected from 1 , 2 and 3,
  • Y is N R51 ' , O, S or C(R25') 2 ,
  • R 51' is a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,
  • R 52' , R 53' , R 54' and R 55' are each, if A 2' , A 3' , A 4' and/or A 5' is N, a free electron pair, or, if A 2' , A 3' , A 4' and/or A 5' is C, each independently hydrogen, linear or branched alkyl radical op- tionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 car- bon atoms and/or heteroatoms, group with donor
  • R 53' and R 54' together with A 3' and A 4' form an optionally substituted, unsaturated ring optionally interrupted by at least one further heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms,
  • R 56' , R 57' , R 58' and R 59' are each independently hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, cycloheteroalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or un- substituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms, group with donor or acceptor action, or
  • R 56' and R 57' , R 57' and R 58' or R 58' and R 59' together with the carbon atoms to which they are bonded, form a saturated, unsaturated or aromatic, optionally substituted ring optionally interrupted by at least one heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms, and/or
  • R 55' and R 56' together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, an aromatic unit, heteroaromatic unit and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which is optionally fused a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms,
  • R 25' is independently a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,
  • K is an uncharged mono- or bidentate ligand
  • L is a mono- or dianionic ligand, preferably monoanionic ligand, which may be mono- or bidentate,
  • ml is 0, 1 or 2, where, when ml is 2, the K ligands may be the same or different, o1 is 0, 1 or 2, where, when o1 is 2, the L ligands may be the same or different.
  • the compound of formula IX is preferably a compound of the formula:
  • the compound of formula IX is more preferably a compound (BE-1), (BE-2), (BE-7), (BE- 12), (BE-16), (BE-64), or (BE-70).
  • the most preferred phosphorescent blue emitters are compounds (BE-1 ) and (BE-12).
  • the homoleptic metal-carbene complexes may be present in the form of facial or meridional isomers, preference being given to the facial isomers.
  • Suitable carbene complexes of formula (IX) and their preparation process are, for example, described in WO2011/073149.
  • the compounds of the present invention can also be used as host for phosphorescent green emitters.
  • Suitable phosphorescent green emitters are, for example, specified in the following publications: WO2006014599, WO20080220265, WO2009073245, WO2010027583, WO2010028151 , US201 10227049, WO201 1090535, WO2012/08881 , WO20100056669, WO20100118029, WO20100244004, WO201 1109042, WO2012166608, US20120292600, EP2551933A1 ; US6687266, US20070190359, US20070190359, US20060008670; WO2006098460, US20110210316, WO2012053627; US6921915, US20090039776; JP2007123392 and European patent application no. 14180422.9.
  • the light-emitting layer may comprise further components in addition to the emitter material.
  • a fluroescent dye may be present in the light-emitting layer in order to alter the emission color of the emitter material.
  • a matrix material can be used. This matrix material may be a polymer, for example poly(N- vinylcarbazole) or polysilane.
  • At least one compound of the formula I is used as matrix material.
  • a compound of formula (ld-1a), (ld-1b), (ld-2a), or (ld-2b), very especially a compound of the formula (ld-1a), or (ld-2a) is used as matrix material.
  • Examples of preferred compounds of formula I are compounds (D-33), (D-34), (D-35), (D-36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) shown above.
  • compounds (D74) to (D131) shown above are compounds (D-33), (D-34), (D-35), (D-36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57
  • the light-emitting layer is formed from 2 to 40% by weight, preferably 5 to 35% by weight, of at least one of the aforementioned emitter materials and 60 to 98% by weight, preferably 75 to 95% by weight, of at least one of the aforementioned matrix materials - in one embodiment at least one compound of the formula I - where the sum total of the emitter material and of the matrix material adds up to 100% by weight.
  • the light-emitting layer is formed from 2 to 40% by weight, preferably 5 to 35% by weight, of BE-1 and 60 to 98% by weight, preferably 65 to 95% by weight, of a compound of the formula I and and HTM-1 , or HTM-2, where the sum total of the carben complexes and of the compound of formula I adds up to 100% by weight.
  • Suitable metal complexes for use together with the compounds of the formula I as matrix material in OLEDs are, for example, also carbene complexes as described in
  • WO2007108459 H-1 to H-37
  • H-20 to H-22 and H-32 to H-37 most preferably H-20, H-32, H-36, H-37
  • WO2008035571 A1 Host 1 to Host 6
  • JP2010135467 compounds 1 to 46 and Host-1 to Host-39 and Host-43
  • WO2009008100 compounds No.1 to No.67 preferably No.3, No.4, No.7 to No. 12, No.55, No.59, No. 63 to No.67, more preferably No. 4, No. 8 to No. 12, No.
  • WO20071 19816 the compounds 1 to 37, WO2010087222 the compounds H-1 to H-31 , WO2010095564 the compounds HOST-1 to HOST-61 , WO2007108362, WO2009003898, WO2009003919, WO2010040777, US2007224446, WO06128800, WO2012014621 ,
  • the above-mentioned small molecules are more preferred than the above-mentioned (co)polymers of the small molecules.
  • one or more compounds of the general formula (X) specified hereinafter are used as second host material.
  • X is NR, S, O or PR
  • R is aryl, heteroaryl, alkyl, cycloalkyi, or heterocycloalkyi;
  • R221 R222 anc are independently of each other aryl, heteroaryl, alkyl, cycloalkyi, or heterocycloalkyi, wherein at least on of the groups R 221 , R 222 , or R 223 is aryl, or heteroaryl;
  • R 224 and R 225 are independently of each other alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl, a group A 200 , or a group having donor, or acceptor characteristics;
  • n2 and m2 are independently of each other 0, 1 , 2, or 3;
  • R 206 and R 207 form together with the nitrogen atom a cyclic residue having 3 to 10 ring at- oms, which can be unsubstituted, or which can be substituted with one, or more substitu- ents selected from alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl and a group having donor, or acceptor characteristics; and/or which can be annulated with one, or more further cyclic residues having 3 to 10 ring atoms, wherein the annulated residues can be unsubstituted, or can be substituted with one, or more substituents selected from alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl and a group having donor, or acceptor characteristics; and 208, 209, R2io_ 2ii _ 212_ 213_ R214 u nc
  • R215 are independently of each other aryl, het, for exam-
  • T is O, or S, preferably O. If T occurs more than one time in a molecule, all groups T have the same meaning.
  • T 1 is O, or S preferably O.
  • Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer.
  • the hole blocking layer may be disposed between the emitting layer (e) and electron transport layer (g), to block holes from leaving layer (e) in the direction of electron transport layer (g).
  • Blocking layers may also be used to block excitons from diffusing out of the emissive layer.
  • Additional hole blocker materials typically used in OLEDs are 2,6-bis(N-carbazolyl)pyridine (mCPy), 2,9-dimethyl-4J-diphenyl-1 ,10-phenanthroline (bathocuproin, (BCP)), bis(2- methyl-8-quinolinato)-4-phenylphenylato)aluminum(lll) (BAIq), phenothiazine S,S-dioxide derivates and 1 ,3,5-tris(N-phenyl-2-benzylimidazolyl)benzene) (TPBI), TPBI also being suitable as electron-transport material.
  • mCPy 2,6-bis(N-carbazolyl)pyridine
  • BCP 2,9-dimethyl-4J-diphenyl-1 ,10-phenanthroline
  • BAIq bis(2- methyl-8-quinolinato)-4-phenylphenylato)aluminum(lll)
  • BAIq bis(2-
  • hole blockers and/or electron conductor materials are 2,2',2"-(1 ,3,5-benzenetriyl)tris(1-phenyl-1-H-benzimidazole), 2-(4- biphenylyl)-5-(4-tert-butylphenyl)-1 ,3,4-oxadiazole, 8-hydroxyquinolinolatolithium, 4- (naphthalen-1-yl)-3,5-diphenyl-4H-1 ,2,4-triazole, 1 ,3-bis[2-(2,2'-bipyridin-6-yl)-1 ,3,4- oxadiazo-5-yl]benzene, 4,7-diphenyl-1 ,10-phenanthroline, 3-(4-biphenylyl)-4-phenyl-5-tert- butylphenyl-1 ,2,4-triazole, 6,6'-bis[5-(biphenyl-4-yl)-1 ,3,4-
  • disilyl compounds selected from the group consisting of disilylcarbazoles, disilylbenzofurans, dis- ilylbenzothiophenes, disilylbenzophospholes, disilylbenzothiophene S-oxides and dis- ilylbenzothiophene S,S-dioxides, as specified, for example, in PCT applications
  • Electron transport layer may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity.
  • EP1970371 or in EP1097981 , and azole compounds such as 2-(4-biphenylyl)-5-(4-t- butylphenyl)-1 ,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4phenyl-5-(4-t-butylphenyl)-1 ,2,4- triazole (TAZ).
  • PBD 2-(4-biphenylyl)-5-(4-t- butylphenyl)-1 ,3,4-oxadiazole
  • TEZ 3-(4-biphenylyl)-4phenyl-5-(4-t-butylphenyl)-1 ,2,4- triazole
  • At least one material is electron-conducting.
  • at least one phenanthroline compound is used, preferably BCP, or at least one pyridine compound according to the formula (VIII) below, preferably a compound of the formula (Vlllaa) below.
  • alkaline earth metal or alkali metal hy- droxyquinolate complexes for example Liq, are used.
  • Suitable alkaline earth metal or alkali metal hydroxyquinolate complexes are specified below (formula VII). Reference is made to WO2011/157779.
  • the electron-transport layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device.
  • Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1 , 1 July 2003 (p- doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No.
  • n-Doping is achieved by the addition of reducing materials.
  • mixtures may, for example, be mixtures of the abovementioned electron transport materials with alkali/alkaline earth metals or alkali/alkaline earth metal salts, for example Li, Cs, Ca, Sr, CS2CO3, with alkali metal complexes, for example 8-hydroxyquinolatolithium (Liq), and with Y, Ce, Sm, Gd, Tb, Er, Tm, Yb, Li 3 N, Rb 2 C0 3 , dipotassium phthalate, W(hpp) 4 from
  • the electron-transport layer comprises at least one compound of the general formula (VII)
  • R 32' and R 33' are each independently F, Ci-Cs-alkyl, or C6-Ci4-aryl, which is optionally substituted by one or more Ci-Cs-alkyl groups, or
  • R 32' and/or R 33' substituents together form a fused benzene ring which is optionally substituted by one or more Ci-Cs-alkyl groups;
  • a and b are each independently 0, or 1 , 2 or 3,
  • M 1 is an alkaline metal atom or alkaline earth metal atom
  • p is 1 when M 1 is an alkali metal atom, p is 2 when M 1 is an earth alkali metal atom.
  • a very particularly preferred compound of the formula (VII) is (Liq), which may be present as a single species, or in other forms such as Li g Q g in which g is an integer, for example LkQe- Q is an 8-hydroxyquinolate ligand or an 8-hydroxyquinolate derivative.
  • the electron-transport layer comprises at least one compound of the formula (VIII),
  • R 34" , Rss", RS6", R 37" , R 34' , R 35' , R 3 6' and R 37' are each independently H, Ci-Cis-alkyl, C1-C18- alkyl which is substituted by E' and/or interrupted by D', C6-C24-aryl, C6-C24-aryl which is substituted by G', C2-C2o-heteroaryl or C2-C2o-heteroaryl which is substituted by G', Q is an arylene or heteroarylene group, each of which is optionally substituted by G';
  • D' is -CO-; -COO-; -S-; -SO-; -S0 2 -; -0-; -NR 4 ° ' -; -SiR 4 5 ' R 4 6'-; -POR 47' -; or - C ⁇ C-;
  • E' is -OR 44' ; -SR 44' ; -NR 4 ° ' R 4 1 ' ; -COR 43' ; -COOR 42' ; -CONR 4 ° ' R 4 i'; -CN; or F;
  • G' is E', Ci-Cis-alkyl, Ci-Cis-alkyl which is interrupted by D', Ci-Ci8-perfluoroalkyl, C1-C18- alkoxy, or Ci-Cis-alkoxy which is substituted by E' and/or interrupted by D', in which R 38' and R 39' are each independently H, C6-Cis-aryl; C6-Cis-aryl which is substituted by Ci-Cis-alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-; R 40' and R 41 ' are each independently C6-Cis-aryl; C6-Cis-aryl which is substituted by C1-C18- alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-; or
  • R 40' and R 41 ' together form a 6-membered ring
  • R 42' and R 43' are each independently C6-Cis-aryl; C6-Cis-aryl which is substituted by Ci-Cis- alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-,
  • R 44' is C6-Ci8-aryl; C6-Cis-aryl which is substituted by Ci-Cis-alkyl or Ci-Cis-alkoxy; C1-C18- alkyl; or Ci-Cis-alkyl which is interrupted by -0-,
  • R 45' and R 46' are each independently Ci-Cis-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cis-alkyl,
  • R 47' is Ci-Cis-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cis-alkyl.
  • Preferred compounds of the formula (VIII) are compounds of the formula (Villa)
  • R 48' is H or Ci-Cis-alkyl
  • R 48" is H, Ci-Cis-alkyl or or
  • the electron-transport layer comprises a compound Liq and a compound ETM-2.
  • the electron-transport layer comprises the compound of the formula (VII) in an amount of 99 to 1 % by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, where the amount of the compounds of the formulae (VII) and the amount of the compounds of the formulae (VIII) adds up to a total of 100% by weight.
  • the preparation of the compounds of the formula (VIII) is described in J. Kido et al., Chem. Commun. (2008) 5821-5823, J. Kido et al., Chem. Mater. 20 (2008) 5951-5953 and JP2008/127326, or the compounds can be prepared analogously to the processes dis- closed in the aforementioned documents.
  • the electron-transport layer comprises Liq in an amount of 99 to 1 % by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, where the amount of Liq and the amount of the dibenzofuran compound(s), especially ETM-1 , adds up to a total of 100% by weight.
  • the electron-transport layer comprises at least one phenanthro- line derivative and/or pyridine derivative.
  • the electron-transport layer comprises at least one phe- nanthroline derivative and/or pyridine derivative and at least one alkali metal hydroxyquinolate complex.
  • the electron-transport layer comprises at least one of the dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described in WO2011/157790, especially ETM-1.
  • the electron-transport layer comprises a compound de- scribed in WO2012/1 11462, WO2012/147397, WO2012014621 , such as, for example, a
  • the electron injection layer may be any layer that improves the injection of electrons into an adjacent organic layer.
  • Lithium-comprising organometallic compounds such as 8- hydroxyquinolatolithium (Liq), CsF, NaF, KF, CS2CO3 or LiF may be applied between the electron transport layer (g) and the cathode (i) as an electron injection layer (h) in order to reduce the operating voltage.
  • the cathode (i) is an electrode which serves to introduce electrons or negative charge carriers.
  • the cathode may be any metal or nonmetal which has a lower work function than the anode. Suitable materials for the cathode are selected from the group consisting of alkali metals of group 1 , for example Li, Cs, alkaline earth metals of group 2, metals of group 12 of the Periodic Table of the Elements, comprising the rare earth metals and the lanthanides and actinides. In addition, metals such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof, may be used.
  • the different layers if present, have the following thicknesses:
  • anode 500 to 5000 A (angstrom), preferably 1000 to 2000 A;
  • the person skilled in the art is aware (for example on the basis of electrochemical studies) of how suitable materials have to be selected. Suitable materials for the individual layers are known to those skilled in the art and are disclosed, for example, in WO 00/70655.
  • the layers used in the inventive OLED have been surface-treated in order to increase the efficiency of charge carrier transport.
  • the selection of the materials for each of the layers mentioned is preferably determined by obtaining an OLED with a high efficiency and lifetime.
  • the inventive OLED can be produced by methods known to those skilled in the art.
  • the inventive OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate.
  • Suitable substrates are, for example, glass, inorganic semiconductors or polymer films.
  • vapor deposition it is possible to use customary tech- niques, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others.
  • the organic layers of the OLED can be applied from solutions or dispersions in suitable solvents, employing coating techniques known to those skilled in the art.
  • the compounds of the formula I in at least one layer of the OLED preferably in the light-emitting layer (preferably as a matrix material), charge transport layer and/or in the charge/exciton blocking layer makes it possible to obtain OLEDs with high efficiency and with low use and operating voltage.
  • the OLEDs obtained by the use of the compounds of the formula I additionally have high lifetimes.
  • the efficiency of the OLEDs can additionally be improved by optimizing the other layers of the OLEDs.
  • high-efficiency cathodes such as Ca or Ba, if appropriate in combination with an intermediate layer of LiF, can be used.
  • additional layers may be present in the OLEDs in order to adjust the energy level of the different layers and to facilitate electroluminescence.
  • the OLEDs may further comprise at least one second light-emitting layer.
  • the overall emission of the OLEDs may be composed of the emission of the at least two light-emitting layers and may also comprise white light.
  • the OLEDs can be used in all apparatus in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile visual display units and illumination units. Stationary visual display units are, for example, visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations and information panels. Mobile visual display units are, for example, visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains. Further devices in which the inventive OLEDs can be used are, for example, keyboards; items of clothing; furniture; wallpaper.
  • the present invention relates to a device selected from the group consisting of stationary visual display units such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations, information panels, and mobile visual display units such as visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising at least one inventive organic light-emitting diode or at least one inventive light-emitting layer.
  • stationary visual display units such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations, information panels
  • mobile visual display units such as visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains
  • illumination units keyboards
  • items of clothing furniture
  • wallpaper comprising at least one inventive organic light-emitting diode or at least one inventive light-emitting layer.
  • a glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode used as an anode is first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate is exposed to an ultraviolet light and ozone for further 30 min. This treatment also improves the hole injection properties of the ITO.
  • the cleaned substrate is mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below are applied by vapor deposition to the ITO substrate a A/sec at about 10 6 -10 8 mbar.
  • As a hole injection layer As a hole injection layer,
  • e xciton and electron blocker, comp (HTM-1 ; for preparation, see Ir complex (7) in the application WO2005/019373) is then applied with a thickness of 10 nm.
  • electroluminescence spectra are recorded at various currents and voltages.
  • the current-voltage characteristic is measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE).
  • CIE Commission In- ternationale de I'Eclairage
  • LT50 50% lifetime
  • the time spent until the initial luminance of 4 ⁇ 00 cd/m 2 is reduced to 50% (2 ⁇ 00 cd/m 2 ) is recorded.

Abstract

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

Description

indole derivatives for electronic applications
Description
The present invention relates to compounds of formula I, a process for their production and their use in electronic devices, especially electroluminescent devices. When used as charge transport material and/or host material for phosphorescent emitters in electroluminescent devices, the compounds of formula I may provide improved efficiency and reduced driving voltage of electroluminescent devices.
US2002117662 discloses a light-emitting device comprising: a pair of electrodes formed on a substrate; and at least one organic compound layer containing a light-emitting layer provided between the electrodes, wherein the at least one organic compound layer comprises a host material, a layer of the host material has an energy gap of not less than 3.6 eV and an ionization potential of the host material is from 5.4 eV to 6.3 eV.
Preferably, the host material compri prising a partial structure repre-
Figure imgf000002_0001
sented by the following formula (II): , wherein
wherein L12 represents one of a from 2- to 6-valent connecting group having a heteroaryl group and a from 2- to 6-valent connecting group comprising a non-conjugate connecting group having an arylene group; n represents an integer of from 2 to 6; R represents one of an alkyl group having from 1 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, a heteroaryl group having from 2 to 20 carbon atoms and a silyl group having from 3 to 20 carbon atoms; and m represents an integer of from 0 to 6. The examples given for L12
Figure imgf000002_0002
do not include a group of formula
WO08066196 is directed to an organic electroluminescent device comprising: a pair of electrodes; and at least one organic layer between the pair of electrodes, the at least one organic layer including a light-emitting layer containing a light-emitting material, wherein the at least one organic layer includes at least one layer containing an indole derivative represented by formula (1):
Figure imgf000003_0001
n 0 , wherein Ri<" , R102, RKH Rio4 anc| Rios each independently represents a hydrogen atom or a substituent; R106 represents an alkyl group having a tertiary or quaternary carbon atom; R101 and R106 may be bonded to each other to form a ring; L101 represents a linking group; and n101 represents an integer of 2 or higher. T ude a group of formula
Figure imgf000003_0002
JP2003277744 relates to a material for an organic electroluminescent element which comprises a compound comprising a group bearing an indole skeleton and, bonded thereto, a group bearing a cycloalkane skeleton or a meta-aromatic ring group. The organic electroluminescent element comprises a monolayered or multi-layered organic thin film layers sandwiched between a cathode and an anode, where at least one layer of the organic thin film layers contains the material for the organic electroluminescent element. JP2009049318 relates to an electroluminescent device which comprises an indole deriva
Figure imgf000003_0003
tive represented by a general formula n (1). R106 denotes a silyl substituent.
JP2012089777 relates to an electroluminescence element which is characterized in that at least one of the organic compound layers contains a compound represented by following
Figure imgf000004_0001
Figure imgf000004_0002
KR20140087805A discloses compounds for organic optoelectronic devices, including or
Figure imgf000004_0003
ganic light-emitting devices, represented by the following formula
n is an integer of 1 to 3 and, R1 is hydrogen, deuterium, halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1-C20 amine group, a nitro group, a carboxyl group, a ferrocenyl group, a substituted or unsubstituted C1- C20alkyl group, a substituted or unsubstituted C6-C30arylgroup, a substituted or unsubstituted C2 to C30heteroaryl group ...
Figure imgf000004_0004
L may be a group of formula (X is O, or S), which is bonded to the indole skeleton by a C-C bond. KR20140103842 discloses an organic light emitting device including a compound repre-
sented by the formula
Figure imgf000005_0001
Figure imgf000005_0002
J. Keruckas et al. Dyes and Pigments 100 (2014) 66-72 disclose3,6-bis(indol-1-yl)-9- phenylcarbazoles as electroactive materials for electrophosphorescent diodes:
Figure imgf000005_0003
BIPC (Ri = R2 =H), BIPC1 (Ri = OCH3, R2 =H), BIPC2 (R2 = OCH3, Ri =H), BIPC3 (Ri = R2 = OCH3). Notwithstanding these developments, there remains a need for organic light emitting devices comprising new charge transport materials to provide improved efficiency, stability, manufacturability, and/or spectral characteristics of electroluminescent devices.
Accordingly, it is an object of the present invention, with respect to the aforementioned prior art, to provide further materials suitable for use in OLEDs and further applications in organic electronics. More particularly, it should be possible to provide charge transport materials, charge/exciton blocker materials and matrix materials for use in OLEDs. The materials should be suitable especially for OLEDs which comprise at least one phosphorescence emitter, especially at least one green emitter or at least one blue emitter. Furthermore, the materials should be suitable for providing OLEDs which ensure good efficiencies, good operative lifetimes and a high stability to thermal stress, and a low use and operating voltage of the OLEDs.
Certain indole derivatives are found to be suitable for use in organo-electroluminescent devices. In particular, said derivatives are suitable charge transport materials, or host materials for phosphorescent emitters with low driving voltage, good efficiency and good operative lifetimes.
S
Figure imgf000006_0001
(I), wherein m is 0, 1 or 2, n is 0, 1 or 2,
Ar1 and Ar2 are independently of each other a C6-C24arylen group, which can optionally be substituted by G, a C2-C3oheteroarylen group, which can optionally be substituted by G, Bi is N, or CR3,
Figure imgf000006_0002
B3 is N, or CRs,
B4 is N, or CR6,
with the proviso that not more than two of B1, B2, B3 and B4 are N;
Bii is N, or CRsi,
Figure imgf000006_0003
with the proviso that not more than two of B11, B12, B13 and B14 are N;
Figure imgf000006_0004
Bi6 is N, or CRse,
Figure imgf000006_0005
Bi8 is N, or CRss,
with the proviso that not more than two of B15, B16, B17 and B18 are N;
R1 and R2 are independently of each other -H, -F, CN, a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24aryloxy group, which can optionally be substituted by G;
Xi is O, S, Se or NR7,
with the proviso that, if at least one of R1, R2, R3, R4, R5, and R6 is -CN, then A is -NR10R11, or -Si(R1 )(R13)(R14), a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
R3, R4, R5 , R6, R5i _ R527 53, 54, R55, R56, R57, anc| R58 are independently of each other -H, -F, CN, a C2-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24 aryloxy group, which can optionally be substituted by G;
R7 is a Ci-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C25cycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G;
R10 and R11 are independently of each other H, a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G; R12, R13 and R14 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by L; a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G; with the proviso that, if all of R1, R2, R3, R4, R5 and R6 are different from -CN, then
A is a C6-C24arylen group, which can optionally be substituted by G, a Ci3-C3oheteroarylen group, which can optionally be substituted by G, an azacarbazolyl, which can optionally be substituted by G, an azaindolyl, which can optionally be substituted by G, a dibenzofuranyl, which can optionally be substituted by G, a dibenzothiophenyl, which can optionally be substituted by G, a benzofuranyl, which can optionally be substituted by G, a benzothio- phenyl, which can optionally be substituted by G, a pyridyl, which can optionally be substituted by G, a pynmidinyl, which can optionally be substituted by G, a pyrazinyl, which can optionally be substituted by G, a triazinyl, which can optionally be substituted by G, a naph- , or a group represented by formula
Figure imgf000007_0001
(IV),
B19 is N or CR61, preferably CR61,
B20 is N or CR62, preferably CR62,
B2i is N or CR63, preferably CR63,
B22 is N or CR64, preferably CR64,
with the proviso that not more than two of B19, B20, B21 and B22 are N;
B23 is N or CR65, preferably CR65,
B24 is N or CR66, preferably CR66,
B25 is N or CR67, preferably CR67,
B26 is N or CR68, preferably CR68,
with the proviso that not more than two of B23, B24, B25 and B26 are N;
B27 is N or CR69, preferably CR69,
B28 is N or CR70, preferably CR70, B29 is N or CR71 , preferably CR71 ,
B30 is N or CR72, preferably CR72,
B3i is N or CR73, preferably CR73,
B32 is N or CR74, preferably CR74,
with the proviso that not more than two of B29, B30, B31 and B32 are N;
with the proviso that N in the groups of formula (III) and (IV) chemically binds to one of B15, B16, B17, or B18, or Ar1 , or Ar2, if present;
R61 , R62, R63, R64, Res, R66, R677 es, 69, /o, R71 , R72, R73 anc| R74 are independently of each other -H, -F, -C≡N, a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2- C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24aryloxy group, which can optionally be substituted by G;
D is -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -NR2S -POR24-, -CR2s=CR26-, or -C≡C-,
E is -ORS1 , -SR31 , -NR32R33, -COR34, -COOR34, -CONR32R33, -C≡N, or -F,
L is D, or -SiR22R23-,
G is E, or a Ci-Cisalkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by -F, Ci-Cisalkyl, or Ci-Cisalkyl which is interrupted by -0-; a C2-C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by -F, Ci-Cisalkyl, or Ci-Cisalkyl which is inter- rupted by O;
R21 , R32 and R33 are independently of each other a C6-Cisaryl group; a C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O-; or R32 and R33 together form a five or six membered ring, R22 and R23 are independently of each other a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl,
R24 is a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl,
R25 and R26 are independently of each other H, C6-Cisaryl; C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; Ci-Cisalkyl; or Ci-Cisalkyl which is interrupted by -0-, R31 is a C6-Cisaryl; a C6-Cisaryl, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci- Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O- and
R34 is a C6-Cisaryl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, or Ci- Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-. The combination of the hole transporting indole group with the dibenzofuranyl group gives rise to materials that are highly suitable in devices that emit green, or blue light. Moreover, the improved amipolar characteristics give rise to more balanced charge transport in devices resulting in lower voltages and higher external quantum efficiencies (EQE's). The compounds of the present invention may be used for electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaics), switching elements, such as organic transistors, for example, organic FETs and organic TFTs, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers and electroluminescent devices, such as, for example, organic light-emitting diodes (OLEDs). Accordingly, a further subject of the present invention is directed to an electronic device, comprising a compound according to the present invention. The electronic device is preferably an electroluminescent device. The compounds of formula I can in principal be used in any layer of an EL device, but are preferably used as host, charge transport and/or charge/exciton blocking material. Particularly, the compounds of formula I are used as host material for green, especially blue light emitting phosphorescent emitters. Hence, a further subject of the present invention is directed to a charge transport layer, comprising a compound of formula I according to the present invention.
A further subject of the present invention is directed to an emitting layer, comprising a compound of formula I according to the present invention. In said embodiment a compound of formula I is preferably used as host material in combination with a phosphorescent emitter.
A further subject of the present invention is directed to a charge/exciton blocking layer, comprising a compound of formula I according to the present invention. D is preferably -CO-, -COO-, -S-, -SO-, -S02-, -0-, -NR21-, wherein R21 is Ci-Ci8alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or Ce-C aryl, such as phenyl, tolyl, naphthyl, or biphenylyl, or C2-C3oheteroaryl, such as, for example, benzimid-
Figure imgf000009_0001
azo[1 ,2-a]benzimidazo-2-yl ( ), carbazolyl, dibenzofuranyl, which can be unsubstituted or substituted especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl; or C2-Ci3heteroaryl.
E is preferably -OR31 ; -SR3i ; -NR32R33; -COR34; -COOR34; -CONR32R33; 0r -CN; wherein R3i , R32, R33 anc| R34 are independently of each other Ci-Cisalkyl, such as methyl, ethyl, n- propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or Ce-C aryl, such as phenyl, tolyl, naphthyl, or biphenylyl.
G is preferably -OR31; -SR3i ; -NR32R33; a Ci-Ci8alkyl group, a C6-Ci4aryl group, a Ce- C aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Ci3heteroaryl group, or a C2- Ci3heteroaryl group, which is substituted by F, or Ci-Cisalkyl; wherein R31, R32, R33 and R34 are independently of each other Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n- butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6-Ci4aryl, such as phenyl, tolyl, naphthyl, or biphenylyl. A C2-Ci3heteroaryl group is for example, benzimidazo[1 ,2-a]benzimidazo-5-yl
(
Figure imgf000010_0001
), benzim- idazolo[2,1-b][1 ,3]benzothiazolyl, carbazolyl, dibenzofuranyl, or dibenzotihophenyl, which can be unsubstituted or substituted, especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl ; or C2-Ci3heteroaryl.
Specific examples of the compound represented by the formula (I) are given below. The compound represented by the formula (I) is not limited to the following specific examples. re shown
(A-2),
Figure imgf000010_0002
Figure imgf000011_0001
Among the compounds of formula (I), compounds of formula
Figure imgf000011_0002
(la) are more pi ferred, wherein R1 , R2, R3, R4, R5, R6, en, B12, B13, B14, B15, B16, B17, B18, χι, Ar1, Ar2, A, and n are defined above and below.
Among the compounds of formula (la), compounds of formula
Figure imgf000012_0001
ferred, wherein R1, R2, R3, R4, R5, R6, X1 , Ar1, Ar2, A, m and n are defined above and below. unds of formula
Figure imgf000012_0002
are more preferred, wherein R1, R2, R3, R4, R5, R6, X1 , Ar1, Ar2, A, m and n are defined above and below. Among the compounds of formula (lc), compounds of formula
Figure imgf000012_0003
(Id) are more preferred, wherein
Xi is NR7, O, or S,
R1, R2, R3, R4, Rs, Re, R7, Ar1 and A are defined above and below, and
m is 0 or 1. Among the compounds of formula (Id), compounds of formula
Figure imgf000013_0001
In a preferred embodiment of the present invention m is 0.
Examples of compounds of formula (I), wherein at least one of R1, R2, R3, R4, R5 and R6 is a carbazolyl group, a diaryl amino group, or an indolyl group are shown below:
Figure imgf000013_0002
Figure imgf000014_0001
Figure imgf000014_0002
Compounds of formula (I), wherein at least one of R1, R2, R3, R4, R5 and R6 is a Ci-C2salkyl group; and/or at least a group Ar1 , Ar2 and/or A is substituted by a Ci-C2salkyl group; are suitable materials for solution processable organic light emitting devices (OLEDs). Exam
Figure imgf000014_0003
Preferably, R1 , R2, R3, R4, R5 and R6 are independently of each other -H, or -CN. Ar1 and Ar2 are independently of each other a C6-C24arylen group, which can optionally be substituted by G, a C2-C3oheteroarylen group, which can optionally be substituted by G,
The C6-C24arylen groups Ar1 and Ar2, which optionally can be substituted by G, are typically phenylene, 4-methylphenylene, 4-methoxyphenylene, naphthylene, especially 1- naphthylene, or 2-naphthylene, biphenylylene, terphenylylene, pyrenylene, 2- or 9- fluorenylene, phenanthrylene, or anthrylene, which may be unsubstituted or substituted.
Figure imgf000015_0001
The C2-C3oheteroarylen groups Ar1 and Ar2, which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms havi ated-electrons such as, for example, benzofu-
Figure imgf000015_0002
ro[2,3-b]pyridylene ( ), benzothiopheno[2,3-b]pyridylene
Figure imgf000015_0003
Figure imgf000016_0001
( ), thienylene, benzothiophenylene, thianthrenylene, furylene, furfu- rylene, 2H-pyranylene, benzofuranylene, isobenzofuranylene, dibenzofuranylene
Figure imgf000016_0002
( ), dibenzothiophenylene ( ), phenoxythienylene, pyrrolylene, imidazolylene, pyrazolylene, pyridylene, bipyridylene, triazinylene, pyrimidi- nylene, pyrazinylene, pyndazinylene, indolizinylene, isoindolylene, indolylene, indazolylene, purinylene, quinolizinylene, chinolylene, isochinolylene, phthalazinylene, naphthyndinylene, chinoxalinylene, chinazolinylene, cinnolinylene, pteridinylene, carbolinylene, benzotriazol- ylene, benzoxazolylene, phenanthridinylene, acridinylene, pyrimidinylene, phenanthroli- nylene, phenazinylene, isothiazolylene, phenothiazinylene, isoxazolylene, furazanylene,
Figure imgf000016_0003
carbazolylene ( , or ), benzimidazo[1 ,2-
Figure imgf000016_0004
a]benzimidazo-2,5-ylene ( ), benzimidazo-1 ,2-ylene ( ), or phenoxazinylene, which can be unsubstituted or substituted. R24' is a C6-C24aryl group, or a C2-C3oheteroaryl group, which can optionally be substituted by G, wherein G is as defined in above.
A further example for a C2-C3oheteroarylen group Ar1 and Ar2 is 2-phenyl pyrimidinylene.
Preferred C6-C24arylen groups are 1 ,3-phenylene, 1 ,4-phenylene, 3,3'-biphenylylene, 3,3'- m-teφhenylene, 2- or 9-fluorenylene, phenanthrylene, which may be unsubstituted or substituted, especially by C6-Cioaryl , C6-Cioaryl which is substituted by Ci-C4alkyl ; or C2- C heteroaryl.
Preferred C2-C3oheteroarylen groups are pyridylene, triazinylene, pyrimidinylene, benzofu- ro[2,3-b]pyridylene, benzothiopheno[2,3-b]pyridylene , pyrido[2,3-b]indolylene , benzofu- ro[2,3-c]pyridylene, benzothiopheno[2,3-c]pyridylene , pyrido[2,3-c]indolylene, furo[3,2- b:4,5-b']dipyridylene, thieno[3,2-b:4,5-b']dipyridylene, pyrrolo[3,2-b:4,5-b']dipyridylene, dibenzofuranylene, dibenzothiophenylene , carbazolylene and benzimidazo[1 ,2- a] benzimidazo-2,5-ylene, benzofuro[3,2-b]pyridylene, indolylene, benzothiopheno[3,2- b] pyridylene, or benzimidazo-1 ,2-ylene, which can be unsubstituted or substituted , espe- cially by C6-Ci4aryl , C6-Ci4aryl which is substituted by Ci-C4alkyl ; or C2-Ci3heteroaryl . The C6-C24arylen and C2-C3oheteroarylen groups may be substituted by G.
G is preferably Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, -CF3, a C6-Ci4aryl group, a Ce-C aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Ci3heteroaryl group, or a C2-Ci3heteroaryl group, which is substituted by F, or Ci-Cisalkyl.
Benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimidazo[1 ,2-a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are examples of a C2-Ci3heteroaryl group. Phenyl, 1-naphthyl and 2- naphthyl are examples of a Ce-C aryl group.
Figure imgf000017_0001
Preferably, Ar1 and Ar2 are independently of each other a group of formula
Figure imgf000017_0002
Further preferred groups Ar1 and Ar2 are:
Figure imgf000017_0003
If at least one of Ri, R2, R3, R4, R5 and R6 is -CN, then A is -NRi°Rii, or -Si(Ri2)(Ri3)(Ri4), a C6-C24ar l group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G. The C6-C24aryl group A, which optionally can be substituted by G, is typically phenyl, 4- methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, or anthryl, or triphenylenyl (especially triphenylen-2-yl), which may be unsubstituted or substituted. The C2-C3oheteroaryl group A, which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated π-electrons such as 9H-pyrido[2,3-b]indolyl, benzofuro[2,3- b]pyridyl, benzothiopheno[2,3-b]pyridyl, 9H-pyrido[2,3-c]indolyl, benzofuro[2,3-c]pyridyl, benzothiopheno[2,3-c]pyridyl, furo[3,2-b:4,5-b']dipyridyl, pyrrolo[3,2-b:4,5-b']dipyridyl, thieno[3,2-b:4,5-b']dipyridyl, thienyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrol- yl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, in- dolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothia- zolyl, phenothiazinyl, isoxazolyl, furazanyl, benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimid- azo[1 ,2-a]benzimidazo-2-yl, benzimidazolo[2,1-b][1 ,3]benzothiazolyl, carbazolyl, 9- phenylcarbazolyl, azabenzimidazo[1 ,2-a]benzimidazolyl, or phenoxazinyl, which can be unsubstituted or substituted.
The C6-C24aryl and C2-C3oheteroaryl groups may be substituted by G.
G is preferably Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl; -CF3, a C6-Ci4aryl group, a Ce-C aryl group, which is substituted by F, or Ci-Cisalkyl; a C2-Ci3heteroaryl group, or a C2-Ci3heteroaryl group, which is substituted by F, or Ci-Cisalkyl.
Prefered C2-C3oheteroaryl groups are pyridyl, triazinyl, pyrimidinyl, especially 9H-pyrido[2,3- b]indolyl, benzofuro[2,3-b]pyridyl, benzothiopheno[2,3-b]pyridyl, 9H-pyrido[2,3-c]indolyl, benzofuro[2,3-c]pyridyl, benzothiopheno[2,3-c]pyridyl, furo[3,2-b:4,5-b']dipyridyl, pyr- rolo[3,2-b:4,5-b']dipyridyl, thieno[3,2-b:4,5-b']dipyridyl, benzimidazo[1 ,2-a]benzimidazo-5-yl
R
Figure imgf000018_0001
), benzimidazo[1 ,2-a]benzimidazo-2-yl ( R" is
C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl), benzimid-
Figure imgf000019_0001
azolo[2,1-b][1 ,3]benzothiazolyl ( , or ), carba- zolyl, dibenzofuranyl, or dibenzothiophenyl, which can be unsubstituted or substituted especially by C6-Cioaryl, or C6-Cioaryl, which is substituted by Ci-C4alkyl; or C2-Ci4heteroaryl .
Figure imgf000019_0002
Figure imgf000020_0001
Figure imgf000021_0001
; wherein R37, R38, R39, R40 and
R41 are independently of each other -H, -CN, or a phenyl group.
Figure imgf000021_0002
If all of R1, R2, R3, R4, Rs and R6 are different from -CN, then A is a C6-C24aryl group, which can optionally be substituted by G, a Ci3-C3oheteroaryl group, which can optionally be sub- stituted by G, an azacarbazolyl, which can optionally be substituted by G, an azaindolyl, which can optionally be substituted by G, a dibenzofuranyl, which can optionally be substituted by G, a dibenzothiophenyl, which can optionally be substituted by G, a benzofuranyl, which can optionally be substituted by G, a benzothiophenyl, which can optionally be substituted by G, a pyridyl, which can optionally be substituted by G, a pyrimidinyl, which can optionally be substituted by G, a pyrazinyl, which can optionally be substituted by G, a tria- zinyl, which can optionally be substituted by G, a naphtyridinyl, which can optionally be substituted by G, or a group represented by formula
Figure imgf000022_0001
(III), or (IV), wherein
B13 B14, Bis, Bis, B17, Bis, Bis, B2o, B21, B22, B23, B2 , B25 and B26are defined above.
Figure imgf000022_0002
The group of formula (III) is preferably a group of formula
Figure imgf000022_0003
Figure imgf000023_0001
R41 are independently of each other -H, -CN, or a phenyl group. In a preferred embodiment the present invention relates to compounds of formula (I), wherein R1, R2, R3, R4, R5 and R6 are H. In said embodiment compounds of formula
Figure imgf000023_0002
Figure imgf000023_0003
Figure imgf000024_0001
Figure imgf000025_0001
Examples of compounds, wherein R1, R2, R3, R4, R5 and R6 are H and X1 is NR7, are shown below.
Figure imgf000025_0002
Figure imgf000026_0001
(C-27), (C-28), (C-29),
Figure imgf000027_0001
In said embodiment compounds of formula (I) are more preferred, wherein R1, R2, R3, R4, R5 and R6 are H and X1 is S.
Figure imgf000027_0002
Figure imgf000028_0001
Figure imgf000029_0001
In said embodiment compounds of formula (I) are most preferred, wherein R1, R2, R3, R4,
,
Figure imgf000029_0002
Figure imgf000029_0003
Figure imgf000030_0001
In another preferred embodiment the present invention relates to compounds of formula (I), wherein at least one of R1, R2, R3, R4, R5 and R6 is -CN. Examples of compounds, wherein R1, R2, R3, R5, or R6 is -CN, are shown below.
Figure imgf000031_0001
Figure imgf000032_0001
Further examples of compounds, wherein one of R1, R2, R3, R5, or R6 is -CN and X1 is O or S, are shown below.
Figure imgf000032_0002
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
I
Figure imgf000039_0002
S, Ar1 and A are defined above and m is 0 or 1.
Figure imgf000040_0001
Further preferred groups Ar1 are:
Figure imgf000040_0002
Figure imgf000041_0001
In said embodiment compounds of formula (I) are more preferred, wherein R4 is -CN. Examples of compounds, wherein R4 is -CN and X1 is NR7, are shown below.
Figure imgf000042_0001
In said embodiment compounds of formula (I) are more preferred, wherein R4 is -CN and Xi is S.
Figure imgf000042_0002
Figure imgf000043_0001
In said embodiment compounds of formula (I) are most preferred, wherein R4 is -CN and Xi is O.
Figure imgf000043_0002
Figure imgf000044_0001
Compounds of formula (ld-1a), (ld-1b), (ld-2a) and (ld-2b) are preferred. Compounds of formula (ld-1a) and (ld-1 b) are most preferred.
Examples of preferred compounds of formula I are compounds (D-33), (D-34), (D-35), (D- 36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) shown above. As well as compounds (D74) to (D131) shown above. Compounds (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) are particularly preferred. Also, compounds (D74) to
(D131 ) are particularly preferred.
Halogen is fluorine, chlorine, bromine and iodine. Ci-C25alkyl (Ci-Cisalkyl) is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3- pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1 -methyl hexyl, 1,1 ,3,3,5,5- hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyl- heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, oroctadecyl. Ci-Csalkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2- ethylhexyl. Ci-C4alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, iso- butyl, tert.-butyl.
Ci-C25alkoxy groups (Ci-Cisalkoxy groups) are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, un- decyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. Examples of Ci-Csalkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2- dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1,1,3,3-tetramethylbutoxy and 2- ethylhexyloxy, preferably Ci-C4alkoxy such as typically methoxy, ethoxy, n-propoxy, iso- propoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy.
The term "cycloalkyl group" is typically C5-Ci2cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted.
C6-C24aryl (C6-Cisaryl), which optionally can be substituted, is typically phenyl, 4- methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, oranthryl, which may be unsubstituted or substituted. Phenyl, 1-naphthyl and 2-naphthyl are examples of a C6-Cioaryl group.
C6-C24aryloxy, which optionally can be substituted, is typically C6-Cioaryloxy, which optionally can be substituted by one, or more Ci-Csalkyl and/or Ci-Csalkoxy groups, such as, for example, phenoxy, 1-naphthoxy, or 2-naphthoxy. C7-C25aralkyl is typically benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-co-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, co-phenyl-eicosyl or ω-phenyl-docosyl, preferably C7-Cisaralkyl such as benzyl, 2-benzyl-2- propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-co-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, and particularly preferred C7-Ci2aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, or ω,ω-dimethyl-co-phenyl-butyl, in which both the aliphatic hydrocarbon group and aromatic hydrocarbon group may be unsubstituted or substituted. Preferred examples are benzyl, 2- phenylethyl, 3-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl. C2-C3oheteroaryl represents a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen , oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated π-electrons such as thienyl , benzothiophenyl , dibenzothiophenyl, thianthrenyl , furyl , furfuryl , 2H-pyranyl, benzo- furanyl , isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl , pyrazolyl , pyridyl , bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl , indolizinyl , isoindolyl , indolyl , indazolyl , purinyl , quinolizinyl, chinolyl, isochinolyl, phthalazinyl , naphthyridinyl , chinoxalinyl, chinazolinyl , cinnolinyl, pteridinyl, carbazolyl , carbolinyl , benzotriazolyl , benzoxazolyl , phe- nanthridinyl , acridinyl , pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl , phenothiazinyl , isoxazolyl , furazanyl, 4-imidazo[1 ,2-a]benzimidazoyl, 5-benzimidazo[1 ,2-a]benzimidazoyl , benzimidazolo[2, 1-b][1 ,3]benzothiazolyl, carbazolyl, or phenoxazinyl , which can be unsubstituted or substituted. Benzimidazo[1 ,2-a]benzimidazo-5-yl, benzimidazo[1 ,2- a]benzimidazo-2-yl , carbazolyl and dibenzofuranyl are examples of a C2-Ci4heteroaryl group.
C6-C24arylen groups, which optionally can be substituted by G, are typically phenylene, 4- methylphenylene, 4-methoxyphenylene, naphthylene, especially 1-naphthylene, or 2- naphthylene, biphenylylene, terphenylylene, pyrenylene, 2- or 9-fluorenylene, phenan- thrylene, or anthrylene, which may be unsubstituted or substituted. Preferred C6-C24arylen groups are 1 ,3-phenylene, 3,3'-biphenylylene, 3,3'-m-terphenylene, 2- or 9-fluorenylene, phenanthrylene, which may be unsubstituted or substituted.
C2-C3oheteroarylen groups, which optionally can be substituted by G, represent a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen , oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated -electrons such as thienylene, benzothiophenylene, dibenzothio- phenylene, thianthrenylene, furylene, furfurylene, 2H-pyranylene, benzofuranylene, isoben- zofuranylene, dibenzofuranylene, phenoxythienylene, pyrrolylene, imidazolylene, pyrazol- ylene, pyridylene, bipyridylene, triazinylene, pyrimidinylene, pyrazinylene, pyridazinylene, indolizinylene, isoindolylene, indolylene, indazolylene, purinylene, quinolizinylene, chinol- ylene, isochinolylene, phthalazinylene, naphthyridinylene, chinoxalinylene, chinazolinylene, cinnolinylene, pteridinylene, carbolinylene, benzotriazolylene, benzoxazolylene, phenan- thridinylene, acridinylene, pyrimidinylene, phenanthrolinylene, phenazinylene, isothiazol- ylene, phenothiazinylene, isoxazolylene, furazanylene, carbazolylene, benzimidazo[1 ,2- a]benzimidazo-2,5-ylene, or phenoxazinylene, which can be unsubstituted or substituted . Preferred C2-C3oheteroarylen groups are pyridylene, triazinylene, pyrimidinylene, carbazolyl ene and benzimidazo[1 ,2-a]benzimidazo-2,5-ylene
Figure imgf000046_0001
( ), which can be unsubstituted or substituted, especially by C6-Cioaryl ,
C6-Cioaryl which is substituted by Ci-C4alkyl ; or C2-Ci4heteroaryl. Possible substituents of the above-mentioned groups are Ci-Csalkyl, a hydroxyl group, a mercapto group, Ci-Csalkoxy, Ci-Csalkylthio, halogen, halo-Ci-Csalkyl, or a cyano group. The C6-C24aryl (C6-Cisaryl) and C2-C3oheteroaryl groups are preferably substituted by one, or more Ci-Csalkyl groups.
If a substituent occurs more than one time in a group, it can be different in each occurrence.
Halo-Ci-Csalkyl is an alkyl group where at least one of the hydrogen atoms is replaced by a halogen atom. Examples are -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -(CF2)3CF3, and -C(CF3)3.
The wording "substituted by G" means that one, or more, especially one to three substituents G might be present.
As described above, the aforementioned groups may be substituted by E and/or, if desired, interrupted by D. Interruptions are of course possible only in the case of groups containing at least 2 carbon atoms connected to one another by single bonds; C6-Cisaryl is not interrupted; interrupted arylalkyl contains the unit D in the alkyl moiety. Ci-Cisalkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (Ch Ch OJi-g- Rx, where R* is H or Ci-Cioalkyl or C2-Ci0alkanoyl (e.g. CO-CH(C2H5)C4H9), CH2-CH(ORy')- CH2-0-Ry, where Ry is Ci-Cisalkyl, C5-Ci2cycloalkyl, phenyl, Cz-Cisphenylalkyl, and Ry' embraces the same definitions as Ry or is H;
Ci-C8alkylene-COO-Rz, e.g. CH2COORz, CH(CH3)COORz, C(CH3)2COORz, where R^ is H, Ci-Cisalkyl, (Ch Ch OJi-g-R*, and Rx embraces the definitions indicated above;
CH2CH2-0-CO-CH=CH2; CH2CH(OH)CH2-0-CO-C(CH3)=CH2.
An alkyl group substituted by E is, for example, an alkyl group where at least one of the hydrogen atoms is replaced by F. Examples are -CF3, -CF2CF3,
-CF2CF2CF3, -CF(CF3)2, -(CF2)3CF3, and -C(CF3)3.
Figure imgf000047_0001
The synthesis of is described, for example, in Achour, Reddouane;
Zniber, Rachid, Bulletin des Societes Chimiques Beiges 96 (1987) 787-92.
Figure imgf000047_0002
Suitable base skeletons of the formula are either commercially available
(especially in the cases when X is S, O, NH), or can be obtained by processes known to those skilled in the art. Reference is made to WO2010079051 and EP1885818.
The halogenation can be performed by methods known to those skilled in the art. Preference is given to brominating or iodinating in the 3 and 6 positions (dibromination) or in the 3 or 6 positions (monobromination) of the base skeleton of the formula 2,8 positions (diben- zofuran and dibenzothiophene) or 3,6 positions (carbazole). Optionally substituted dibenzofurans, dibenzothiophenes and carbazoles can be dibromin- ated in the 2,8 positions (dibenzofuran and dibenzothiophene) or 3,6 positions (carbazole) with bromine or NBS in glacial acetic acid or in chloroform. For example, the bromination with Br2 can be effected in glacial acetic acid or chloroform at low temperatures, e.g. 0°C. Suitable processes are described, for example, in M. Park, J.R. Buck, C.J. Rizzo, Tetrahedron, 54 (1998) 12707-12714 for X= NPh, and in W. Yang et al., J. Mater. Chem. 13 (2003) 1351 for X= S. In addition, 3,6-dibromocarbazole, 3,6-dibromo-9-phenylcarbazole, 2,8- dibromodibenzothiophene, 2,8-dibromodibenzofuran, 2-bromocarbazole, 3- bromodibenzothiophene, 3-bromodibenzofuran, 3-bromocarbazole, 2- bromodibenzothiophene and 2-bromodibenzofuran are commercially available.
Monobromination in the 4 position of dibenzofuran (and analogously for dibenzothiophene) is described, for example, in J. Am. Chem. Soc. 1984, 106, 7150. Dibenzofuran (diben- zothiophene) can be monobrominated in the 3 position by a sequence known to those skilled in the art, comprising a nitration, reduction and subsequent Sandmeyer reaction.
Monobromination in the 2 position of dibenzofuran or dibenzothiophene and monobromination in the 3 position of carbazole are effected analogously to the dibromination, with the exception that only one equivalent of bromine or NBS is added.
Alternatively, it is also possible to utilize iodinated dibenzofurans, dibenzothiophenes and carbazoles. The preparation is described, inter alia, in Tetrahedron. Lett. 47 (2006) 6957- 6960, Eur. J. Inorg. Chem. 24 (2005) 4976-4984, J. Heterocyclic Chem. 39 (2002) 933-941 , J. Am. Chem. Soc. 124 (2002) 1 1900-1 1907, J. Heterocyclic Chem, 38 (2001) 77-87.
For the nucleophilic substitution, CI- or F-substituted dibenzofurans, dibenzothiophenes and carbazoles are required. The chlorination is described, inter alia, in J. Heterocyclic
Chemistry, 34 (1997) 891-900, Org. Lett., 6 (2004) 3501-3504; J. Chem. Soc. [Section] C: Organic, 16 (1971) 2775-7, Tetrahedron Lett. 25 (1984) 5363-6, J. Org. Chem. 69 (2004)
8177-8182. The fluorination is described in J. Org. Chem. 63 (1998) 878-880 and J. Chem.
Soc, Perkin Trans. 2, 5 (2002) 953-957.
H
The introduction of the group ¾ is performed in the presence of a base.
Suitable bases are known to those skilled in the art and are preferably selected from the group consisting of alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca(OH)2, alkali metal hydrides such as NaH, KH, alkali metal amides such as NaNH2, alkali metal or alkaline earth metal carbonates such as K2CO3 or CS2CO3, and alkali metal alkox- ides such as NaOMe, NaOEt. In addition, mixtures of the aforementioned bases are suitable. Particular preference is given to NaOH, KOH, NaH or K2CO3.
The synthesis of of the compounds of formula (I) can be done in analogy to methods known in the literature. Heteroarylation of can be affected, for
Figure imgf000049_0001
example, by copper-catalyzed coupling of (R4 = H, or CN; Ullmann reaction). Indole and 5-cyanoindole derivatives are commercially available. The synthesis
Figure imgf000049_0002
2-bromo-8-iodo-dibenzofurane, and 2-bromo-8-iodo-
Figure imgf000049_0003
dibenzofurane, , is described in EP1885818. er-catalyzed coupling of
to the brominated com
Figure imgf000049_0004
(R4 = H, or CN; Ullmann reaction).
The N-arylation is, for example, disclosed in H. Gilman and D. A. Shirley, J. Am. Chem. Soc. 66 (1944) 888; D. Li et al., Dyes and Pigments 49 (2001) 181 - 186 and Eur. J. Org. Chem. (2007) 2147-2151. The reaction can be performed in solvent or in a melt. Suitable solvents are, for example, (polar) aprotic solvents such as dimethyl sulfoxide, dimethylfor- mamide, N-methyl-2-pyrrolidone (NMP), tridecane or alcohols.
Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and car- bazoles can be readily prepared by an increasing number of routes. An overview of the synthetic routes is, for example, given in Angew. Chem. Int. Ed. 48 (2009) 9240 - 9261.
By one common route diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes, and carbazoles can be obtained by reacting halogenated dibenzofurans, dibenzothiophenes and carbazoles with (Y10)2B-B(OY1)2,
Figure imgf000050_0001
Υ ο'Β"Β^γ
or in the presence of a catalyst, such as, for example, [1 ,1'- bis(diphenylphosphino)ferrocene]dichloropalladium(ll), complex (Pd(CI)2(dppf)), and a base, such as, for example, potassium acetate, in a solvent, such as, for example, dimethyl formamide, dimethyl sulfoxide, dioxane and/or toluene (cf. Prasad Appukkuttan et al., Syn- lett 8 (2003) 1204), wherein Y1 is independently in each occurrence a C1-C1 sal kylg roup and Y2 is independently in each occurrence a C2-Cioalkylene group, such as -CY3Y4-CY5Y6-, or -CY7Y8-CY9Y10- CY11Y12-, wherein Y3, Y4, Y¾, γβ, γ , γβ_ γ9 γιο_ γιι and Y^ are independently of each other hydrogen, or a Ci-Cisalkylgroup, especially -C(CH3)2C(CH3)2-, - C(CH3)2CH2C(CH3)2-, or -CH2C(CH3)2CH2-, and Y« and Y^ are independently of each other hydrogen, or a Ci-Cisalkylgroup.
Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting halogenated dibenzofurans, dibenzothiophenes and carbazoles with alkyl lithium reagents, such as, for example, n-butyl lithium, or t-buthyl lithium, followed nic esters, such as, for example, B(isopropoxy)3,
B(methoxy)3, or
Figure imgf000050_0002
(cf. Synthesis (2000) 442-446).
Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting dibenzofurans, dibenzothiophenes and carbazoles with lithium amides, such as, for example, lithium diisopropylamide (LDA) followed by reaction with boronic esters such as, for example, B(isopropoxy)3, B(methoxy)3, or
,
Figure imgf000050_0003
(J. Org. Chem. 73 (2008) 2176-2181 ).
Compounds of formula
Figure imgf000050_0004
(ID are starting materials in the synthesis of the compounds of formula (I) and form a further subject of the present invention. A is CI, Br, or I. R1, R2, R3, R4, R5, R6, X1, Ar1, Ar2, m and n are defined above.
Figure imgf000051_0001
Xi is NR7, O, or S,
A' is CI, Br, or I,
R1, R2, R3, R4, R5, R67 R7 anc| Ari are defined above, and
m is 0 or 1. For R1, R2, R3, R4, R5, R6, R7 and Ar1 the same preferences apply as described above for the compounds of formula (I).
Figure imgf000051_0002
It has been found that the compounds of the formula I are particularly suitable for use in applications in which charge carrier conductivity is required, especially for use in organic electronics applications, for example selected from switching elements such as organic transistors, e.g. organic FETs and organic TFTs, organic solar cells and organic light- emitting diodes (OLEDs), the compounds of the formula I being particularly suitable in OLEDs for use as matrix material in a light-emitting layer and/or as electron and/or exciton blocker material and/or as hole and/or exciton blocker material, especially in combination with a phosphorescence emitter. In the case of use of the inventive compounds of the formula I in OLEDs, OLEDs which have good efficiencies and a long lifetime and which can be operated especially at a low use and operating voltage are obtained. The inventive compounds of the formula I are suitable especially for use as matrix and/or charge/exciton blocker materials for blue and green emitters, for example light blue or deep blue emitters, these being especially phosphorescence emitters. Furthermore, the compounds of the formula I can be used as conductor/complementary materials in organic electronics applica- tions selected from switching elements and organic solar cells.
The compounds of the formula I can be used as matrix material and/or charge/exciton blocker material and/or charge transport material (charge conductor material). The inventive compounds of the formula I are preferably used as matrix materials in organic elec- tronics applications, especially in OLEDs.
In the emission layer or one of the emission layers of an OLED, it is also possible to combine an emitter material with a matrix material of the compound of the formula I and a further matrix material. This may achieve a high quantum efficiency of this emission layer.
When a compound of the formula I is used as matrix (host) material in an emission layer and additionally as charge/exciton blocker material, owing to the chemical identity or similarity of the materials, an improved interface between the emission layer and the adjacent charge/exciton blocker material, which can lead to a decrease in the voltage with equal luminance and to an extension of the lifetime of the OLED. Moreover, the use of the same material for charge/exciton blocker material and for the matrix of an emission layer allows the production process of an OLED to be simplified, since the same source can be used for the vapor deposition process of the material of one of the compounds of the formula I. Suitable structures of organic electronic devices are known to those skilled in the art and are specified below.
The organic transistor generally includes a semiconductor layer formed from an organic layer with charge transport capacity; a gate electrode formed from a conductive layer; and an insulat- ing layer introduced between the semiconductor layer and the conductive layer. A source electrode and a drain electrode are mounted on this arrangement in order thus to produce the transistor element. In addition, further layers known to those skilled in the art may be present in the organic transistor. The organic solar cell (photoelectric conversion element) generally comprises an organic layer present between two plate-type electrodes arranged in parallel. The organic layer may be configured on a comb-type electrode. There is no particular restriction regarding the site of the organic layer and there is no particular restriction regarding the material of the electrodes. When, however, plate-type electrodes arranged in parallel are used, at least one electrode is preferably formed from a transparent electrode, for example an ITO electrode or a fluorine-doped tin oxide electrode. The organic layer is formed from two sublayers, i.e. a layer with p-type semiconductor properties or hole transport capacity, and a layer formed with n-type semiconductor properties or charge transport capacity. In addition, it is possible for further layers known to those skilled in the art to be present in the organic solar cell. The layers with charge transport capacity may com- prise the compounds of formula I. It is likewise possible that the compounds of the formula I are present both in the light- emitting layer (preferably as matrix material) and in the blocking layers (as charge/exciton blockers).
The present invention further provides an organic light-emitting diode comprising an anode (a) and a cathode (i) and a light-emitting layer (e) arranged between the anode (a) and the cathode (i), and if appropriate at least one further layer selected from the group consisting of at least one blocking layer for holes/excitons, at least one blocking layer for elec- trons/excitons, at least one hole injection layer, at least one hole transport layer, at least one electron injection layer and at least one electron transport layer, wherein the at least one compound of the formula I is present in the light-emitting layer (e) and/or in at least one of the further layers. The at least one compound of the formula I is preferably present in the light-emitting layer and/or the charge/exciton blocking layers.
In a preferred embodiment of the present invention, at least one compound of the formula I, especially a compound of formula (ld-1a), (ld-1b), (ld-2a), or (ld-2b), very especially a compound of the formula (ld-1b), or (ld-2b) is used as charge transport material. Examples of preferred compounds of formula I are compounds (D-33), (D-34), (D-35), (D-36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) shown above. As well as compounds (D74) to (D131) shown above. Compounds (D-44), (D-45), (D-49), (D- 50), (D-51 ), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) are particularly preferred. Also, compounds (D74) to (D131) are particu- lariy preferred.
In another preferred embodiment of the present invention, at least one compound of the formula I, especially a compound of formula (ld-1a), (ld-1b), (ld-2a), or (ld-2b), very especially a compound of the formula (ld-1b), or (ld-2b), is used as charge/exciton blocker mate- rial. Examples of preferred compounds of formula I are compounds (D-33), (D-34), (D-35), (D-36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) shown above. As well as compounds (D74) to (D131) shown above. Compounds (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) are particularly preferred. Also, compounds (D74) to
(D131 ) are particularly preferred.
The present application further relates to a light-emitting layer comprising at least one compound of the formula I.
Structure of the inventive OLED
The inventive organic light-emitting diode (OLED) thus generally has the following structure: an anode (a) and a cathode (i) and a light-emitting layer (e) arranged between the anode (a) and the cathode (i). The inventive OLED may, for example - in a preferred embodiment - be formed from the following layers:
1. Anode (a)
2. Hole transport layer (c)
3. Light-emitting layer (e)
4. Blocking layer for holes/excitons (f)
5. Electron transport layer (g)
6. Cathode (i)
Layer sequences different than the aforementioned structure are also possible, and are known to those skilled in the art. For example, it is possible that the OLED does not have all of the layers mentioned; for example, an OLED with layers (a) (anode), (e) (light-emitting layer) and (i) (cathode) is likewise suitable, in which case the functions of the layers (c) (hole transport layer) and (f) (blocking layer for holes/excitons) and (g) (electron transport layer) are assumed by the adjacent layers. OLEDs which have layers (a), (c), (e) and (i), or layers (a), (e), (f), (g) and (i), are likewise suitable. In addition, the OLEDs may have a blocking layer for electrons/excitons (d) between the hole transport layer (c) and the Light- emitting layer (e).
It is additionally possible that a plurality of the aforementioned functions (electron/exciton blocker, hole/exciton blocker, hole injection, hole conduction, electron injection, electron conduction) are combined in one layer and are assumed, for example, by a single material present in this layer. For example, a material used in the hole transport layer, in one em- bodiment, may simultaneously block excitons and/or electrons.
Furthermore, the individual layers of the OLED among those specified above may in turn be formed from two or more layers. For example, the hole transport layer may be formed from a layer into which holes are injected from the electrode, and a layer which transports the holes away from the hole-injecting layer into the light-emitting layer. The electron conduction layer may likewise consist of a plurality of layers, for example a layer in which electrons are injected by the electrode, and a layer which receives electrons from the electron injection layer and transports them into the light-emitting layer. These layers mentioned are each selected according to factors such as energy level, thermal resistance and charge carrier mobility, and also energy difference of the layers specified with the organic layers or the metal electrodes. The person skilled in the art is capable of selecting the structure of the OLEDs such that it is matched optimally to the organic compounds used in accordance with the invention. In a preferred embodiment the OLED according to the present invention comprises in this order:
(a) an anode,
(b) optionally a hole injection layer,
(c) optionally a hole transport layer,
(d) optionally an exciton blocking layer (e) an emitting layer,
(f) optionally a hole/ exciton blocking layer
(g) optionally an electron transport layer,
(h) optionally an electron injection layer, and
(i) a cathode.
In a particularly preferred embodiment the OLED according to the present invention comprises in this order:
(a) an anode,
(b) optionally a hole injection layer,
(c) a hole transport layer,
(d) an exciton blocking layer
(e) an emitting layer,
(f) a hole/ exciton blocking layer
(g) an electron transport layer, and
(h) optionally an electron injection layer, and
(i) a cathode.
The properties and functions of these various layers, as well as example materials are known from the prior art and are described in more detail below on basis of preferred embodiments.
Anode (a):
The anode is an electrode which provides positive charge carriers. It may be composed, for example, of materials which comprise a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides. Alternatively, the anode may be a conductive polymer. Suitable metals comprise the metals of groups 1 1 , 4, 5 and 6 of the Periodic Table of the Elements, and also the transition metals of groups 8 to 10. When the anode is to be transparent, mixed metal oxides of groups 12, 13 and 14 of the Periodic Table of the Elements are generally used, for example indium tin oxide (ITO). It is likewise possible that the anode (a) comprises an organic material, for example polyaniline, as described, for example, in Nature, Vol. 357, pages 477 to 479 (June 11 , 1992). Preferred anode materials include conductive metal oxides, such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AlZnO), and metals. Anode (and substrate) may be sufficiently transparent to create a bottom-emitting device. A preferred transparent substrate and anode combination is commercially available ITO (anode) deposited on glass or plastic (substrate). A reflective anode may be preferred for some top-emitting devices, to increase the amount of light emitted from the top of the device. At least either the anode or the cathode should be at least partly transparent in order to be able to emit the light formed. Other anode materials and structures may be used.
Hole injection layer (b):
Generally, injection layers are comprised of a material that may improve the injection of charge carriers from one layer, such as an electrode or a charge generating layer, into an adjacent organic layer. Injection layers may also perform a charge transport function. The hole injection layer may be any layer that improves the injection of holes from anode into an adjacent organic layer. A hole injection layer may comprise a solution deposited material, such as a spin-coated polymer, or it may be a vapor deposited small molecule material, such as, for example, CuPc or MTDATA. Polymeric hole-injection materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers, such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]- 2,5-diyl) (Plexcore® OC Conducting Inks commercially available from Plextronics), and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PEDOT/PSS.
Hole transport layer (c):
Either hole-transporting molecules or polymers may be used as the hole transport material. Suitable hole transport materials for layer (c) of the inventive OLED are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996, US20070278938, US2008/0106190, US2011/0163302 (triarylamines with (di)benzothiophen/(di)benzofuran; Nan-Xing Hu et al. Synth. Met. 111 (2000) 421 (in- dolocarbazoles), WO2010002850 (substituted phenylamine compounds) and
WO2012/16601 (in particular the hole transport materials mentioned on pages 16 and 17 of WO2012/16601 ). Combination of different hole transport material may be used. Reference
is m (HTL1-1)
and
Figure imgf000056_0001
(HTL2-1 ) constitute the hole transport layer.
Customarily used hole-transporting molecule sisting of
Figure imgf000056_0002
(4-phenyl-N-(4-phenylphenyl)-N-[4-[4-(N-[4-(4-phenyl- phenyl)phenyl]anilino)phenyl]phenyl]aniline),
Figure imgf000057_0001
(4-phenyl-N-(4- (4-phenyl-N-(4-phenylphenyl)anilino)phenyl]phenyl]anilin
Figure imgf000057_0002
(4-phenyl-N-[4-(9-phenylcarbazol-3-yl)phenyl]-N-(4-
phenylphenyl)aniline), diazasilole-
2,2'-3a,7a-dihydro-1 ,3,2
Figure imgf000057_0003
-benzodiazasilole]),
(N2,N2,N2\N2\N7,N7,N7\N7'-octakis(p olyl)-9,9'-spirobi[fluorene]-2,2\7J' etramine), 4,4'- bis[N-(1-naphthyl)-N-phenylamino]biphenyl (a-NPD), N,N'-diphenyl-N,N'-bis(3- methylphenyl)-[1 ,1 '-biphenyl]-4,4'-diamine (TPD), 1 ,1-bis[(di-4-tolylamino)phenyl]- cyclohexane (TAPC), N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1 ,1 '-(3,3'-dimethyl)- biphenyl]-4,4'-diamine (ETPD), tetrakis(3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA), a-phenyl-4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehyde diphe- nylhydrazone (DEH), triphenylamine (TPA), bis[4-(N,N-diethylamino)2-methylphenyl](4- methylphenyl)methane (MPMP), 1-phenyl-3-[p-(diethylamino)styryl]5-[p- (diethylamino)phenyl]pyrazoline (PPR or DEASP), 1 ,2-trans-bis(9H-carbazol9-yl)- cyclobutane (DCZB), N,N,N',N'-tetrakis(4-methylphenyl)-(1 ,1 '-biphenyl)-4,4'-diamine (TTB), fluorine compounds such as 2,2',7J'-tetra(N,N-di-tolyl)amino9,9-spirobifluorene (spiro- TTB), N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)9,9-spirobifluorene (spiro-NPB) and 9,9- bis(4-(N,N-bis-biphenyl-4-yl-amino)phenyl-9Hfluorene, benzidine compounds such as Ν,Ν'- bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine and porphyrin compounds such as copper phthalocyanines. In addition, polymeric hole-injection materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, self-doping polymers, such as, for example, sulfonated poly(thiophene-3-[2[(2-methoxyethoxy)ethoxy]-2,5- diyl) (Plexcore® OC Conducting Inks commercially available from Plextronics), and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PE- DOT/PSS. Preferred examples of a material of the hole injecting layer are a porphyrin compound, an aromatic tertiary amine compound, or a styrylamine compound. Particularly preferable examples include an aromatic tertiary amine compound such as hexacyanohex- aazatriphenylene (HAT).
In a preferred embodiment it is possible to use metal carbene complexes as hole transport materials. Suitable carbene complexes are, for example, carbene complexes as described in WO2005/019373A2, WO2006/056418 A2, WO2005/113704, WO2007/115970,
WO2007/115981 , WO2008/000727 and PCT/EP One example of a suitable
carbene complex is lr(DPBIC)3 with the formula:
Figure imgf000058_0001
(HTM-1). Another exa ne complex is lr(ABIC)3 with the formu-
la:
Figure imgf000058_0002
M-2).
The hole-transporting layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device. Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, 2003, 359 (p-doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 2003, 4495 and Pfeiffer et al., Organic Electronics 2003, 4, 89 - 103 and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233. For ex- ample it is possible to use mixtures in the hole-transporting layer, in particular mixtures which lead to electrical p-doping of the hole-transporting layer. p-Doping is achieved by the addition of oxidizing materials. These mixtures may, for example, be the following mixtures: mixtures of the abovementioned hole transport materials with at least one metal oxide, for example M0O2, M0O3, WOx, Re03 and/or V2O5, preferably M0O3 and/or Re03, more pref- erably M0O3, or mixtures comprising the aforementioned hole transport materials and one or more compounds selected from 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6- tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), 2,5-bis(2-hydroxyethoxy)-7,7,8,8- tetracyanoquinodimethane, bis(tetra-n-butylammonium)tetracyanodiphenoquinodimethane, 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene, 1 1 ,11 ,12, 12- tetracyanonaphtho2,6-quinodimethane, 2-fluoro-7,7,8,8-tetracyanoquino-dimethane, 2,5- difluoro-7,7,8,8etracyanoquinodimethane, dicyanomethylene-1 ,3,4,5,7,8-hexafluoro-6H- naphthalen-2-ylidene)malononitrile (F6-TNAP), Mo(tfd)3 (from Kahn et al., J. Am. Chem. Soc. 2009, 131 (35), 12530-12531), compounds as described in EP1988587, US2008265216, EP2180029, US20100102709, WO2010132236, EP2180029 and quinone compounds as mentioned in EP2401254. Preferred mixtures comprise the aforementioned carbene complexes, such as, for example, the carbene complexes HTM-1 and HTM-2, and M0O3 and/or ReC>3, especially M0O3. In a particularly preferred embodiment the hole transport layer comprises from 0.1 to 10 wt % of M0O3 and 90 to 99.9 wt % carbene complex, especially of the carbene complex HTM-1 and HTM-2, wherein the total amount of the M0O3 and the carbene complex is 100 wt %.
Exciton blocking layer (d):
Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer. An electron/exciton blocking layer (d) may be disposed between the first emitting layer (e) and the hole transport layer (c), to block electrons from emitting layer (e) in the direction of hole transport layer (c). Blocking layers may also be used to block excitons from diffusing out of the emissive layer. Suitable metal com- plexes for use as electron/exciton blocker material are, for example, carbene complexes as described in WO2005/019373A2, WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981 , WO2008/000727 and PCT/EP2014/055520. Explicit reference is made here to the disclosure of the WO applications cited, and these disclosures shall be considered to be incorporated into the content of the present application. One example of a suita- ble carbene complex is compound HTM-1 and HTM-2.
Emitting layer (e)
The light-emitting layer (e) comprises at least one emitter material. In principle, it may be a fluorescence or phosphorescence emitter, suitable emitter materials being known to those skilled in the art. The at least one emitter material is preferably a phosphorescence emitter. The phosphorescence emitter compounds used with preference are based on metal complexes, and especially the complexes of the metals Ru, Rh, Ir, Pd and Pt, in particular the complexes of Ir, have gained significance. The compounds of the formula I can be used as the matrix in the light-emitting layer.
Suitable metal complexes for use in the inventive OLEDs are described, for example, in documents WO 02/60910 A1 , US 2001/0015432 A1 , US 2001/0019782 A1 ,
US 2002/0055014 A1 , US 2002/0024293 A1 , US 2002/0048689 A1 , EP 1 191 612 A2, EP 1 191 613 A2, EP 1 21 1 257 A2, US 2002/0094453 A1 , WO 02/02714 A2,
WO 00/70655 A2, WO 01/41512 A1 , WO 02/15645 A1 , WO 2005/019373 A2,
WO 2005/113704 A2, WO 2006/115301 A1 , WO 2006/067074 A1 , WO 2006/056418, WO 200612181 1 A1 , WO 2007095118 A2, WO 2007/115970, WO 2007/1 15981 ,
WO 2008/000727, WO2010129323, WO2010056669, WO10086089, US2011/0057559, WO2011/106344, US2011/0233528, WO2012/048266 and WO2012/172482.
Further suitable metal complexes are the commercially available metal complexes tris(2- phenylpyridine)iridium(lll), iridium(lll) tris(2-(4-tolyl)pyridinato-N,C2'), bis(2- phenylpyridine)(acetylacetonato)iridium(lll), iridium(lll) tris(l-phenylisoquinoline), iridium(lll) bis(2,2'-benzothienyl)pyridinato-N,C3')(acetylacetonate), tris(2-phenylquinoline)iridium(lll), iridium(lll) bis(2-(4,6-difluorophenyl)pyridinato-N,C2)picolinate, iridium(lll) bis(1- phenylisoquinoline)(acetylacetonate), bis(2-phenylquinoline)(acetylacetonato)iridium(lll), iridium(lll) bis(di-benzo[f,h]quinoxaline)(acetylacetonate), iridium(lll) bis(2-methyldi- benzo[f,h]quinoxaline)(acetylacetonate) and tris(3-methyl-1-phenyl-4-trimethylacetyl-5- pyrazolino)terbium(lll), bis[1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinoline](acetyl- acetonato)iridium(lll), bis(2-phenylbenzothiazolato)(acetylacetonato)iridium(lll), bis(2-(9,9- dihexylfluorenyl)-1-pyridine)(acetylacetonato)iridium(lll), bis(2-benzo[b]thiophen-2-yl- pyridine)(acetylacetonato)iridium(lll).
In addition, the following commercially available materials are suitable:
tris(dibenzoylacetonato)mono(phenanthroline)europium(lll), tris(dibenzoylmethane)- mono(phenanthroline)europium(lll), tris(dibenzoylmethane)mono(5-aminophenanthroline)- europium(lll), tris(di-2-naphthoylmethane)mono(phenanthroline)europium(lll), tris(4- bromobenzoylmethane)mono(phenanthroline)europium(lll), tris(di(biphenyl)methane)- mono(phenanthroline)europium(lll), tris(dibenzoylmethane)mono(4J-diphenyl- phenanthroline)europium(lll), tris(dibenzoylmethane)mono(4J-di-methyl- phenanthroline)europium(lll), tris(dibenzoylmethane)mono(4J-dimethylphenan- throlinedisulfonic acid)europium(lll) disodium salt, tris[di(4-(2-(2-ethoxyethoxy)ethoxy)- benzoylmethane)]mono(phenanthroline)europium(lll) and tris[di[4-(2-(2-ethoxy- ethoxy)ethoxy)benzoylmethane)]mono(5-aminophenanthroline)europium(lll), osmium(ll) bis(3-(trifluoromethyl)-5-(4-tert-butylpyridyl)-1 ,2,4-triazolato)diphenylmethylphosphine, os- mium(ll) bis(3-(trifluoromethyl)-5-(2-pyridyl)-1 ,2,4-triazole)dimethylphenylphosphine, osmi- um(ll) bis(3-(trifluoromethyl)-5-(4-tert-butylpyridyl)-1 ,2,4- triazolato)dimethylphenylphosphine, osmium(ll) bis(3-(trifluoromethyl)-5-(2-pyridyl)- pyrazolato)dimethylphenylphosphine, tris[4,4'-di-tert-butyl(2,2')-bipyridine]ruthenium(lll), osmium(ll) bis(2-(9,9-dibutylfluorenyl)-1-isoquinoline(acetylacetonate).
Preferred phosphorescence emitters are carbene complexes. Suitable phosphorescent blue emitters are specified in the following publications: WO2006/056418A2,
WO2005/113704, WO2007/1 15970, WO2007/115981 , WO2008/000727, WO2009050281 , WO2009050290, WO201 1051404, US2011/057559 WO201 1/073149, WO2012/121936A2, US2012/0305894A1 , WO2012/170571 , WO2012/170461 , WO2012/170463,
WO2006/121811 , WO2007/095118, WO2008/156879, WO2008/156879, WO2010/068876, US201 1/0057559, WO201 1/106344, US201 1/0233528, WO2012/048266,
WO2012/172482, PCT/EP2014/064054 and PCT/EP2014/066272.
Preferably, the light emitting layer (e) comprises at least one carbine complex as phosphorescence emitter. Suitable carbine complexes are, for example, compounds of the
M[carbene]n 1
formula 0 (IX), which are described in WO 2005/019373 A2, wherein the symbols have the following meanings:
M is a metal atom selected from the group consisting of Co, Rh, Ir, Nb, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re, Cu, Ag and Au in any oxidation state possible for the respective metal atom; Carbene is a carbene ligand which may be uncharged or monoanionic and monodentate, bidentate or tridentate, with the carbene ligand also being able to be a biscarbene or triscarbene ligand;
L is a monoanionic or dianionic ligand, which may be monodentate or bidentate;
K is an uncharged monodentate or bidentate ligand selected from the group consisting of phosphines; phosphonates and derivatives thereof, arsenates and derivatives thereof; phosphites; CO; pyridines; nitriles and conjugated dienes which form a π complex with M1; n1 is the number of carbene ligands, where n1 is at least 1 and when n1 > 1 the carbene ligands in the complex of the formula I can be identical or different;
ml is the number of ligands L, where ml can be 0 or≥ 1 and when ml > 1 the ligands L can be identical or different;
o is the number of ligands K, where o can be 0 or≥ 1 and when o > 1 the ligands K can be identical or different;
where the sum n1 + ml + o is dependent on the oxidation state and coordination number of the metal atom and on the denticity of the ligands carbene, L and K and also on the charge on the ligands, carbene and L, with the proviso that n1 is at least 1. lexes of the general formula
Figure imgf000061_0001
IXa), which are described in WO2011/073149, where M is Ir, or Pt,
n1 is an integer selected from 1 , 2 and 3,
Y is N R51', O, S or C(R25')2,
A2', A3', A4', and A5'are each independently N or C, where 2 A = nitrogen atoms and at least one carbon atom is present between two nitrogen atoms in the ring,
R51' is a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,
R52', R53', R54' and R55' are each, if A2', A3', A4' and/or A5' is N, a free electron pair, or, if A2', A3', A4' and/or A5' is C, each independently hydrogen, linear or branched alkyl radical op- tionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 car- bon atoms and/or heteroatoms, group with donor or acceptor action, or
R53' and R54' together with A3' and A4' form an optionally substituted, unsaturated ring optionally interrupted by at least one further heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms,
R56', R57', R58' and R59' are each independently hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, cycloheteroalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or un- substituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms, group with donor or acceptor action, or
R56' and R57', R57' and R58' or R58' and R59', together with the carbon atoms to which they are bonded, form a saturated, unsaturated or aromatic, optionally substituted ring optionally interrupted by at least one heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms, and/or
if A5' is C, R55' and R56' together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, an aromatic unit, heteroaromatic unit and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which is optionally fused a substituted or unsubstituted, five- to eight-membered ring comprising carbon atoms and/or heteroatoms,
R25' is independently a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,
K is an uncharged mono- or bidentate ligand,
L is a mono- or dianionic ligand, preferably monoanionic ligand, which may be mono- or bidentate,
ml is 0, 1 or 2, where, when ml is 2, the K ligands may be the same or different, o1 is 0, 1 or 2, where, when o1 is 2, the L ligands may be the same or different.
The compound of formula IX is preferably a compound of the formula:
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
-81), (BE-82),
Figure imgf000070_0001
(BE-94), (BE-95),
Figure imgf000071_0001
(BE-104), (BE-105),
Figure imgf000072_0001
18),
Figure imgf000073_0001
(BE-125), or (BE-126). The compound of formula IX is more preferably a compound (BE-1), (BE-2), (BE-7), (BE- 12), (BE-16), (BE-64), or (BE-70). The most preferred phosphorescent blue emitters are compounds (BE-1 ) and (BE-12). The homoleptic metal-carbene complexes may be present in the form of facial or meridional isomers, preference being given to the facial isomers.
Suitable carbene complexes of formula (IX) and their preparation process are, for example, described in WO2011/073149.
The compounds of the present invention can also be used as host for phosphorescent green emitters. Suitable phosphorescent green emitters are, for example, specified in the following publications: WO2006014599, WO20080220265, WO2009073245, WO2010027583, WO2010028151 , US201 10227049, WO201 1090535, WO2012/08881 , WO20100056669, WO20100118029, WO20100244004, WO201 1109042, WO2012166608, US20120292600, EP2551933A1 ; US6687266, US20070190359, US20070190359, US20060008670; WO2006098460, US20110210316, WO2012053627; US6921915, US20090039776; JP2007123392 and European patent application no. 14180422.9.
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Host (matrix) materials
The light-emitting layer may comprise further components in addition to the emitter material. For example, a fluroescent dye may be present in the light-emitting layer in order to alter the emission color of the emitter material. In addition - in a preferred embodiment - a matrix material can be used. This matrix material may be a polymer, for example poly(N- vinylcarbazole) or polysilane. The matrix material may, however, be a small molecule, for example 4,4'-N,N'-dicarbazolebiphenyl (CDP=CBP) or tertiary aromatic amines, for example TCTA. In another preferred embodiment of the present invention, at least one compound of the formula I, especially a compound of formula (ld-1a), (ld-1b), (ld-2a), or (ld-2b), very especially a compound of the formula (ld-1a), or (ld-2a), is used as matrix material. Examples of preferred compounds of formula I are compounds (D-33), (D-34), (D-35), (D-36), (D-37), (D-38), (D-39), (D-40), (D-41), (D-44), (D-45), (D-49), (D-50), (D-51), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) shown above. As well as compounds (D74) to (D131) shown above. Compounds (D-44), (D-45), (D-49), (D- 50), (D-51 ), (D-52), (D-53), (D-54), (D-55), (D-56), (D-57), (D-58), (D-62), (D-63), (D-67), (D-68) and (D-70) are particularly preferred. Also, compounds (D74) to (D131) are particularly preferred.
In a preferred embodiment, the light-emitting layer is formed from 2 to 40% by weight, preferably 5 to 35% by weight, of at least one of the aforementioned emitter materials and 60 to 98% by weight, preferably 75 to 95% by weight, of at least one of the aforementioned matrix materials - in one embodiment at least one compound of the formula I - where the sum total of the emitter material and of the matrix material adds up to 100% by weight.
In particularly preferred embod r comprises a compound of for-
mula I, such as, for example,
Figure imgf000078_0001
(C-80), and two carbene complexes, preferably BE-1 and HTM-1 , or HTM-2. In said embodiment, the light-emitting layer is formed from 2 to 40% by weight, preferably 5 to 35% by weight, of BE-1 and 60 to 98% by weight, preferably 65 to 95% by weight, of a compound of the formula I and and HTM-1 , or HTM-2, where the sum total of the carben complexes and of the compound of formula I adds up to 100% by weight.
Suitable metal complexes for use together with the compounds of the formula I as matrix material in OLEDs are, for example, also carbene complexes as described in
WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/113704, WO 2007/1 15970,
WO 2007/115981 and WO 2008/000727.
Further suitable host materials, which may be small molecules or (co)polymers of the small molecules mentioned, are specified in the following publications: WO2007108459 (H-1 to H-37), preferably H-20 to H-22 and H-32 to H-37, most preferably H-20, H-32, H-36, H-37, WO2008035571 A1 (Host 1 to Host 6), JP2010135467 (compounds 1 to 46 and Host-1 to Host-39 and Host-43), WO2009008100 compounds No.1 to No.67, preferably No.3, No.4, No.7 to No. 12, No.55, No.59, No. 63 to No.67, more preferably No. 4, No. 8 to No. 12, No. 55, No. 59, No.64, No.65, and No. 67, WO2009008099 compounds No. 1 to No. 110, WO2008140114 compounds 1-1 to 1-50, WO2008090912 compounds OC-7 to OC-36 and the polymers of Mo-42 to Mo-51 , JP2008084913 H-1 to H-70, WO2007077810 compounds 1 to 44, preferably 1 , 2, 4-6, 8, 19-22, 26, 28-30, 32, 36, 39-44, WO201001830 the polymers of monomers 1-1 to 1-9, preferably of 1-3, 1-7, and 1-9, WO2008029729 the (poly- mens of) compounds 1-1 to 1-36, WO20100443342 HS-1 to HS-101 and BH-1 to BH-17, preferably BH-1 to BH-17, J P2009182298 the (co)polymers based on the monomers 1 to 75, JP2009170764, JP2009135183 the (co)polymers based on the monomers 1-14, WO2009063757 preferably the (co)polymers based on the monomers 1-1 to 1-26, WO2008146838 the compounds a-1 to a-43 and 1-1 to 1-46, JP2008207520 the
(co)polymers based on the monomers 1-1 to 1-26, JP2008066569 the (co)polymers based on the monomers 1-1 to 1-16, WO2008029652 the (co)polymers based on the monomers 1-1 to 1-52, WO20071 14244 the (co)polymers based on the monomers 1-1 to 1-18, JP2010040830 the compounds HA-1 to HA-20, HB-1 to HB-16, HC-1 to HC-23 and the (co)polymers based on the monomers HD-1 to HD-12, JP2009021336, WO2010090077 the compounds 1 to 55, WO2010079678 the compounds H1 to H42, WO2010067746, WO2010044342 the compounds HS-1 to HS-101 and Poly-1 to Poly-4, JP2010114180 the compounds PH-1 to PH-36, US2009284138 the compounds 1 to 11 1 and H1 to H71 , WO2008072596 the compounds 1 to 45, JP2010021336 the compounds H-1 to H-38, pref- erably H-1 , WO2010004877 the compounds H-1 to H-60, JP2009267255 the compounds 1-1 to 1-105, WO2009104488 the compounds 1-1 to 1-38, WO2009086028,
US2009153034, US2009134784, WO2009084413 the compounds 2-1 to 2-56,
JP2009114369 the compounds 2-1 to 2-40, JP20091 14370 the compounds 1 to 67, WO2009060742 the compounds 2-1 to 2-56, WO2009060757 the compounds 1-1 to 1-76, WO2009060780 the compounds 1-1 to 1-70, WO2009060779 the compounds 1-1 to 1-42, WO2008156105 the compounds 1 to 54, JP2009059767 the compounds 1 to 20,
JP2008074939 the compounds 1 to 256, JP2008021687 the compounds 1 to 50,
WO20071 19816 the compounds 1 to 37, WO2010087222 the compounds H-1 to H-31 , WO2010095564 the compounds HOST-1 to HOST-61 , WO2007108362, WO2009003898, WO2009003919, WO2010040777, US2007224446, WO06128800, WO2012014621 ,
WO2012105310, WO2012/130709 and European patent applications EP12175635.7 and EP12185230.5. and EP12191408.9 (in particular page 25 to 29 of EP12191408.9).
The above-mentioned small molecules are more preferred than the above-mentioned (co)polymers of the small molecules.
Further suitable second host materials, are described in WO201 1137072 (for example,
Figure imgf000079_0001
Figure imgf000080_0001
In a particularly preferred embodiment, one or more compounds of the general formula (X) specified hereinafter are used as second host material.
224
Figure imgf000080_0002
(X), wherein
X is NR, S, O or PR;
R is aryl, heteroaryl, alkyl, cycloalkyi, or heterocycloalkyi;
A200 jS .N R206 207, _p(O)R208R209 _pR210R211 _ -S(0)2R212, -S(0)R213, -SR214, 0r -OR215;
R221 R222 anc| R223 are independently of each other aryl, heteroaryl, alkyl, cycloalkyi, or heterocycloalkyi, wherein at least on of the groups R221, R222, or R223 is aryl, or heteroaryl; R224 and R225 are independently of each other alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl, a group A200, or a group having donor, or acceptor characteristics;
n2 and m2 are independently of each other 0, 1 , 2, or 3;
R206 and R207 form together with the nitrogen atom a cyclic residue having 3 to 10 ring at- oms, which can be unsubstituted, or which can be substituted with one, or more substitu- ents selected from alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl and a group having donor, or acceptor characteristics; and/or which can be annulated with one, or more further cyclic residues having 3 to 10 ring atoms, wherein the annulated residues can be unsubstituted, or can be substituted with one, or more substituents selected from alkyl, cycloalkyl, heterocycloalkyi, aryl, heteroaryl and a group having donor, or acceptor characteristics; and 208, 209, R2io_ 2ii _ 212_ 213_ R214 u nc| R215 are independently of each other aryl, het, for exam-
(SH-5), or
Figure imgf000081_0001
(SH-6), are described in WO2010079051 (in particular pages on 19 to 26 and in tables on pages 27 to 34, pages 35 to 37 and pages 42 to 43).
Additional host materials on basis of dibenzofurane are, for example, described in
US2009066226, EP1885818B1 , EP1970976, EP1998388, EP2034538 and European pa- tent application no. 14160197.1. Examples of particularly preferred host materials are shown below:
Figure imgf000081_0002
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
In the above-mentioned compounds T is O, or S, preferably O. If T occurs more than one time in a molecule, all groups T have the same meaning. T1 is O, or S preferably O. T1 and
Figure imgf000084_0002
independently of each other
Figure imgf000085_0001
Figure imgf000086_0001
Hole/exciton blocking layer (f):
Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer. The hole blocking layer may be disposed between the emitting layer (e) and electron transport layer (g), to block holes from leaving layer (e) in the direction of electron transport layer (g). Blocking layers may also be used to block excitons from diffusing out of the emissive layer.
Additional hole blocker materials typically used in OLEDs are 2,6-bis(N-carbazolyl)pyridine (mCPy), 2,9-dimethyl-4J-diphenyl-1 ,10-phenanthroline (bathocuproin, (BCP)), bis(2- methyl-8-quinolinato)-4-phenylphenylato)aluminum(lll) (BAIq), phenothiazine S,S-dioxide derivates and 1 ,3,5-tris(N-phenyl-2-benzylimidazolyl)benzene) (TPBI), TPBI also being suitable as electron-transport material. Further suitable hole blockers and/or electron conductor materials are 2,2',2"-(1 ,3,5-benzenetriyl)tris(1-phenyl-1-H-benzimidazole), 2-(4- biphenylyl)-5-(4-tert-butylphenyl)-1 ,3,4-oxadiazole, 8-hydroxyquinolinolatolithium, 4- (naphthalen-1-yl)-3,5-diphenyl-4H-1 ,2,4-triazole, 1 ,3-bis[2-(2,2'-bipyridin-6-yl)-1 ,3,4- oxadiazo-5-yl]benzene, 4,7-diphenyl-1 ,10-phenanthroline, 3-(4-biphenylyl)-4-phenyl-5-tert- butylphenyl-1 ,2,4-triazole, 6,6'-bis[5-(biphenyl-4-yl)-1 ,3,4-oxadiazo-2-yl]-2,2'-bipyridyl, 2- phenyl-9,10-di(naphthalene-2-yl)anthracene, 2,7-bis[2-(2,2'-bipyridin-6-yl)-1 ,3,4-oxadiazo- 5-yl]-9,9-dimethylfluorene, 1 ,3-bis[2-(4-tert-butylphenyl)-1 ,3,4-oxadiazo-5-yl]benzene, 2- (naphthalene-2-yl)-4J-diphenyl-1 ,10-phenanthroline, tris(2,4,6-trimethyl-3-(pyridin-3- yl)phenyl)borane, 2, 9-bis(naphthalene-2-yl)-4,7-diphenyl-1 ,10-phenanthroline, 1-methyl-2- (4-(naphthalene-2-yl)phenyl)-1 H-imidazo[4,5-f][1 ,10]phenanthroline. In a further embodiment, it is possible to use compounds which comprise aromatic or heteroaromatic rings joined via groups comprising carbonyl groups, as disclosed in WO2006/100298, disilyl compounds selected from the group consisting of disilylcarbazoles, disilylbenzofurans, dis- ilylbenzothiophenes, disilylbenzophospholes, disilylbenzothiophene S-oxides and dis- ilylbenzothiophene S,S-dioxides, as specified, for example, in PCT applications
WO2009/003919 and WO2009003898 and disilyl compounds as disclosed in
WO2008/034758, as a blocking layer for holes/excitons (f). In another preferred embodiment compounds (SH-1), (SH-2), (SH-3), SH-4, SH-5, SH-6, (SH-7), (SH-8), (SH-9), (SH-10) and (SH-11) may be used as hole/exciton blocking materials. Electron transport layer (g):
Electron transport layer may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Suitable electron-transporting materials for layer (g) of the inventive OLEDs comprise metals chelated with oxinoid compounds, such as tris(8- hydroxyquinolato)aluminum (Alq3), compounds based on phenanthroline such as 2,9- dimethyl-4J-diphenyl-1 ,10-phenanthroline (DDPA = BCP), 4,7-diphenyl-1 ,10- phenanthroline (Bphen), 2,4,7,9-tetraphenyl-1 ,10-phenanthroline, 4,7-diphenyl-1 ,10- phenanthroline (DPA) or phenanthroline derivatives disclosed in EP1786050, in
EP1970371 , or in EP1097981 , and azole compounds such as 2-(4-biphenylyl)-5-(4-t- butylphenyl)-1 ,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4phenyl-5-(4-t-butylphenyl)-1 ,2,4- triazole (TAZ).
It is likewise possible to use mixtures of at least two materials in the electron-transporting layer, in which case at least one material is electron-conducting. Preferably, in such mixed electron-transport layers, at least one phenanthroline compound is used, preferably BCP, or at least one pyridine compound according to the formula (VIII) below, preferably a compound of the formula (Vlllaa) below. More preferably, in mixed electron-transport layers, in addition to at least one phenanthroline compound, alkaline earth metal or alkali metal hy- droxyquinolate complexes, for example Liq, are used. Suitable alkaline earth metal or alkali metal hydroxyquinolate complexes are specified below (formula VII). Reference is made to WO2011/157779.
The electron-transport layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device. Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1 , 1 July 2003 (p- doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 23 June 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89 - 103 and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233. For example, it is possible to use mixtures which lead to electrical n-doping of the electron- transport layer. n-Doping is achieved by the addition of reducing materials. These mixtures may, for example, be mixtures of the abovementioned electron transport materials with alkali/alkaline earth metals or alkali/alkaline earth metal salts, for example Li, Cs, Ca, Sr, CS2CO3, with alkali metal complexes, for example 8-hydroxyquinolatolithium (Liq), and with Y, Ce, Sm, Gd, Tb, Er, Tm, Yb, Li3N, Rb2C03, dipotassium phthalate, W(hpp)4 from
EP1786050, or with compounds described in EP1837926B1 , EP1837927, EP2246862 and WO2010132236. In a preferred embodiment, the electron-transport layer comprises at least one compound of the general formula (VII)
Figure imgf000088_0001
, in which
R32' and R33' are each independently F, Ci-Cs-alkyl, or C6-Ci4-aryl, which is optionally substituted by one or more Ci-Cs-alkyl groups, or
two R32' and/or R33' substituents together form a fused benzene ring which is optionally substituted by one or more Ci-Cs-alkyl groups;
a and b are each independently 0, or 1 , 2 or 3,
M1 is an alkaline metal atom or alkaline earth metal atom,
p is 1 when M1 is an alkali metal atom, p is 2 when M1 is an earth alkali metal atom.
A very particularly preferred compound of the formula (VII) is
Figure imgf000088_0002
(Liq), which may be present as a single species, or in other forms such as LigQg in which g is an integer, for example LkQe- Q is an 8-hydroxyquinolate ligand or an 8-hydroxyquinolate derivative.
In a further preferred embodiment, the electron-transport layer comprises at least one compound of the formula (VIII),
Figure imgf000088_0003
(VIII), in which
R34", Rss", RS6", R37", R34', R35', R36' and R37'are each independently H, Ci-Cis-alkyl, C1-C18- alkyl which is substituted by E' and/or interrupted by D', C6-C24-aryl, C6-C24-aryl which is substituted by G', C2-C2o-heteroaryl or C2-C2o-heteroaryl which is substituted by G', Q is an arylene or heteroarylene group, each of which is optionally substituted by G';
D' is -CO-; -COO-; -S-; -SO-; -S02-; -0-; -NR4°'-; -SiR45'R46'-; -POR47'-;
Figure imgf000088_0004
or - C≡C-;
E' is -OR44'; -SR44'; -NR4°'R41'; -COR43'; -COOR42'; -CONR4°'R4i'; -CN; or F;
G' is E', Ci-Cis-alkyl, Ci-Cis-alkyl which is interrupted by D', Ci-Ci8-perfluoroalkyl, C1-C18- alkoxy, or Ci-Cis-alkoxy which is substituted by E' and/or interrupted by D', in which R38' and R39' are each independently H, C6-Cis-aryl; C6-Cis-aryl which is substituted by Ci-Cis-alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-; R40' and R41 ' are each independently C6-Cis-aryl; C6-Cis-aryl which is substituted by C1-C18- alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-; or
R40' and R41 ' together form a 6-membered ring;
R42' and R43' are each independently C6-Cis-aryl; C6-Cis-aryl which is substituted by Ci-Cis- alkyl or Ci-Cis-alkoxy; Ci-Cis-alkyl; or Ci-Cis-alkyl which is interrupted by -0-,
R44' is C6-Ci8-aryl; C6-Cis-aryl which is substituted by Ci-Cis-alkyl or Ci-Cis-alkoxy; C1-C18- alkyl; or Ci-Cis-alkyl which is interrupted by -0-,
R45' and R46' are each independently Ci-Cis-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cis-alkyl,
R47' is Ci-Cis-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cis-alkyl.
Preferred compounds of the formula (VIII) are compounds of the formula (Villa)
Figure imgf000089_0001
(Villa)
Figure imgf000089_0002
R48' is H or Ci-Cis-alkyl and
Figure imgf000089_0003
R48" is H, Ci-Cis-alkyl or or
Particular preferenc
Figure imgf000089_0004
(ETM-2).
In a further, very particularly preferred embodiment, the electron-transport layer comprises a compound Liq and a compound ETM-2.
In a preferred embodiment, the electron-transport layer comprises the compound of the formula (VII) in an amount of 99 to 1 % by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, where the amount of the compounds of the formulae (VII) and the amount of the compounds of the formulae (VIII) adds up to a total of 100% by weight. The preparation of the compounds of the formula (VIII) is described in J. Kido et al., Chem. Commun. (2008) 5821-5823, J. Kido et al., Chem. Mater. 20 (2008) 5951-5953 and JP2008/127326, or the compounds can be prepared analogously to the processes dis- closed in the aforementioned documents.
It is likewise possible to use mixtures of alkali metal hydroxyquinolate complexes, preferably Liq, and dibenzofuran compounds in the electron-transport layer. Reference is made to WO2011/157790. Dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described in WO2011/157790 are preferred, wherein dibenzofuran compound
Figure imgf000090_0001
(A-10; = ETM-1) is most preferred.
In a preferred embodiment, the electron-transport layer comprises Liq in an amount of 99 to 1 % by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, where the amount of Liq and the amount of the dibenzofuran compound(s), especially ETM-1 , adds up to a total of 100% by weight.
In a preferred embodiment, the electron-transport layer comprises at least one phenanthro- line derivative and/or pyridine derivative.
In a further preferred embodiment, the electron-transport layer comprises at least one phe- nanthroline derivative and/or pyridine derivative and at least one alkali metal hydroxyquinolate complex. In a further preferred embodiment, the electron-transport layer comprises at least one of the dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described in WO2011/157790, especially ETM-1.
In a further preferred embodiment, the electron-transport layer comprises a compound de- scribed in WO2012/1 11462, WO2012/147397, WO2012014621 , such as, for example, a
Figure imgf000090_0002
compound of formula (ETM-3), US2012/0261654, such as, for example, a compound of
Figure imgf000091_0001
Figure imgf000091_0002
Electron injection layer (h):
The electron injection layer may be any layer that improves the injection of electrons into an adjacent organic layer. Lithium-comprising organometallic compounds such as 8- hydroxyquinolatolithium (Liq), CsF, NaF, KF, CS2CO3 or LiF may be applied between the electron transport layer (g) and the cathode (i) as an electron injection layer (h) in order to reduce the operating voltage.
Cathode (i):
The cathode (i) is an electrode which serves to introduce electrons or negative charge carriers. The cathode may be any metal or nonmetal which has a lower work function than the anode. Suitable materials for the cathode are selected from the group consisting of alkali metals of group 1 , for example Li, Cs, alkaline earth metals of group 2, metals of group 12 of the Periodic Table of the Elements, comprising the rare earth metals and the lanthanides and actinides. In addition, metals such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof, may be used.
In general, the different layers, if present, have the following thicknesses:
anode (a): 500 to 5000 A (angstrom), preferably 1000 to 2000 A;
hole injection layer (b): 50 to 1000 A, preferably 200 to 800 A,
hole-transport layer (c): 50 to 1000 A, preferably 100 to 800 A,
exciton blocking layer (d): 10 to 500 A, preferably 50 to 100 A,
light-emitting layer (e): 10 to 1000 A, preferably 50 to 600 A,
hole/ exciton blocking layer (f): 10 to 500 A, preferably 50 to 100 A,
electron-transport layer (g): 50 to 1000 A, preferably 200 to 800 A,
electron injection layer (h): 10 to 500 A, preferably 20 to 100 A,
cathode (i): 200 to 10 000 A, preferably 300 to 5000 A. The person skilled in the art is aware (for example on the basis of electrochemical studies) of how suitable materials have to be selected. Suitable materials for the individual layers are known to those skilled in the art and are disclosed, for example, in WO 00/70655.
In addition, it is possible that some of the layers used in the inventive OLED have been surface-treated in order to increase the efficiency of charge carrier transport. The selection of the materials for each of the layers mentioned is preferably determined by obtaining an OLED with a high efficiency and lifetime.
The inventive OLED can be produced by methods known to those skilled in the art. In general, the inventive OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate. Suitable substrates are, for example, glass, inorganic semiconductors or polymer films. For vapor deposition, it is possible to use customary tech- niques, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others. In an alternative process, the organic layers of the OLED can be applied from solutions or dispersions in suitable solvents, employing coating techniques known to those skilled in the art. Use of the compounds of the formula I in at least one layer of the OLED, preferably in the light-emitting layer (preferably as a matrix material), charge transport layer and/or in the charge/exciton blocking layer makes it possible to obtain OLEDs with high efficiency and with low use and operating voltage. Frequently, the OLEDs obtained by the use of the compounds of the formula I additionally have high lifetimes. The efficiency of the OLEDs can additionally be improved by optimizing the other layers of the OLEDs. For example, high-efficiency cathodes such as Ca or Ba, if appropriate in combination with an intermediate layer of LiF, can be used. Moreover, additional layers may be present in the OLEDs in order to adjust the energy level of the different layers and to facilitate electroluminescence. The OLEDs may further comprise at least one second light-emitting layer. The overall emission of the OLEDs may be composed of the emission of the at least two light-emitting layers and may also comprise white light.
The OLEDs can be used in all apparatus in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile visual display units and illumination units. Stationary visual display units are, for example, visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations and information panels. Mobile visual display units are, for example, visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains. Further devices in which the inventive OLEDs can be used are, for example, keyboards; items of clothing; furniture; wallpaper. In addition, the present invention relates to a device selected from the group consisting of stationary visual display units such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations, information panels, and mobile visual display units such as visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising at least one inventive organic light-emitting diode or at least one inventive light-emitting layer.
The following examples are included for illustrative purposes only and do not limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight.
Examples
Example 1
Figure imgf000093_0001
1 ,2-Diaminocyclohexane
1 ,4-Dioxane
a) 15.7 g of indole (134mmol) were combined with 2-bromo-8-iododibenzofuran (50.0 g, 134 mmol), Cul (0.255 g, 1.34 mmol), K3PO4 (59.7 g, 281 mmol) and 1 ,2- diaminocyclohexane (1.61 ml, 13.4 mmol) in 1 ,4-dioxane (615 ml.) and the resulting mixture was heated at 1 15 °C for 14 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with ethyl acetate. The resulting solution was evaporated to give a crude material as a red solid. The crude material was purified by chromatography on neutral silica gel using hexane/Ch C (4/1 ) as eluent to give 1 as a slightly yellow oil (25.5 g, 54 % yield). Product confirmed by LCMS m/z = 362 (
Figure imgf000093_0002
b) 2.60 g of Indole (22.2 mmol) were combined with 1 (8.04 g, 22.2 mmol), Cul (0.211 g, 1.1 1 mmol), K3PO4 (9.90 g, 46.6 mmol) and 1 ,2-diaminocyclohexane (0.533 ml, 4.44 mmol) in 1 ,4-dioxane (30 ml.) and the resulting mixture was heated at 1 15 °C for 72 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with CH2CI2. The resulting solution was evaporated to give a crude material as a red solid. The crude material was purified by chromatography on neutral silica gel using hexane/Ch C (4/1) as eluent to give C-79 as a white solid (7.19 g, 81 % yield) in 99.6 % purity by HPLC. Product confirmed by LCMS m/z = 399 (M+1). Ή NMR (300 MHz, Chloroform-d) δ 8.09 (dd, J = 2.1 , 0.6 Hz, 1 H), 7.83-7.72 (m, 2H), 7.68 (dd, J = 8.7, 2.1 Hz, 1 H), 7.60-7.54 (m, 1 H), 7.43 (d, J = 3.3 Hz, 1 H), 7.33-7.15 (m, 2H), 6.75 (dd, J = 3.3, 0.9 Hz, 1 H).
Example 2
Figure imgf000094_0001
3.71 g of carbazole (22.2 mmol) were combined with 1 (8.04 g, 22.2 mmol), Cul (0.21 1 g, 1.1 1 mmol), K3PO4 (9.90 g, 46.6 mmol) and 1 ,2-diaminocyclohexane (0.533 ml, 4.44 mmol) in 1 ,4-dioxane (30 mL) and the resulting mixture was heated at 1 15 °C for 48 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with CH2CI2. The resulting solution was evaporated to give a crude material as a red solid. The crude material was purified by chromatography on neutral silica gel using hexane/Ch C (4/1 ) as eluent and was then recrystallized by toluene to give B-2 as a white solid (7.48 g, 76 % yield) in 99.8 % purity by HPLC. Product confirmed by LCMS m/z = 449 (M+1 ). 1H NMR (300 MHz, Chloroform-d) δ 8.21 (m, 1 H), 8.19 (m, 1 H), 8.16 (dd, J = 2.2, 0.6 Hz, 1 H), 8.07 (dd, J = 2.2, 0.6 Hz, 1 H), 7.87 (dd, J = 8.7, 0.6 Hz, 1 H), 7.81 (dd, J = 8.7, 0.6 Hz, 1 H), 7.76-7.65 (m, 3H), 7.60-7.54 (m, 1 H), 7.50-7.12 (m, 9H), 6.74 (dd, J = 3.3, 0.8 Hz, 1 H). Example 3
Figure imgf000094_0002
3.16 g of 5-cyanoindole (22.2 mmol) were combined with 1 (8.04 g, 22.2 mmol), Cul (0.211 g, 1.11 mmol), K3PO4 (9.90 g, 46.6 mmol) and 1 ,2-diaminocyclohexane (0.267 ml, 2.22 mmol) in 1 ,4-dioxane (25 mL) and the resulting mixture was heated at 1 15 °C for 30 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with CH2CI2. The resulting solution was evaporated to give a crude material as a slightly yellow oil. The crude material was purified by chromatography on neutral silica gel using toluene/ethyl acetate (100/1 ) as eluent and was then recrystallized by toluene to give 3 as a white solid (6.58 g, 70 % yield) in 99.5 % purity by HPLC. Product confirmed by LCMS m/z = 424 (M+1 ). Ή NMR (300 MHz, Chloroform-d) δ 8.11-8.08 (m, 2H), 8.06 (dd, J = 2.1 , 0.6 Hz, 1 H), 7.85-7.67 (m, 4H), 7.63 (dd, J = 8.7, 2.1 Hz, 1 H), 7.59- 7.52 (m, 3H), 7.48 (dd, J = 8.7, 1.5 Hz, 1 H), 7.42 (d, J = 3.3 Hz, 1 H), 7.33 - 7.16 (m, 2H), 6.83 (dd, J = 3.3, 0.8 Hz, 1 H), 6.76 (dd, J = 3.3, 0.8 Hz, 1 H). Example 4
Figure imgf000094_0003
1 ,2-Diaminocyclohexane
1 ,4-Dioxane
a) 13.3 g of 5-cyanoindole (93.8 mmol) were combined with 2-bromo-8-iododibenzofuran (35.0 g, 93.8 mmol), Cul (0.179 g, 0.938 mmol), K3PO4 (41.8 g, 197 mmol) and 1 ,2- diaminocyclohexane (1 .13 ml, 9.38 mmol) in 1 ,4-dioxane (120 ml.) and the resulting mixture was heated at 1 15 °C for 5 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with CH2CI2. The resulting solution was evaporated to give a crude material as a grey solid. The crude material was purified by chromatography on neutral silica gel using hexane/toluene (1/1 ) to hex- ane/Ch C (1/1 ) as eluent to give 2 as a colorless oil (23.1 g, 64 % yield). Product confirmed b LCMS m/z = 387 (M+1 ).
Figure imgf000095_0001
b) 4.00 g of 5-cyanoindole (28.1 mmol) were combined with 5 (10.9 g, 28.1 mmol), Cul (0.268 g, 1.41 mmol), K3PO4 (12.5 g, 59.0 mmol) and 1 ,2-diaminocyclohexane (0.676 ml, 5.62 mmol) in 1 ,4-dioxane (100 ml.) and the resulting mixture was heated at 1 15 °C for 10 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with CH2CI2. The resulting solution was evaporated to give a crude material as a grey solid. The crude material was purified by chromatography on neu- tral silica gel using Ch C /MeOH (10/1 ) as eluent and was then recrystallized by xylene to give D-58 as a slightly yellow solid (3.20 g, 25 % yield) in 99.6 % purity by HPLC. Product confirmed by LCMS m/z = 449 (M+1 ). Ή NMR (300 MHz, Chloroform-d) δ 8.1 1-8.08 (m, 1 H), 8.07 (dd, J = 2.2, 0.6 Hz, 1 H), 7.84 (dd, J = 8.7, 0.6 Hz, 1 H), 7.66 (dd, J = 8.7, 2.2 Hz, 1 H), 7.60-7.43 (m, 3H), 6.83 (dd, J = 3.3, 0.8 Hz, 1 H)
Figure imgf000095_0002
4.71 g of carbazole (28.1 mmol) were combined with 5 (10.9 g, 28.1 mmol), Cul (0.268 g, 1.41 mmol), K3PO4 (12.5 g, 59.0 mmol) and 1 ,2-diaminocyclohexane (0.676 ml, 5.62 mmol) in 1 ,4-dioxane (100 mL) and the resulting mixture was heated at 1 15 °C for 40 hours. The reaction was allowed to cool to room temperature and was then filtered through a pad of celite washing well with CH2CI2. The resulting solution was evaporated to give a crude material as a grey solid. The crude material was purified by chromatography on neutral silica gel using toluene to ethyl acetate as eluent and was then recrystallized by toluene to give B-5 as a white solid (4.00 g, 30 % yield) in 99.8 % purity by HPLC. Product confirmed by LCMS m/z = 474 (M+1 ). Ή NMR (300 MHz, Chloroform-d) δ 8.23-8.20 (m, 1 H), 8.20-8.17 (m, 1 H), 8.17 (dd, J = 2.2, 0.6 Hz, 1 H), 8.09-8.06 (m, 1 H), 8.05 (dd, J = 2.2, 0.6 Hz, 1 H), 7.89 (dd, J = 8.7, 0.5 Hz, 1 H), 7.85 (dd, J = 8.7, 0.5 Hz, 1 H), 7.74 (dd, J = 8.7, 2.2 Hz, 1 H), 7.65 (dd, J = 8.7, 2.2 Hz, 1 H), 7.59-7.30 (m, 9H), 6.81 (dd, J = 3.3, 0.8 Hz, 1 H).
Example 6
Figure imgf000096_0001
a) 6.27 g of B-5 (14.0 mmol) was combined with /V-iodosuccinimide (3.15 g, 14.0 mmol) in THF (140 ml_). The resulting mixture was heated at 60 °C over night. The reaction was allowed to cool to room temperature and added 10% aqueous sodium thiosulfate solution (200 ml.) and extracted with toluene (3 x 100 ml_). The combined organic phase was washed with saturated aqueous sodium hydrogencarbonate solution (100 ml.) and then water (100 ml_). The organic phase was dried over anhydrous MgS04 and the solvent was evaporated to give the crude product as a light brown solid. The crude product was washed with heptane and filtered off. 7.04 g of 3 was collected as a light brown solid (87.5% yield). Product confirmed by LCMS m/z = 575 (M+1 ).
Figure imgf000096_0002
b) 1.84 g of carbazole (1 1 .0 mmol) was combined with 3 (6.32 g, 1 1.0 mmol), Cul (2.10 g, 1 1.0 mmol), K3PO4 (7.00 g, 33.0 mmol) and 1 ,2-diaminocyclohexane (2.64 ml, 22.0 mmol) in 1 ,4-dioxane (70 ml.) and the resulting mixture was heated at 100 °C for a day. The mix- ture was filtered through a pad of Celite washing well with toluene and the solvent was evaporated to give the crude product as a brown solid. The crude material was purified by chromatography on neutral silica gel using heptane/toluene (9/1 to 4/1 ) as eluent to give B- 1 as a colorless solid (2.48 g, 36.7 % yield) in 99.6 % purity by HPLC. Product confirmed by LCMS m/z = 614 (M+1 ). Ή NMR (400 MHz, Chloroform-d) δ 8.22 (m, 2H), 8.22 (m, 2H), 8.20 (m, 1 H), 8.20 (m, 1 H), 7.90 (d, J = 8.8 Hz, 1 H), 7.89 (d, J = 8.8 Hz, 1 H), 7.82 (dd, J = 8.8, 2.0 Hz, 1 H), 7.75 (m, 1 H), 7.74 (dd, J = 8.8, 2.0 Hz, 1 H), 7.71 (m, 1 H), 7.48-7.16 (m, 15H).
Comparative Application Example 1
A glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode used as an anode is first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate is exposed to an ultraviolet light and ozone for further 30 min. This treatment also improves the hole injection properties of the ITO. The cleaned substrate is mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below are applied by vapor deposition to the ITO substrate a A/sec at about 10 6 -10 8 mbar. As a hole injection layer,
compound
Figure imgf000096_0003
with 30 nm thickness is applied. Then compound a hole transporting layer. As an
e
Figure imgf000097_0001
xciton and electron blocker, comp (HTM-1 ; for preparation, see Ir complex (7) in the application WO2005/019373) is then applied with a thickness of 10 nm.
Figure imgf000097_0002
Subsequently, a mixture of 20% by weight of emitter compound, (BE-
1 pound (HTM-1) and 65% by weight of host
Figure imgf000097_0003
(SH-1) are applied by vapor deposition in a thickness of 40 nm. Subsequently, material (SH-1) is applied by vapour
5 nm as an exciton and hole blocker. Thereafter, compound
Figure imgf000097_0004
with 20 nm thickness is deposited as an electron transport layer. Finally, 1 nm-thick LiF is deposited as an electron injection layer and 80 nm-thick Al is then deposited as a cathode to complete the device. The device is sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen. OLED characterization
To characterize the OLED, electroluminescence spectra are recorded at various currents and voltages. In addition, the current-voltage characteristic is measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). Driving voltage U and EQE are given at luminance (L) = 1000 cd/m2 and Commission In- ternationale de I'Eclairage (CIE) coordinate are given at 5mA/cm2 except otherwise stated. Furthermore, 50% lifetime (LT50), the time spent until the initial luminance of 4Ό00 cd/m2 is reduced to 50% (2Ό00 cd/m2), is recorded. Application Example 1 , 2 and 3
Comparative Application Example 1 is repeated except and the exciton
(C-79),
pound
Figure imgf000098_0001
device results are shown in Table 1.
Table 1
Figure imgf000098_0003
The results shown in Table 1 demonstrate that the driving voltage and EQE are improved when compounds (C-79), (C-80), or (D-51) are used as a host and an exciton blocker instead of reference compound (SH-1). Application Example 4, 5, 6 and 7
Comparative Application Example 1 is repeated except that the exciton and hole blocker,
(D-50), compound
Figure imgf000098_0002
(D-58), or compound (D-51) compound
Figure imgf000099_0001
(B-1 ) (see preparation example 6) for example 4,
6, or 7, respectively. The device results are shown in Table 2.
Table 2
Figure imgf000099_0002
The results shown in Table 2 demonstrate that the driving voltage, EQE and lifetime are improved when compounds (D-50), (B-51), (D-58), or (B-1) are used as an exciton and hole blocker instead of reference compound (SH-1).

Claims

Claims
1. A compound of the formula
Figure imgf000100_0001
(I), wherein m is 0, 1 or 2, n is 0, 1 or 2,
Ar1 and Ar2 are independently of each other a C6-C24arylen group, which can optionally be substituted by G, a C2-C3oheteroarylen group, which can optionally be substituted by G,
Bi is N, or CR3,
B2 is N, or CR4,
B3 is N, or CRs,
B4 is N, or CR6,
with the proviso that not more than two of B1 , B2, B3 and B4 are N;
Bi i is N, or CRsi ,
Figure imgf000100_0002
Bis is N, or CRss,
Figure imgf000100_0003
with the proviso that not more than two of B11 , B12, B13 and B14 are N;
Figure imgf000100_0004
Bi6 is N, or CRse,
Figure imgf000100_0005
with the proviso that not more than two of B15, B16, B17 and B18 are N;
R1 and R2 are independently of each other -H, -F, CN, a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24aryloxy group, which can optionally be substituted by G;
Xi is O, S, Se or NR7,
with the proviso that, if at least one of R1 , R2, R3, R4, R5, and R6 is -CN, then
A is -NR10R11 , or -Si(R1 )(R13)(R14), a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G; R3, R4, R5 , R6, R5i , R52, 53, 54, 55, 56, R57, anc| R58 are independently of each other -H, -F, CN, a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24 ar- yloxy group, which can optionally be substituted by G;
R7 is a Ci-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G;
R10 and R11 are independently of each other H, a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
R12, R13 and R14 are independently of each other a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by L; a C6-C24aryl group, which can optionally be substituted by G; or a C2-C3oheteroaryl group, which can optionally be substituted by G;
with the proviso that, if all of R1 , R2, R3, R4, R5 and R6 are different from -CN, then A is a C6-C24aryl group, which can optionally be substituted by G, a Ci3-C3oheteroaryl group, which can optionally be substituted by G, an azacarbazolyl, which can optionally be substituted by G, an azaindolyl, which can optionally be substituted by G, a dibenzofuranyl, which can optionally be substituted by G, a dibenzothiophenyl, which can optionally be substituted by G, a benzofuranyl, which can optionally be substituted by G, a benzothiophenyl, which can optionally be substituted by G, a pyridyl, which can optionally be substituted by G, a pyrimidinyl, which can optionally be substituted by G, a pyrazinyl, which can optionally be substituted by G, a triazinyl, which can optionally be substituted by G, a naphtyridinyl, which can optionally be substitute
Figure imgf000101_0001
(IV),
Bis is N or CR61 , preferably CR61 ,
B20 is N or CR62, preferably CR62,
B21 is N or CR63, preferably CR63,
B22 is N or CR64, preferably CR64,
with the proviso that not more than two of B19, B2°, B2i and B22 are N;
B23 is N or CR65, preferably CR65,
B24 is N or CR66, preferably CR66,
B25 is N or CR67, preferably CR67,
B26 is N or CR68, preferably CR68,
with the proviso that not more than two of B23, B24, B25 and B26 are N;
B27 is N or CR69, preferably CR69,
B28 is N or CR70, preferably CR70,
B29 is N or CR7i , preferably CR7i ,
B3° is N or CR72, preferably CR72,
B31 is N or CR73, preferably CR73, B32 is N or CR74, preferably CR74,
with the proviso that not more than two of B29, B30, B31 and B32 are N;
with the proviso that N in the groups of formula (III) and (IV) chemically binds to one of B15, B16, B17, or B18, or Ar1 , or Ar2, if present;
R61 , R62, R63, R64, Res, R66, R67, es, 69, /o, R 1 , R72, R73 anc| R74 are independently of each other -H, -F, -C≡N, a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24aryloxy group, which can optionally be substituted by G;
D is -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -N R2S -POR24-, -CR2s=CR26-, or -C≡C-, E is -OR31 , -SR31 , -N R32R33, -COR34, -COOR34, -CONR32R33, -C≡N , or -F,
L is D, or -Si R22R23-,
G is E, or a Ci-Cisalkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by -F, Ci-Cisalkyl, or Ci-Cisalkyl which is interrupted by -0-; a C2- C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by -F, Ci- Cisalkyl , or Ci-Cisalkyl which is interrupted by O;
R21 , R32 and R33 are independently of each other a C6-Cisaryl group; a C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci- Cisalkyl group, which is interrupted by -O-; or R32 and R33 together form a five or six membered ring ,
R22 and R23 are independently of each other a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl,
R24 is a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl ,
R25 and R26 are independently of each other H , C6-Cisaryl ; C6-Cisaryl which is substituted by Ci-Cisalkyl , or Ci-Cisalkoxy; Ci-Cisalkyl; or Ci-Cisalkyl which is interrupted by -0-,
R31 is a C6-Cisaryl ; a C6-Cisaryl , which is substituted by Ci-Cisalkyl , or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O- and
R34 is a C6-Cisaryl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl , or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-.
T
Figure imgf000102_0001
(la), wherein
Ri , R2, R3, R4, R5, R6, B11 , B12, B13, B14, Bis, Bis, B17, Ari , Ar2, A, m and n are defined in claim 1.
3. The compound according to claim 2, which is a compound of formula
Figure imgf000103_0001
(lb), wherein
R2, R3, R4, R5 R6 χι A , Ar2, A, m and n are defined in claim 1.
4. T formula
Figure imgf000103_0002
(lc), wherein
R2, R3, R4, R5, 6_ χι, Ar1, ΑΓ2, A, m and n are defined in claim 1.
5. T s a compound of formula
Figure imgf000103_0003
(Id), wherein
Xi is NR7, O, orS,
R1, R2, R3, R4, R5, R67 R77 Ar1 and A are defined in claim 1, and
m is 0 or 1.
6.
Figure imgf000104_0001
Xi is NR7, O, orS,
R1, R2, R3, R4, R5, R67 R77 Ar1 and A are defined in claim 1, and m is 0 or 1.
Figure imgf000104_0002
Figure imgf000105_0001
pendently of each other -H, -CN, or a phenyl group.
9. The compound according to any of claims 1 to 8 or 21 or 22, wherein R1, R2, R3, R4, R5 and R6 are independently of each other -H, or -CN.
10. The compound according to any of claims 1 to 9 or 21 or 22, wherein at least one of Ri, R2, R3, R4, R5 and R6 is -CN. 11. The compound according to any of claims 1 to 10 or 21 or 22, wherein m is 0.
12. The compound according to any of claims 1 to 11 or 21 or 22, wherein X1 is O, or S.
13. T ich is a compound of formula
Figure imgf000106_0001
(ld-1), wherein
Xi is O,
R4is CN and R1, R2, R3, R5 and R6are H, or
Ri, R2, R3, R4, R5 and RSare H,
Figure imgf000106_0002
Figure imgf000107_0001
m is 0 or 1.
Figure imgf000107_0002
An electronic device, comprising a compound according to any of claims 1 to 13 or
15. The electronic device according to claim 14, which is an electroluminescent device.
16. A charge transport layer, a charge/exciton blocker layer, or an emitting layer comprising a compound according to any of claims 1 to 13 or 21 to 23.
17. The emitting layer according to claim 16, comprising a compound according to any of claims 1 to 13 or 21 to 23 as host material in combination with a phosphorescent emitter.
18. An apparatus selected from the group consisting of stationary visual display units; mobile visual display units; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising the organic electronic device according to claim 14, or 15, or the charge transport layer, the charge/exciton blocker layer, or the emitting layer according to claim 16, or 17.
19. Use of the compounds according to any of claims 1 to 13 or 21 to 23 for electrophotographic photoreceptors, photoelectric converters, organic solar cells, switching elements, organic light emitting field effect transistors, image sensors, dye lasers and electroluminescent devices.
Figure imgf000108_0001
(II), wherein
A' is CI, Br, or I, and
R1 and R2 are independently of each other -H, -F, CN, a Ci-C2salkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2-C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24aryloxy group, which can optionally be substituted by G;
R3, R4, R5 and R6 are independently of each other -H , -F, CN , a Ci-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C3- C25cycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G; a C2- C3oheteroaryl group, which can optionally be substituted by G; or a C6-C24 aryloxy group, which can optionally be substituted by G;
Xi is O, S, Se or NR7,
R7 is a Ci-C25alkyl group, which can optionally be substituted by E and or interrupted by D; a C3-C2scycloalkyl group, which can optionally be substituted by E and or interrupted by D; a C6-C24aryl group, which can optionally be substituted by G;
m is 0, 1 or 2, n is 0, 1 or 2,
Ar1 and Ar2 are independently of each other a C6-C24arylen group, which can optionally be substituted by G, a C2-C3oheteroarylen group, which can optionally be substituted by G,
D is -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -NR2S -POR24-, -CR2s=CR26-, or -C≡C-, E is -OR31 , -SR31 , -NR32R33, -COR34, -COOR34, -CONR32R33, -C≡N, or -F,
G is E, or a Ci-Cisalkyl group, a C6-C24aryl group, a C6-C24aryl group, which is substituted by -F, Ci-Cisalkyl, or Ci-Cisalkyl which is interrupted by -0-; a C2- C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by -F, Ci- Cisalkyl, or Ci-Cisalkyl which is interrupted by O;
R21 , R32 and R33 are independently of each other a C6-Cisaryl group; a C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci- Cisalkyl group, which is interrupted by -O-; or R32 and R33 together form a five or six membered ring,
R24 is a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl,
R25 and R26 are independently of each other H, C6-Cisaryl; C6-Cisaryl which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; Ci-Cisalkyl; or Ci-Cisalkyl which is interrupted by -0-, R31 is a Ce-Cisaryl; a Ce-Cisaryl, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O- and
R34 is a C6-Cisaryl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -0-.
The compound according to any of claims 1 to 6 wherein Ar1 and Ar2 are inde
22. la
Figure imgf000110_0001
23. ich is a compound of formula
Figure imgf000110_0002
(ld-1), wherein
Xi is O,
R4is CN and Ri Rz, R3, R5 and R6are H,
110
Figure imgf000111_0001
111
Figure imgf000112_0001
PCT/IB2015/058877 2014-11-17 2015-11-17 Indole derivatives for electronic applications WO2016079667A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14193401 2014-11-17
EP14193401.8 2014-11-17

Publications (1)

Publication Number Publication Date
WO2016079667A1 true WO2016079667A1 (en) 2016-05-26

Family

ID=51900294

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2015/058877 WO2016079667A1 (en) 2014-11-17 2015-11-17 Indole derivatives for electronic applications

Country Status (1)

Country Link
WO (1) WO2016079667A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200011911A (en) * 2018-07-25 2020-02-04 주식회사 엘지화학 Multicyclic compound and organic light emitting device comprising the same
US11807632B2 (en) 2018-10-22 2023-11-07 Lg Chem, Ltd. Heterocyclic compound and organic light emitting device comprising the same

Citations (159)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000070655A2 (en) 1999-05-13 2000-11-23 The Trustees Of Princeton University Very high efficiency organic light emitting devices based on electrophosphorescence
EP1097981A2 (en) 1999-11-02 2001-05-09 Sony Corporation Organic electroluminescent device
WO2001041512A1 (en) 1999-12-01 2001-06-07 The Trustees Of Princeton University Complexes of form l2mx as phosphorescent dopants for organic leds
US20010015432A1 (en) 2000-02-10 2001-08-23 Tatsuya Igarashi Light emitting device material comprising iridium complex and light emitting device using same material
US20010019782A1 (en) 1999-12-27 2001-09-06 Tatsuya Igarashi Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex
WO2002002714A2 (en) 2000-06-30 2002-01-10 E.I. Du Pont De Nemours And Company Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds
WO2002015645A1 (en) 2000-08-11 2002-02-21 The Trustees Of Princeton University Organometallic compounds and emission-shifting organic electrophosphorescence
US20020024293A1 (en) 2000-07-17 2002-02-28 Fuji Photo Film Co., Ltd. Light-emitting element and iridium complex
EP1191613A2 (en) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Luminescence device, display apparatus and metal coordination compound
EP1191612A2 (en) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Luminescence device, display apparatus and metal coordination compound
US20020048689A1 (en) 2000-09-21 2002-04-25 Fuji Photo Film Co., Ltd. Light-emitting device and iridium complex
US20020055014A1 (en) 2000-08-24 2002-05-09 Fuji Photo Film Co., Ltd. Light-emitting device and material therefor
EP1211257A2 (en) 2000-12-01 2002-06-05 Canon Kabushiki Kaisha Metal coordination compound, luminescence device and display apparatus
US20020094453A1 (en) 2000-11-29 2002-07-18 Takao Takiguchi Metal coordination compound, luminescence device and display apparatus
WO2002060910A1 (en) 2001-02-01 2002-08-08 Covion Organic Semiconductors Gmbh Method for the production of highly pure, tris-ortho-metalated organo-iridium compounds
US20020117662A1 (en) 2000-12-25 2002-08-29 Fuji Photo Film Co., Ltd. Novel indole derivative, material for light-emitting device and light-emitting device using the same
JP2003277744A (en) 2002-03-27 2003-10-02 Idemitsu Kosan Co Ltd Material for organic electroluminescent element and organic electroluminescent element obtained using the same
US6687266B1 (en) 2002-11-08 2004-02-03 Universal Display Corporation Organic light emitting materials and devices
WO2005019373A2 (en) 2003-08-19 2005-03-03 Basf Aktiengesellschaft Transition metal complexes comprising carbene ligands serving as emitters for organic light-emitting diodes (oled's)
US6921915B2 (en) 2001-03-08 2005-07-26 Canon Kabushiki Kaisha Metal coordination compound, luminescence device and display apparatus
WO2005113704A2 (en) 2004-05-18 2005-12-01 The University Of Southern California Luminescent compounds with carbene ligands
US20060008670A1 (en) 2004-07-06 2006-01-12 Chun Lin Organic light emitting materials and devices
WO2006014599A2 (en) 2004-07-07 2006-02-09 Universal Display Corporation Stable and efficient electroluminescent materials
WO2006056418A2 (en) 2004-11-25 2006-06-01 Basf Aktiengesellschaft Use of transition metal carbene complexes in organic light-emitting diodes (oleds)
WO2006067074A1 (en) 2004-12-23 2006-06-29 Ciba Specialty Chemicals Holding Inc. Electroluminescent metal complexes with nucleophilic carbene ligands
WO2006098460A1 (en) 2005-03-17 2006-09-21 Semiconductor Energy Laboratory Co., Ltd. Organometallic complex, and light-emitting element, light-emitting device and electronic device using the organometallic complex
WO2006100298A1 (en) 2005-03-24 2006-09-28 Basf Aktiengesellschaft Use of compounds containing aromatic or heteroaromatic rings linked via carbonyl group-containing groups, for use as matrix materials in organic light-emitting diodes
WO2006115301A1 (en) 2005-04-25 2006-11-02 Fujifilm Corporation Organic electroluminescent device
WO2006121811A1 (en) 2005-05-06 2006-11-16 Universal Display Corporation Stability oled materials and devices with improved stability
WO2006128800A1 (en) 2005-05-30 2006-12-07 Ciba Specialty Chemicals Holding Inc. Electroluminescent device
EP1786050A1 (en) 2005-11-10 2007-05-16 Novaled AG Doped organic semiconductor material
JP2007123392A (en) 2005-10-26 2007-05-17 Konica Minolta Holdings Inc Organic electroluminescence device, display device and lighting device
WO2007077810A1 (en) 2006-01-05 2007-07-12 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
US20070190359A1 (en) 2006-02-10 2007-08-16 Knowles David B Metal complexes of cyclometallated imidazo[1,2-ƒ]phenanthridine and diimidazo[1,2-a:1',2'-c]quinazoline ligands and isoelectronic and benzannulated analogs thereof
EP1837927A1 (en) 2006-03-22 2007-09-26 Novaled AG Use of heterocyclic radicals for doping of organic semiconductors
US20070224446A1 (en) 2006-03-24 2007-09-27 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence device and organic electroluminescence device using the same
WO2007108362A1 (en) 2006-03-17 2007-09-27 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
WO2007108459A1 (en) 2006-03-23 2007-09-27 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
WO2007114244A1 (en) 2006-03-30 2007-10-11 Konica Minolta Holdings, Inc. Organic electroluminescent device, illuminating device and display device
WO2007115981A1 (en) 2006-04-04 2007-10-18 Basf Se Transition metal complexes comprising one noncarbene ligand and one or two carbene ligands and their use in oleds
WO2007115970A1 (en) 2006-04-05 2007-10-18 Basf Se Heteroleptic transition metal-carbene complexes and their use in organic light-emitting diodes (oleds)
WO2007119816A1 (en) 2006-04-19 2007-10-25 Konica Minolta Holdings, Inc. Organic electroluminescence element material, organic electroluminescence element, display device and lighting apparatus
US20070278938A1 (en) 2006-04-26 2007-12-06 Idemitsu Kosan Co., Ltd. Aromatic amine derivative and electroluminescence device using the same
WO2008000727A1 (en) 2006-06-26 2008-01-03 Basf Se Use in oleds of transition metal carbene complexes that contain no cyclometallation via non-carbenes
JP2008021687A (en) 2006-07-10 2008-01-31 Mitsubishi Chemicals Corp Material for organic electric field light emitting element, composition for organic electric field light emitting element and organic electric field light emitting element
WO2008029652A1 (en) 2006-09-08 2008-03-13 Konica Minolta Holdings, Inc. Organic electroluminescent device, illuminating device and display
WO2008029729A1 (en) 2006-09-08 2008-03-13 Konica Minolta Holdings, Inc. Organic electroluminescent device, illuminating device and display
JP2008066569A (en) 2006-09-08 2008-03-21 Konica Minolta Holdings Inc Organic electroluminescence element, lighting system and display device
WO2008035571A1 (en) 2006-09-20 2008-03-27 Konica Minolta Holdings, Inc. Organic electroluminescence element
WO2008034758A2 (en) 2006-09-21 2008-03-27 Basf Se Oled display with extended lifetime
JP2008074939A (en) 2006-09-21 2008-04-03 Konica Minolta Holdings Inc Organic electroluminescence element material, organic electroluminescence element, display device and illumination device
JP2008084913A (en) 2006-09-26 2008-04-10 Konica Minolta Holdings Inc Organic electroluminescence element, display device, and lighting device
EP1837926B1 (en) 2006-03-21 2008-05-07 Novaled AG Heterocyclic radicals or diradicals and their dimers, oligomers, polymers, di-spiro and polycyclic derivatives as well as their use in organic semiconductor materials and electronic devices.
US20080106190A1 (en) 2006-08-23 2008-05-08 Idemitsu Kosan Co., Ltd. Aromatic amine derivatives and organic electroluminescent device using same
JP2008127326A (en) 2006-11-20 2008-06-05 Chemiprokasei Kaisha Ltd New di(pyridylphenyl) derivative, electron transport material comprising the same and organic electroluminescent device containing the same
WO2008066196A1 (en) 2006-11-27 2008-06-05 Fujifilm Corporation Organic electroluminescent device and indole derivative
WO2008072596A1 (en) 2006-12-13 2008-06-19 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
WO2008090912A1 (en) 2007-01-23 2008-07-31 Konica Minolta Holdings, Inc. Method for manufacturing organic electroluminescent device, organic electroluminescent device manufactured by the method, display device and illuminating device
JP2008207520A (en) 2007-02-28 2008-09-11 Konica Minolta Holdings Inc Organic thin film, method for producing the same, electronic device, organic luminescence element, display device and lightening equipment
EP1970371A1 (en) 2007-03-16 2008-09-17 Novaled AG Pyrido(3,2-h)chinazolins and/or 5,6-Dihydro derivatives thereof, method for their manufacture and endowed organic semiconductor material containing them
US20080265216A1 (en) 2007-04-30 2008-10-30 Novaled Ag Oxocarbon-, pseudooxocarbon- and radialene compounds and their use
WO2008140114A1 (en) 2007-05-16 2008-11-20 Konica Minolta Holdings, Inc. Organic electroluminescence element, display device and illuminating device
WO2008146838A1 (en) 2007-05-30 2008-12-04 Konica Minolta Holdings, Inc. Organic electroluminescent device, display device and illuminating device
WO2008156105A1 (en) 2007-06-21 2008-12-24 Konica Minolta Holdings, Inc. Organic electroluminescence element material, organic electroluminescence element, display device and illuminating device
WO2008156879A1 (en) 2007-06-20 2008-12-24 Universal Display Corporation Blue phosphorescent imidazophenanthridine materials
WO2009003898A1 (en) 2007-07-05 2009-01-08 Basf Se Organic light-emitting diodes containing carbene transition metal complex emitters and at least one compound selected from disilylcarbazoles, disilyldibenzofurans, disilyldibenzothiophenes, disilyldibenzophospholes, disilyldibenzothiophene s-oxides and disilyldibenzothiophene s,s-dioxides
WO2009003919A1 (en) 2007-07-05 2009-01-08 Basf Se Organic light-emitting diodes comprising at least one disilyl compound selected from disilylcarbazoles, disilyldibenzofurans, disilyldibenzothiophenes, disilyldibenzophospholes, disilyldibenzothiophene s-oxides and disilyldibenzothiophene s,s-dioxides
WO2009008100A1 (en) 2007-07-10 2009-01-15 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence element, and organic electroluminescence element prepared by using the material
JP2009021336A (en) 2007-07-11 2009-01-29 Konica Minolta Holdings Inc Organic electroluminescent element, display device, and lighting device
US20090039776A1 (en) 2007-08-09 2009-02-12 Canon Kabushiki Kaisha Organometallic complex and organic light-emitting element using same
JP2009049318A (en) 2007-08-22 2009-03-05 Fujifilm Corp Organic electroluminescent device and novel indole derivative
EP2034538A1 (en) 2006-06-02 2009-03-11 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence element, and organic electroluminescence element using the material
US20090066226A1 (en) 2005-04-18 2009-03-12 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
JP2009059767A (en) 2007-08-30 2009-03-19 Konica Minolta Holdings Inc Organic electroluminescent element, illumination apparatus, and display device
WO2009050281A1 (en) 2007-10-17 2009-04-23 Basf Se Transition metal complexes with bridged carbene ligands and use thereof in oleds
WO2009050290A1 (en) 2007-10-17 2009-04-23 Basf Se Transition metal complexes having bridged carbene ligands and the use thereof in oleds
WO2009060780A1 (en) 2007-11-08 2009-05-14 Konica Minolta Holdings, Inc. Organic electroluminescence element, display device, and lighting system
WO2009060779A1 (en) 2007-11-08 2009-05-14 Konica Minolta Holdings, Inc. Organic electroluminescent device material, organic electroluminescent device, display device and illuminating device
WO2009060742A1 (en) 2007-11-08 2009-05-14 Konica Minolta Holdings, Inc. Organic electroluminescent device, display device, and illuminating device
WO2009060757A1 (en) 2007-11-08 2009-05-14 Konica Minolta Holdings, Inc. Organic electroluminescent device, display device and illuminating device
WO2009063757A1 (en) 2007-11-14 2009-05-22 Konica Minolta Holdings, Inc. Organic electroluminescent device material, organic electroluminescent device, method for manufacturing organic electroluminescent device, display device and illuminating device
JP2009114369A (en) 2007-11-08 2009-05-28 Konica Minolta Holdings Inc Organic electroluminescent material, organic electroluminescent element, display and illuminator
US20090134784A1 (en) 2004-10-21 2009-05-28 Universal Display Corporation Carbazole-containing materials in phosphorescent light emitting diodes
JP2009114370A (en) 2007-11-08 2009-05-28 Konica Minolta Holdings Inc Organic electroluminescence element material, organic electroluminescence element, display device, and lighting system
WO2009073245A1 (en) 2007-12-06 2009-06-11 Universal Display Corporation Light-emitting organometallic complexes
US20090153034A1 (en) 2007-12-13 2009-06-18 Universal Display Corporation Carbazole-containing materials in phosphorescent light emittinig diodes
JP2009135183A (en) 2007-11-29 2009-06-18 Konica Minolta Holdings Inc Organic electroluminescence element, display, and lighting device
WO2009084413A1 (en) 2007-12-28 2009-07-09 Konica Minolta Holdings, Inc. Organic electroluminescent device and method for manufacturing organic electroluminescent device
JP2009170764A (en) 2008-01-18 2009-07-30 Konica Minolta Holdings Inc Material for organic electroluminescent element, organic electroluminescent element, method of manufacturing organic electroluminescent element, display device, and illumination device
JP2009182298A (en) 2008-02-01 2009-08-13 Konica Minolta Holdings Inc Organic electroluminescence element, lighting device, and display device
WO2009104488A1 (en) 2008-02-20 2009-08-27 コニカミノルタホールディングス株式会社 White light-emitting organic electroluminescent device
JP2009267255A (en) 2008-04-28 2009-11-12 Idemitsu Kosan Co Ltd Material for organic electroluminescent element and organic electroluminescent element using the material
US20090284138A1 (en) 2008-05-13 2009-11-19 Konica Minolta Holdings, Inc. Organic electroluminescent element, display device and lighting device
WO2010002850A1 (en) 2008-06-30 2010-01-07 Universal Display Corporation Hole transport materials containing triphenylene
WO2010001830A1 (en) 2008-07-01 2010-01-07 コニカミノルタホールディングス株式会社 White light-emitting organic electroluminescent element, illuminating device and display device
WO2010004877A1 (en) 2008-07-10 2010-01-14 コニカミノルタホールディングス株式会社 Organic electroluminescent element, display device and illuminating device
JP2010021336A (en) 2008-07-10 2010-01-28 Konica Minolta Holdings Inc Organic electroluminescence device, illuminator, and display device
JP2010040830A (en) 2008-08-06 2010-02-18 Konica Minolta Holdings Inc Organic electroluminescent element, display device, and lighting system
WO2010024404A1 (en) 2008-08-28 2010-03-04 旭硝子株式会社 Abrasive composition and method for manufacturing semiconductor integrated circuit device
WO2010028151A1 (en) 2008-09-03 2010-03-11 Universal Display Corporation Phosphorescent materials
WO2010040777A1 (en) 2008-10-07 2010-04-15 Osram Opto Semiconductors Gmbh Siloles substituted with condensed ring systems and use thereof in organic electronics
WO2010044342A1 (en) 2008-10-15 2010-04-22 コニカミノルタホールディングス株式会社 Organic el element, organic el element manufacturing method, white organic el element, display device, and illumination device
EP2180029A1 (en) 2008-10-23 2010-04-28 Novaled AG Radialene compounds and their use
US20100102709A1 (en) 2008-04-29 2010-04-29 Olaf Zeika Radialene compounds and their use
JP2010114180A (en) 2008-11-05 2010-05-20 Konica Minolta Holdings Inc Organic electroluminescent element, white organic electroluminescent element, display device and illuminator
WO2010056669A1 (en) 2008-11-11 2010-05-20 Universal Display Corporation Phosphorescent emitters
JP2010135467A (en) 2008-12-03 2010-06-17 Konica Minolta Holdings Inc Organic electroluminescent element, lighting system equipped with the element, and display device
WO2010067746A1 (en) 2008-12-08 2010-06-17 コニカミノルタホールディングス株式会社 Organic electroluminescence element, display device and illumination device
WO2010068876A1 (en) 2008-12-12 2010-06-17 Universal Display Corporation BLUE EMITTER WITH HIGH EFFICIENCY BASED ON IMIDAZO [1,2-f] PHENANTHRIDINE IRIDIUM COMPLEXES
WO2010079051A1 (en) 2009-01-07 2010-07-15 Basf Se Silyl and heteroatom substituted compounds selected from carbazoles, dibenzofurans, dibenzothiophenes and dibenzo phospholes and the application thereof in organic electronics
WO2010079678A1 (en) 2009-01-09 2010-07-15 コニカミノルタホールディングス株式会社 Organic electroluminescent element, display device, and lighting device
WO2010086089A1 (en) 2009-02-02 2010-08-05 Merck Patent Gmbh Metal complexes
WO2010087222A1 (en) 2009-01-28 2010-08-05 コニカミノルタホールディングス株式会社 Organic electroluminescent element, display device, and illumination device
WO2010090077A1 (en) 2009-02-06 2010-08-12 コニカミノルタホールディングス株式会社 Organic electroluminescent element, and illumination device and display device each comprising the element
WO2010095564A1 (en) 2009-02-18 2010-08-26 コニカミノルタホールディングス株式会社 Organic electroluminescent element, and illuminating device and display device each comprising the element
WO2010118029A1 (en) 2009-04-06 2010-10-14 Universal Display Corporation Metal complex comprising novel ligand structures
EP2246862A1 (en) 2009-04-27 2010-11-03 Novaled AG Organic electronic device comprising an organic semiconducting material
WO2010129323A1 (en) 2009-04-28 2010-11-11 Universal Display Corporation Iridium complex with methyl-d3 substitution
WO2010132236A1 (en) 2009-05-13 2010-11-18 Global Oled Technology Llc. Internal connector for organic electronic devices
US20110057559A1 (en) 2007-12-28 2011-03-10 Universal Display Corporation Phosphorescent emitters and host materials with improved stability
WO2011051404A1 (en) 2009-10-28 2011-05-05 Basf Se Heteroleptic carbene complexes and use thereof in organic electronics
WO2011073149A1 (en) 2009-12-14 2011-06-23 Basf Se Metal complexes comprising diazabenzimidazol carbene-ligands and the use thereof in oleds
US20110163302A1 (en) 2008-06-30 2011-07-07 Universal Display Corporation Hole transport materials having a sulfur-containing group
WO2011090535A1 (en) 2010-01-20 2011-07-28 Universal Display Corporation Electroluminescent devices for lighting applications
WO2011106344A1 (en) 2010-02-25 2011-09-01 Universal Display Corporation Phosphorescent emitters
US20110210316A1 (en) 2010-03-01 2011-09-01 Semiconductor Energy Laboratory Co., Ltd. Heterocyclic compound, light-emitting element, light-emitting device, electronic device, and lighting device
WO2011109042A1 (en) 2010-03-03 2011-09-09 Universal Display Corporation Phosphorescent materials
US20110233528A1 (en) 2010-03-24 2011-09-29 Universal Display Corporation Novel oled display architecture
WO2011137072A1 (en) 2010-04-26 2011-11-03 Universal Display Corporation Bicarbazole containing compounds for oleds
WO2011157790A1 (en) 2010-06-18 2011-12-22 Basf Se Organic electronic devices comprising a layer of a dibenzofurane compound and a 8-hydroxyquinolinolato earth alkaline metal, or alkali metal complex
WO2011157779A1 (en) 2010-06-18 2011-12-22 Basf Se Organic electronic devices comprising a layer of a pyridine compound and a 8-hydroxyquinolinolato earth alkaline metal, or alkali metal complex
EP2401254A1 (en) 2009-02-26 2012-01-04 Novaled AG Quinone compounds as dopants in organic electronics
WO2012008881A1 (en) 2010-07-15 2012-01-19 Kuznetsov Andrey Leionidovich Piezoelectric pump
WO2012014621A1 (en) 2010-07-29 2012-02-02 コニカミノルタホールディングス株式会社 Transparent conductive film and organic electroluminescent element
WO2012016601A1 (en) 2010-08-06 2012-02-09 Telefonica, S.A. A method for managing presence information
WO2012048266A1 (en) 2010-10-08 2012-04-12 Universal Display Corporation Novel 3, 9-linked oligocarbazole-based hosts, containing dbt and dbr fragments, separated by aromatic spacers
WO2012053627A1 (en) 2010-10-22 2012-04-26 Semiconductor Energy Laboratory Co., Ltd. Organometallic complex, light-emitting element, light-emitting device, electronic device and lighting device
JP2012089777A (en) 2010-10-22 2012-05-10 Konica Minolta Holdings Inc Organic electroluminescence element, lighting device, and display device
WO2012105310A1 (en) 2011-02-02 2012-08-09 コニカミノルタホールディングス株式会社 Organic electroluminescence element and illumination device
WO2012111462A1 (en) 2011-02-15 2012-08-23 コニカミノルタホールディングス株式会社 Organic electroluminescence element and illumination device
WO2012115034A1 (en) 2011-02-22 2012-08-30 コニカミノルタホールディングス株式会社 Organic electroluminescent element, illumination device, and display device
WO2012121936A2 (en) 2011-03-08 2012-09-13 Universal Display Corporation Pyridyl carbene phosphorescent emitters
WO2012130709A1 (en) 2011-03-25 2012-10-04 Basf Se 4h-imidazo[1,2-a]imidazoles for electronic applications
WO2012147397A1 (en) 2011-04-26 2012-11-01 コニカミノルタホールディングス株式会社 Organic electroluminescent element and illuminating apparatus
US20120292600A1 (en) 2011-05-19 2012-11-22 Universal Display Corporation Phosphorescent heteroleptic phenylbenzimidazole dopants
WO2012162325A1 (en) 2011-05-25 2012-11-29 Universal Display Corporation Host materials for oleds
WO2012166608A1 (en) 2011-05-27 2012-12-06 Universal Display Corporation High efficiency yellow light emitters for oled devices
US20120305894A1 (en) 2011-06-01 2012-12-06 Do-Han Kim Blue phosphorescent compound and organic electroluminescent device using the same
WO2012170463A1 (en) 2011-06-08 2012-12-13 Universal Display Corporation Heteroleptic iridium carbene complexes and light emitting device using them
WO2012172482A1 (en) 2011-06-14 2012-12-20 Basf Se Metal complexes comprising azabenzimidazole carbene ligands and the use thereof in oleds
EP2551932A2 (en) 2011-07-28 2013-01-30 Universal Display Corporation Host materials for phosphorescent oleds
EP2551933A1 (en) 2011-07-28 2013-01-30 Universal Display Corporation Heteroleptic iridium complexes as dopants
WO2013022419A1 (en) 2011-08-05 2013-02-14 Universal Display Corporation Phosphorescent organic light emitting devices combined with hole transport material having high operating stability
WO2014044722A1 (en) * 2012-09-20 2014-03-27 Basf Se Azadibenzofurans for electronic applications
KR20140087805A (en) 2012-12-31 2014-07-09 제일모직주식회사 COMPOUND FOR ORGANIC OPTOELECTRONIC DEVICE, ORGANIC LiGHT EMITTING DIODE INCLUDING THE SAME AND DISPLAY INCLUDING THE ORGANIC LiGHT EMITTING DIODE
KR20140103842A (en) 2013-02-15 2014-08-27 에스에프씨 주식회사 Novel organic compounds for organic light-emitting diode and organic light-emitting diode including the same
KR20140114489A (en) * 2013-03-14 2014-09-29 에스에프씨 주식회사 An electroluminescen compound and an electroluminescent device comprising the same
KR20150014286A (en) * 2013-07-29 2015-02-06 덕산하이메탈(주) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
WO2015030469A1 (en) * 2013-08-26 2015-03-05 덕산네오룩스 주식회사 Compound for organic electrical element, organic electrical element using same, and electronic device thereof

Patent Citations (172)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000070655A2 (en) 1999-05-13 2000-11-23 The Trustees Of Princeton University Very high efficiency organic light emitting devices based on electrophosphorescence
EP1097981A2 (en) 1999-11-02 2001-05-09 Sony Corporation Organic electroluminescent device
WO2001041512A1 (en) 1999-12-01 2001-06-07 The Trustees Of Princeton University Complexes of form l2mx as phosphorescent dopants for organic leds
US20010019782A1 (en) 1999-12-27 2001-09-06 Tatsuya Igarashi Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex
US20010015432A1 (en) 2000-02-10 2001-08-23 Tatsuya Igarashi Light emitting device material comprising iridium complex and light emitting device using same material
WO2002002714A2 (en) 2000-06-30 2002-01-10 E.I. Du Pont De Nemours And Company Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds
US20020024293A1 (en) 2000-07-17 2002-02-28 Fuji Photo Film Co., Ltd. Light-emitting element and iridium complex
WO2002015645A1 (en) 2000-08-11 2002-02-21 The Trustees Of Princeton University Organometallic compounds and emission-shifting organic electrophosphorescence
US20020055014A1 (en) 2000-08-24 2002-05-09 Fuji Photo Film Co., Ltd. Light-emitting device and material therefor
US20020048689A1 (en) 2000-09-21 2002-04-25 Fuji Photo Film Co., Ltd. Light-emitting device and iridium complex
EP1191613A2 (en) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Luminescence device, display apparatus and metal coordination compound
EP1191612A2 (en) 2000-09-26 2002-03-27 Canon Kabushiki Kaisha Luminescence device, display apparatus and metal coordination compound
US20020094453A1 (en) 2000-11-29 2002-07-18 Takao Takiguchi Metal coordination compound, luminescence device and display apparatus
EP1211257A2 (en) 2000-12-01 2002-06-05 Canon Kabushiki Kaisha Metal coordination compound, luminescence device and display apparatus
US20020117662A1 (en) 2000-12-25 2002-08-29 Fuji Photo Film Co., Ltd. Novel indole derivative, material for light-emitting device and light-emitting device using the same
WO2002060910A1 (en) 2001-02-01 2002-08-08 Covion Organic Semiconductors Gmbh Method for the production of highly pure, tris-ortho-metalated organo-iridium compounds
US6921915B2 (en) 2001-03-08 2005-07-26 Canon Kabushiki Kaisha Metal coordination compound, luminescence device and display apparatus
JP2003277744A (en) 2002-03-27 2003-10-02 Idemitsu Kosan Co Ltd Material for organic electroluminescent element and organic electroluminescent element obtained using the same
US6687266B1 (en) 2002-11-08 2004-02-03 Universal Display Corporation Organic light emitting materials and devices
WO2005019373A2 (en) 2003-08-19 2005-03-03 Basf Aktiengesellschaft Transition metal complexes comprising carbene ligands serving as emitters for organic light-emitting diodes (oled's)
WO2005113704A2 (en) 2004-05-18 2005-12-01 The University Of Southern California Luminescent compounds with carbene ligands
US20060008670A1 (en) 2004-07-06 2006-01-12 Chun Lin Organic light emitting materials and devices
WO2006014599A2 (en) 2004-07-07 2006-02-09 Universal Display Corporation Stable and efficient electroluminescent materials
US20090134784A1 (en) 2004-10-21 2009-05-28 Universal Display Corporation Carbazole-containing materials in phosphorescent light emitting diodes
WO2006056418A2 (en) 2004-11-25 2006-06-01 Basf Aktiengesellschaft Use of transition metal carbene complexes in organic light-emitting diodes (oleds)
WO2006067074A1 (en) 2004-12-23 2006-06-29 Ciba Specialty Chemicals Holding Inc. Electroluminescent metal complexes with nucleophilic carbene ligands
WO2006098460A1 (en) 2005-03-17 2006-09-21 Semiconductor Energy Laboratory Co., Ltd. Organometallic complex, and light-emitting element, light-emitting device and electronic device using the organometallic complex
WO2006100298A1 (en) 2005-03-24 2006-09-28 Basf Aktiengesellschaft Use of compounds containing aromatic or heteroaromatic rings linked via carbonyl group-containing groups, for use as matrix materials in organic light-emitting diodes
US20090066226A1 (en) 2005-04-18 2009-03-12 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
WO2006115301A1 (en) 2005-04-25 2006-11-02 Fujifilm Corporation Organic electroluminescent device
WO2006121811A1 (en) 2005-05-06 2006-11-16 Universal Display Corporation Stability oled materials and devices with improved stability
WO2006128800A1 (en) 2005-05-30 2006-12-07 Ciba Specialty Chemicals Holding Inc. Electroluminescent device
EP1885818B1 (en) 2005-05-30 2010-01-13 Basf Se Electroluminescent device
EP1885818A1 (en) 2005-05-30 2008-02-13 Ciba Specialty Chemicals Holding Inc. Electroluminescent device
JP2007123392A (en) 2005-10-26 2007-05-17 Konica Minolta Holdings Inc Organic electroluminescence device, display device and lighting device
EP1786050A1 (en) 2005-11-10 2007-05-16 Novaled AG Doped organic semiconductor material
EP1970976A1 (en) 2006-01-05 2008-09-17 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
WO2007077810A1 (en) 2006-01-05 2007-07-12 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
WO2007095118A2 (en) 2006-02-10 2007-08-23 Universal Display Corporation METAL COMPLEXES OF CYCLOMETALLATED IMIDAZO[1,2-f]PHENANTHRIDINE AND DIIMIDAZO[1,2-A:1',2'-C]QUINAZOLINE LIGANDS AND ISOELECTRONIC AND BENZANNULATED ANALOGS THEREOF
US20070190359A1 (en) 2006-02-10 2007-08-16 Knowles David B Metal complexes of cyclometallated imidazo[1,2-ƒ]phenanthridine and diimidazo[1,2-a:1',2'-c]quinazoline ligands and isoelectronic and benzannulated analogs thereof
WO2007108362A1 (en) 2006-03-17 2007-09-27 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
EP1837926B1 (en) 2006-03-21 2008-05-07 Novaled AG Heterocyclic radicals or diradicals and their dimers, oligomers, polymers, di-spiro and polycyclic derivatives as well as their use in organic semiconductor materials and electronic devices.
EP1837927A1 (en) 2006-03-22 2007-09-26 Novaled AG Use of heterocyclic radicals for doping of organic semiconductors
WO2007108459A1 (en) 2006-03-23 2007-09-27 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
EP1998388A1 (en) 2006-03-23 2008-12-03 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
US20070224446A1 (en) 2006-03-24 2007-09-27 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence device and organic electroluminescence device using the same
WO2007114244A1 (en) 2006-03-30 2007-10-11 Konica Minolta Holdings, Inc. Organic electroluminescent device, illuminating device and display device
WO2007115981A1 (en) 2006-04-04 2007-10-18 Basf Se Transition metal complexes comprising one noncarbene ligand and one or two carbene ligands and their use in oleds
WO2007115970A1 (en) 2006-04-05 2007-10-18 Basf Se Heteroleptic transition metal-carbene complexes and their use in organic light-emitting diodes (oleds)
WO2007119816A1 (en) 2006-04-19 2007-10-25 Konica Minolta Holdings, Inc. Organic electroluminescence element material, organic electroluminescence element, display device and lighting apparatus
US20070278938A1 (en) 2006-04-26 2007-12-06 Idemitsu Kosan Co., Ltd. Aromatic amine derivative and electroluminescence device using the same
EP2034538A1 (en) 2006-06-02 2009-03-11 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence element, and organic electroluminescence element using the material
WO2008000727A1 (en) 2006-06-26 2008-01-03 Basf Se Use in oleds of transition metal carbene complexes that contain no cyclometallation via non-carbenes
JP2008021687A (en) 2006-07-10 2008-01-31 Mitsubishi Chemicals Corp Material for organic electric field light emitting element, composition for organic electric field light emitting element and organic electric field light emitting element
US20080106190A1 (en) 2006-08-23 2008-05-08 Idemitsu Kosan Co., Ltd. Aromatic amine derivatives and organic electroluminescent device using same
WO2008029729A1 (en) 2006-09-08 2008-03-13 Konica Minolta Holdings, Inc. Organic electroluminescent device, illuminating device and display
WO2008029652A1 (en) 2006-09-08 2008-03-13 Konica Minolta Holdings, Inc. Organic electroluminescent device, illuminating device and display
JP2008066569A (en) 2006-09-08 2008-03-21 Konica Minolta Holdings Inc Organic electroluminescence element, lighting system and display device
WO2008035571A1 (en) 2006-09-20 2008-03-27 Konica Minolta Holdings, Inc. Organic electroluminescence element
WO2008034758A2 (en) 2006-09-21 2008-03-27 Basf Se Oled display with extended lifetime
JP2008074939A (en) 2006-09-21 2008-04-03 Konica Minolta Holdings Inc Organic electroluminescence element material, organic electroluminescence element, display device and illumination device
JP2008084913A (en) 2006-09-26 2008-04-10 Konica Minolta Holdings Inc Organic electroluminescence element, display device, and lighting device
JP2008127326A (en) 2006-11-20 2008-06-05 Chemiprokasei Kaisha Ltd New di(pyridylphenyl) derivative, electron transport material comprising the same and organic electroluminescent device containing the same
WO2008066196A1 (en) 2006-11-27 2008-06-05 Fujifilm Corporation Organic electroluminescent device and indole derivative
WO2008072596A1 (en) 2006-12-13 2008-06-19 Konica Minolta Holdings, Inc. Organic electroluminescent device, display and illuminating device
WO2008090912A1 (en) 2007-01-23 2008-07-31 Konica Minolta Holdings, Inc. Method for manufacturing organic electroluminescent device, organic electroluminescent device manufactured by the method, display device and illuminating device
JP2008207520A (en) 2007-02-28 2008-09-11 Konica Minolta Holdings Inc Organic thin film, method for producing the same, electronic device, organic luminescence element, display device and lightening equipment
EP1970371A1 (en) 2007-03-16 2008-09-17 Novaled AG Pyrido(3,2-h)chinazolins and/or 5,6-Dihydro derivatives thereof, method for their manufacture and endowed organic semiconductor material containing them
US20080265216A1 (en) 2007-04-30 2008-10-30 Novaled Ag Oxocarbon-, pseudooxocarbon- and radialene compounds and their use
EP1988587A1 (en) 2007-04-30 2008-11-05 Novaled AG Oxocarbon, pseudo oxocarbon and radialene compounds and their use
WO2008140114A1 (en) 2007-05-16 2008-11-20 Konica Minolta Holdings, Inc. Organic electroluminescence element, display device and illuminating device
WO2008146838A1 (en) 2007-05-30 2008-12-04 Konica Minolta Holdings, Inc. Organic electroluminescent device, display device and illuminating device
WO2008156879A1 (en) 2007-06-20 2008-12-24 Universal Display Corporation Blue phosphorescent imidazophenanthridine materials
WO2008156105A1 (en) 2007-06-21 2008-12-24 Konica Minolta Holdings, Inc. Organic electroluminescence element material, organic electroluminescence element, display device and illuminating device
WO2009003919A1 (en) 2007-07-05 2009-01-08 Basf Se Organic light-emitting diodes comprising at least one disilyl compound selected from disilylcarbazoles, disilyldibenzofurans, disilyldibenzothiophenes, disilyldibenzophospholes, disilyldibenzothiophene s-oxides and disilyldibenzothiophene s,s-dioxides
WO2009003898A1 (en) 2007-07-05 2009-01-08 Basf Se Organic light-emitting diodes containing carbene transition metal complex emitters and at least one compound selected from disilylcarbazoles, disilyldibenzofurans, disilyldibenzothiophenes, disilyldibenzophospholes, disilyldibenzothiophene s-oxides and disilyldibenzothiophene s,s-dioxides
WO2009008099A1 (en) 2007-07-10 2009-01-15 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence element, and organic electroluminescence element prepared by using the material
WO2009008100A1 (en) 2007-07-10 2009-01-15 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence element, and organic electroluminescence element prepared by using the material
JP2009021336A (en) 2007-07-11 2009-01-29 Konica Minolta Holdings Inc Organic electroluminescent element, display device, and lighting device
US20090039776A1 (en) 2007-08-09 2009-02-12 Canon Kabushiki Kaisha Organometallic complex and organic light-emitting element using same
JP2009049318A (en) 2007-08-22 2009-03-05 Fujifilm Corp Organic electroluminescent device and novel indole derivative
JP2009059767A (en) 2007-08-30 2009-03-19 Konica Minolta Holdings Inc Organic electroluminescent element, illumination apparatus, and display device
WO2009050281A1 (en) 2007-10-17 2009-04-23 Basf Se Transition metal complexes with bridged carbene ligands and use thereof in oleds
WO2009050290A1 (en) 2007-10-17 2009-04-23 Basf Se Transition metal complexes having bridged carbene ligands and the use thereof in oleds
JP2009114369A (en) 2007-11-08 2009-05-28 Konica Minolta Holdings Inc Organic electroluminescent material, organic electroluminescent element, display and illuminator
WO2009060757A1 (en) 2007-11-08 2009-05-14 Konica Minolta Holdings, Inc. Organic electroluminescent device, display device and illuminating device
WO2009060742A1 (en) 2007-11-08 2009-05-14 Konica Minolta Holdings, Inc. Organic electroluminescent device, display device, and illuminating device
WO2009060779A1 (en) 2007-11-08 2009-05-14 Konica Minolta Holdings, Inc. Organic electroluminescent device material, organic electroluminescent device, display device and illuminating device
JP2009114370A (en) 2007-11-08 2009-05-28 Konica Minolta Holdings Inc Organic electroluminescence element material, organic electroluminescence element, display device, and lighting system
WO2009060780A1 (en) 2007-11-08 2009-05-14 Konica Minolta Holdings, Inc. Organic electroluminescence element, display device, and lighting system
WO2009063757A1 (en) 2007-11-14 2009-05-22 Konica Minolta Holdings, Inc. Organic electroluminescent device material, organic electroluminescent device, method for manufacturing organic electroluminescent device, display device and illuminating device
JP2009135183A (en) 2007-11-29 2009-06-18 Konica Minolta Holdings Inc Organic electroluminescence element, display, and lighting device
WO2009073245A1 (en) 2007-12-06 2009-06-11 Universal Display Corporation Light-emitting organometallic complexes
US20090153034A1 (en) 2007-12-13 2009-06-18 Universal Display Corporation Carbazole-containing materials in phosphorescent light emittinig diodes
WO2009084413A1 (en) 2007-12-28 2009-07-09 Konica Minolta Holdings, Inc. Organic electroluminescent device and method for manufacturing organic electroluminescent device
WO2009086028A2 (en) 2007-12-28 2009-07-09 Universal Display Corporation Carbazole-containing materials in phosphorescent light emitting diodes
US20110057559A1 (en) 2007-12-28 2011-03-10 Universal Display Corporation Phosphorescent emitters and host materials with improved stability
JP2009170764A (en) 2008-01-18 2009-07-30 Konica Minolta Holdings Inc Material for organic electroluminescent element, organic electroluminescent element, method of manufacturing organic electroluminescent element, display device, and illumination device
JP2009182298A (en) 2008-02-01 2009-08-13 Konica Minolta Holdings Inc Organic electroluminescence element, lighting device, and display device
WO2009104488A1 (en) 2008-02-20 2009-08-27 コニカミノルタホールディングス株式会社 White light-emitting organic electroluminescent device
JP2009267255A (en) 2008-04-28 2009-11-12 Idemitsu Kosan Co Ltd Material for organic electroluminescent element and organic electroluminescent element using the material
US20100102709A1 (en) 2008-04-29 2010-04-29 Olaf Zeika Radialene compounds and their use
US20090284138A1 (en) 2008-05-13 2009-11-19 Konica Minolta Holdings, Inc. Organic electroluminescent element, display device and lighting device
US20120261654A1 (en) 2008-05-13 2012-10-18 Konica Minolta Holdings, Inc. Organic electroluminescent element, display device and lighting device
WO2010002850A1 (en) 2008-06-30 2010-01-07 Universal Display Corporation Hole transport materials containing triphenylene
US20110163302A1 (en) 2008-06-30 2011-07-07 Universal Display Corporation Hole transport materials having a sulfur-containing group
WO2010001830A1 (en) 2008-07-01 2010-01-07 コニカミノルタホールディングス株式会社 White light-emitting organic electroluminescent element, illuminating device and display device
WO2010004877A1 (en) 2008-07-10 2010-01-14 コニカミノルタホールディングス株式会社 Organic electroluminescent element, display device and illuminating device
JP2010021336A (en) 2008-07-10 2010-01-28 Konica Minolta Holdings Inc Organic electroluminescence device, illuminator, and display device
JP2010040830A (en) 2008-08-06 2010-02-18 Konica Minolta Holdings Inc Organic electroluminescent element, display device, and lighting system
WO2010024404A1 (en) 2008-08-28 2010-03-04 旭硝子株式会社 Abrasive composition and method for manufacturing semiconductor integrated circuit device
WO2010028151A1 (en) 2008-09-03 2010-03-11 Universal Display Corporation Phosphorescent materials
US20110227049A1 (en) 2008-09-03 2011-09-22 Universal Display Corporation Phosphorescent materials
WO2010027583A1 (en) 2008-09-03 2010-03-11 Universal Display Corporation Phosphorescent materials
WO2010040777A1 (en) 2008-10-07 2010-04-15 Osram Opto Semiconductors Gmbh Siloles substituted with condensed ring systems and use thereof in organic electronics
WO2010044342A1 (en) 2008-10-15 2010-04-22 コニカミノルタホールディングス株式会社 Organic el element, organic el element manufacturing method, white organic el element, display device, and illumination device
EP2180029A1 (en) 2008-10-23 2010-04-28 Novaled AG Radialene compounds and their use
JP2010114180A (en) 2008-11-05 2010-05-20 Konica Minolta Holdings Inc Organic electroluminescent element, white organic electroluminescent element, display device and illuminator
WO2010056669A1 (en) 2008-11-11 2010-05-20 Universal Display Corporation Phosphorescent emitters
JP2010135467A (en) 2008-12-03 2010-06-17 Konica Minolta Holdings Inc Organic electroluminescent element, lighting system equipped with the element, and display device
WO2010067746A1 (en) 2008-12-08 2010-06-17 コニカミノルタホールディングス株式会社 Organic electroluminescence element, display device and illumination device
WO2010068876A1 (en) 2008-12-12 2010-06-17 Universal Display Corporation BLUE EMITTER WITH HIGH EFFICIENCY BASED ON IMIDAZO [1,2-f] PHENANTHRIDINE IRIDIUM COMPLEXES
WO2010079051A1 (en) 2009-01-07 2010-07-15 Basf Se Silyl and heteroatom substituted compounds selected from carbazoles, dibenzofurans, dibenzothiophenes and dibenzo phospholes and the application thereof in organic electronics
WO2010079678A1 (en) 2009-01-09 2010-07-15 コニカミノルタホールディングス株式会社 Organic electroluminescent element, display device, and lighting device
WO2010087222A1 (en) 2009-01-28 2010-08-05 コニカミノルタホールディングス株式会社 Organic electroluminescent element, display device, and illumination device
WO2010086089A1 (en) 2009-02-02 2010-08-05 Merck Patent Gmbh Metal complexes
WO2010090077A1 (en) 2009-02-06 2010-08-12 コニカミノルタホールディングス株式会社 Organic electroluminescent element, and illumination device and display device each comprising the element
WO2010095564A1 (en) 2009-02-18 2010-08-26 コニカミノルタホールディングス株式会社 Organic electroluminescent element, and illuminating device and display device each comprising the element
EP2401254A1 (en) 2009-02-26 2012-01-04 Novaled AG Quinone compounds as dopants in organic electronics
WO2010118029A1 (en) 2009-04-06 2010-10-14 Universal Display Corporation Metal complex comprising novel ligand structures
EP2246862A1 (en) 2009-04-27 2010-11-03 Novaled AG Organic electronic device comprising an organic semiconducting material
WO2010129323A1 (en) 2009-04-28 2010-11-11 Universal Display Corporation Iridium complex with methyl-d3 substitution
WO2010132236A1 (en) 2009-05-13 2010-11-18 Global Oled Technology Llc. Internal connector for organic electronic devices
WO2011051404A1 (en) 2009-10-28 2011-05-05 Basf Se Heteroleptic carbene complexes and use thereof in organic electronics
WO2011073149A1 (en) 2009-12-14 2011-06-23 Basf Se Metal complexes comprising diazabenzimidazol carbene-ligands and the use thereof in oleds
WO2011090535A1 (en) 2010-01-20 2011-07-28 Universal Display Corporation Electroluminescent devices for lighting applications
WO2011106344A1 (en) 2010-02-25 2011-09-01 Universal Display Corporation Phosphorescent emitters
US20110210316A1 (en) 2010-03-01 2011-09-01 Semiconductor Energy Laboratory Co., Ltd. Heterocyclic compound, light-emitting element, light-emitting device, electronic device, and lighting device
WO2011109042A1 (en) 2010-03-03 2011-09-09 Universal Display Corporation Phosphorescent materials
US20110233528A1 (en) 2010-03-24 2011-09-29 Universal Display Corporation Novel oled display architecture
WO2011137072A1 (en) 2010-04-26 2011-11-03 Universal Display Corporation Bicarbazole containing compounds for oleds
WO2011157790A1 (en) 2010-06-18 2011-12-22 Basf Se Organic electronic devices comprising a layer of a dibenzofurane compound and a 8-hydroxyquinolinolato earth alkaline metal, or alkali metal complex
WO2011157779A1 (en) 2010-06-18 2011-12-22 Basf Se Organic electronic devices comprising a layer of a pyridine compound and a 8-hydroxyquinolinolato earth alkaline metal, or alkali metal complex
WO2012008881A1 (en) 2010-07-15 2012-01-19 Kuznetsov Andrey Leionidovich Piezoelectric pump
WO2012014621A1 (en) 2010-07-29 2012-02-02 コニカミノルタホールディングス株式会社 Transparent conductive film and organic electroluminescent element
WO2012016601A1 (en) 2010-08-06 2012-02-09 Telefonica, S.A. A method for managing presence information
WO2012048266A1 (en) 2010-10-08 2012-04-12 Universal Display Corporation Novel 3, 9-linked oligocarbazole-based hosts, containing dbt and dbr fragments, separated by aromatic spacers
WO2012053627A1 (en) 2010-10-22 2012-04-26 Semiconductor Energy Laboratory Co., Ltd. Organometallic complex, light-emitting element, light-emitting device, electronic device and lighting device
JP2012089777A (en) 2010-10-22 2012-05-10 Konica Minolta Holdings Inc Organic electroluminescence element, lighting device, and display device
WO2012105310A1 (en) 2011-02-02 2012-08-09 コニカミノルタホールディングス株式会社 Organic electroluminescence element and illumination device
WO2012111462A1 (en) 2011-02-15 2012-08-23 コニカミノルタホールディングス株式会社 Organic electroluminescence element and illumination device
WO2012115034A1 (en) 2011-02-22 2012-08-30 コニカミノルタホールディングス株式会社 Organic electroluminescent element, illumination device, and display device
WO2012121936A2 (en) 2011-03-08 2012-09-13 Universal Display Corporation Pyridyl carbene phosphorescent emitters
WO2012130709A1 (en) 2011-03-25 2012-10-04 Basf Se 4h-imidazo[1,2-a]imidazoles for electronic applications
WO2012147397A1 (en) 2011-04-26 2012-11-01 コニカミノルタホールディングス株式会社 Organic electroluminescent element and illuminating apparatus
US20120292600A1 (en) 2011-05-19 2012-11-22 Universal Display Corporation Phosphorescent heteroleptic phenylbenzimidazole dopants
WO2012162325A1 (en) 2011-05-25 2012-11-29 Universal Display Corporation Host materials for oleds
WO2012166608A1 (en) 2011-05-27 2012-12-06 Universal Display Corporation High efficiency yellow light emitters for oled devices
US20120305894A1 (en) 2011-06-01 2012-12-06 Do-Han Kim Blue phosphorescent compound and organic electroluminescent device using the same
WO2012170463A1 (en) 2011-06-08 2012-12-13 Universal Display Corporation Heteroleptic iridium carbene complexes and light emitting device using them
WO2012170461A1 (en) 2011-06-08 2012-12-13 Universal Display Corporation Heteroleptic iridium carbene complexes and light emitting device using them
WO2012170571A1 (en) 2011-06-08 2012-12-13 Universal Display Corporation Heteroleptic iridium carbene complexes and light emitting device using them
WO2012172482A1 (en) 2011-06-14 2012-12-20 Basf Se Metal complexes comprising azabenzimidazole carbene ligands and the use thereof in oleds
EP2551932A2 (en) 2011-07-28 2013-01-30 Universal Display Corporation Host materials for phosphorescent oleds
EP2551933A1 (en) 2011-07-28 2013-01-30 Universal Display Corporation Heteroleptic iridium complexes as dopants
WO2013022419A1 (en) 2011-08-05 2013-02-14 Universal Display Corporation Phosphorescent organic light emitting devices combined with hole transport material having high operating stability
WO2014044722A1 (en) * 2012-09-20 2014-03-27 Basf Se Azadibenzofurans for electronic applications
KR20140087805A (en) 2012-12-31 2014-07-09 제일모직주식회사 COMPOUND FOR ORGANIC OPTOELECTRONIC DEVICE, ORGANIC LiGHT EMITTING DIODE INCLUDING THE SAME AND DISPLAY INCLUDING THE ORGANIC LiGHT EMITTING DIODE
KR20140103842A (en) 2013-02-15 2014-08-27 에스에프씨 주식회사 Novel organic compounds for organic light-emitting diode and organic light-emitting diode including the same
KR20140114489A (en) * 2013-03-14 2014-09-29 에스에프씨 주식회사 An electroluminescen compound and an electroluminescent device comprising the same
KR20150014286A (en) * 2013-07-29 2015-02-06 덕산하이메탈(주) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
WO2015030469A1 (en) * 2013-08-26 2015-03-05 덕산네오룩스 주식회사 Compound for organic electrical element, organic electrical element using same, and electronic device thereof

Non-Patent Citations (40)

* Cited by examiner, † Cited by third party
Title
"Kirk-Othmer Encyclopedia of Chemical Technology", vol. 18, 1996, pages: 837 - 860
A. G. WERNER; F. LI; K. HARADA; M. PFEIFFER; T. FRITZ; K. LEO, APPL. PHYS. LETT., vol. 82, no. 25, 2003, pages 4495
A. G. WERNER; F. LI; K. HARADA; M. PFEIFFER; T. FRITZ; K. LEO, APPL. PHYS. LETT., vol. 82, no. 25, 23 June 2003 (2003-06-23)
ACHOUR, REDDOUANE; ZNIBER, RACHID, BULLETIN DES SOCIETES CHIMIQUES BELGES, vol. 96, 1987, pages 787 - 92
ANGEW. CHEM. INT. ED, vol. 48, 2009, pages 9240 - 9261
DMYTRO VOLYNIUK ET AL: "Highly Efficient Blue Organic Light-Emitting Diodes Based on Intermolecular Triplet-Singlet Energy Transfer", JOURNAL OF PHYSICAL CHEMISTRY C, vol. 117, no. 44, 7 November 2013 (2013-11-07), pages 22538 - 22544, XP055189137, ISSN: 1932-7447, DOI: 10.1021/jp407397y *
EUR. J. INORG. CHEM., vol. 24, 2005, pages 4976 - 4984
EUR. J. ORG. CHEM., 2007, pages 2147 - 2151
H. GILMAN; D. A. SHIRLEY, J. AM. CHEM. SOC., vol. 66, 1944, pages 888
J. AM. CHEM. SOC., vol. 106, 1984, pages 7150
J. AM. CHEM. SOC., vol. 124, 2002, pages 11900 - 11907
J. CHEM. SOC. [SECTION] C: ORGANIC, vol. 16, 1971, pages 2775 - 7
J. CHEM. SOC., PERKIN TRANS., vol. 2, no. 5, 2002, pages 953 - 957
J. HETEROCYCLIC CHEM, vol. 38, 2001, pages 77 - 87
J. HETEROCYCLIC CHEM, vol. 39, 2002, pages 933 - 941
J. HETEROCYCLIC CHEMISTRY, vol. 34, 1997, pages 891 - 900
J. KERUCKAS ET AL., DYES AND PIGMENTS, vol. 100, 2014, pages 66 - 72
J. KIDO ET AL., CHEM. COMMUN., 2008, pages 5821 - 5823
J. KIDO ET AL., CHEM. MATER., vol. 20, 2008, pages 5951 - 5953
J. ORG. CHEM., vol. 63, 1998, pages 878 - 880
J. ORG. CHEM., vol. 69, 2004, pages 8177 - 8182
J. ORG. CHEM., vol. 73, 2008, pages 2176 - 2181
K. WALZER; B. MAENNIG; M. PFEIFFER; K. LEO, CHEM. SOC. REV., vol. 107, 2007, pages 1233
KAHN ET AL., J. AM. CHEM. SOC., vol. 131, no. 35, 2009, pages 12530 - 12531
KERUCKAS J ET AL: "3,6-Bis(indol-1-yl)-9-phenylcarbazoles as electroactive materials for electrophosphorescent diodes", DYES AND PIGMENTS, vol. 100, 30 July 2013 (2013-07-30), pages 66 - 72, XP028779986, ISSN: 0143-7208, DOI: 10.1016/J.DYEPIG.2013.07.020 *
LI E, DYES AND PIGMENTS, vol. 49, 2001, pages 181 - 186
M. PARK; J.R. BUCK; C.J. RIZZO, TETRAHEDRON, vol. 54, 1998, pages 12707 - 12714
NAN-XING HU ET AL., SYNTH. MET., vol. 111, 2000, pages 421
NATURE, vol. 357, 11 June 1992 (1992-06-11), pages 477 - 479
ORG. LETT., vol. 6, 2004, pages 3501 - 3504
PECIURAITE V ET AL: "Indolyl-substituted carbazole derivatives as amorphous electro-active materials for optoelectronics", JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY, A: CHEMISTRY, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 182, no. 1, 20 August 2006 (2006-08-20), pages 38 - 42, XP028008391, ISSN: 1010-6030, [retrieved on 20060820], DOI: 10.1016/J.JPHOTOCHEM.2006.01.009 *
PFEIFFER ET AL., ORGANIC ELECTRONICS, vol. 4, 2003, pages 89 - 103
PRASAD APPUKKUTTAN ET AL., SYN-LETT, vol. 8, 2003, pages 1204
QIANQIAN LI ET AL: "New indole-containing luminophores: convenient synthesis and aggregation-induced emission enhancement", JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, vol. 22, no. 3, 1 March 2009 (2009-03-01), pages 241 - 246, XP055011969, ISSN: 0894-3230, DOI: 10.1002/poc.1461 *
SYNTHESIS, 2000, pages 442 - 446
TETRAHEDRON LETT., vol. 25, 1984, pages 5363 - 6
TETRAHEDRON. LETT., vol. 47, 2006, pages 6957 - 6960
W. GAO; A. KAHN, J. APPL. PHYS., vol. 94, 2003, pages 359
W. GAO; A. KAHN, J. APPL. PHYS., vol. 94, no. 1, 1 July 2003 (2003-07-01)
W. YANG ET AL., J. MATER. CHEM., vol. 13, 2003, pages 1351

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200011911A (en) * 2018-07-25 2020-02-04 주식회사 엘지화학 Multicyclic compound and organic light emitting device comprising the same
KR102170390B1 (en) 2018-07-25 2020-10-27 주식회사 엘지화학 Multicyclic compound and organic light emitting device comprising the same
US11807632B2 (en) 2018-10-22 2023-11-07 Lg Chem, Ltd. Heterocyclic compound and organic light emitting device comprising the same

Similar Documents

Publication Publication Date Title
JP6730470B2 (en) 4H-imidazo[1,2-a]imidazole for electronics applications
EP3318566B1 (en) Azadibenzofurans for electronic applications
EP3119770B1 (en) New dibenzofurans and dibenzothiophenes
EP2776443B1 (en) 4h-imidazo[1,2-a]imidazoles for electronic applications
EP3075737B1 (en) Benzimidazolo[1,2-a]benzimidazole carrying aryl- or heteroarylnitril groups for organic light emitting diodes
EP3072943B1 (en) Dibenzofuran/carbazole-substituted benzonitriles
EP2872512A1 (en) Benzimidazo[1,2-a]benzimidazole derivatives for electronic applications
EP3150604B1 (en) Benzimidazolo[1,2-a]benzimidazole carrying benzimidazolo[1,2-a]benzimidazolylyl groups, carbazolyl groups, benzofurane groups or benzothiophene groups for organic light emitting diodes
WO2015014791A1 (en) Benzimidazolo[2,1-b][1,3]benzothiazoles for electronic applications
WO2016097983A1 (en) 1-functionalized dibenzofurans and dibenzothiophenes for organic light emitting diodes (oleds)
EP3356368B1 (en) Benzimidazolo[1,2-a]benzimidazole carrying benzimidazolo[1,2-a]benzimidazolyl groups, carbazolyl groups, benzofurane groups or benzothiophene groups for organic light emitting diodes
WO2016016791A1 (en) 2,9-functionalized benzimidazolo[1,2-a]benzimidazoles as hosts for organic light emitting diodes (oleds)
WO2017093958A1 (en) Benzimidazolo[1,2-a]benzimidazole derivatives for organic light emitting diodes
EP3356369B1 (en) Benzimidazolo[1,2-a]benzimidazole carrying triazine groups for organic light emitting diodes
EP3034506A1 (en) 4-functionalized carbazole derivatives for electronic applications
WO2015114102A1 (en) Silyl substituted azadibenzofurans and azadibenzothiophenes
WO2016079667A1 (en) Indole derivatives for electronic applications
EP3070144B1 (en) Seven-membered ring compounds
EP3061759B1 (en) Nitrile substituted dibenzofurans
WO2016067261A1 (en) 5-((benz)imidazol-2-yl)benzimidazo[1,2-a]benzimidazoles for electronic applications
US10968229B2 (en) Seven-membered ring compounds
EP3150606B1 (en) Benzimidazolo[1,2-a]benzimidazoles carrying benzofurane or benzothiophene groups for organic light emitting diodes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15801946

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15801946

Country of ref document: EP

Kind code of ref document: A1