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WO2015114102A1 - Azadibenzofuranes substitués par silyle et azadibenzothiophènes - Google Patents

Azadibenzofuranes substitués par silyle et azadibenzothiophènes Download PDF

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WO2015114102A1
WO2015114102A1 PCT/EP2015/051953 EP2015051953W WO2015114102A1 WO 2015114102 A1 WO2015114102 A1 WO 2015114102A1 EP 2015051953 W EP2015051953 W EP 2015051953W WO 2015114102 A1 WO2015114102 A1 WO 2015114102A1
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group
formula
compound
substituted
compounds
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PCT/EP2015/051953
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Ilona STENGEL
Annemarie Wolleb
Heinz Wolleb
Ute HEINEMEYER
Hideaki Nagashima
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Basf Se
Idemitsu Kosan Co., Ltd.
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Publication of WO2015114102A1 publication Critical patent/WO2015114102A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
    • 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
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • 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
    • 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
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting 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 When used as electron transport material, hole blocking material and/or host material for phosphorescent emitters in electroluminescent devices, the compounds of formula I may provide improved efficiency, stability, manufacturability, or spectral characteristics of electroluminescent de- vices.
  • US20090134784 provides carbazole-containing compounds.
  • the compounds are oligocarbazole-containing compounds having an unsymmetrical structure.
  • the compounds may be substituted by azadibenzofuranyl and are useful as hosts in the emissive layer of organic light emitting devices.
  • ing compou is used as host and exciton blocking material.
  • US20100187984 discloses a process for making an aza-dibenzothiophene compound or an aza-dibenzofuran compound, comprising:
  • Ri and R2 may represent mono, di, tri, or tetra substitutions; wherein Ri is selected from the group consisting of hydrogen, alkyl, aryl, het- eroaryl and halide; and wherein R2 is selected from the group consisting of hydrogen, alkyl, aryl and halide.
  • the aza-dibenzothiophene and aza-dibenzofuran compounds disclosed in US20100187984 are used as hosts in OLEDs.
  • WO2014044722 relates to compounds of formula (I), which are characterized in that they substituted by benzimidazo[1 ,2-a]benzimidazo-5-yl and/or benzimidazo[1 ,2-a]benzimidazo-2,5-ylene groups and in that at least one of the substitu- ents B 1 , B 2 , B 3 , B 4 , B 5 , B 6 , B 7 and B 8 represents N; a process for their production and their use in electronic devices, especially electroluminescent devices.
  • WO2007142038 discloses triphenylsilyl substituted dibenzothiophenes and dibenzofurans for use in OLEDs.
  • WO2009003919A1 relates to an organic light-emitting diode comprising an anode An and a cathode Ka and a light-emitting layer E arranged between the anode An and the cathode Ka, and if appropriate at least one further layer, wherein the light-emitting layer E and/or the at least one further layer comprises at least one compound selected from disilylcarbazoles, disilyl-dibenzofurans, disilyldibenzothiophenes, disilyldibenzophospholes, disilyldibenzothi- ophene S-oxides and disilyldibenzothiophene S,S-dioxides.
  • WO2010079051 relates to silyl and heteroatom substituted compounds, selected from car- apeloles, dibenzofurans, dibenzothiophenes and disilylbenzophospholes and to the application of these compounds in organic-electronic applications, preferably in organic light diodes.
  • WO2010140801 discloses silyl-substituted dibenzothiophen and dibenzofuran heterocycles for use in electronic devices.
  • WO2012102967 relates to compounds comprising an aza-dibenzo moiety and a condensed aromatic moiety having at least three benzene rings are provided.
  • the compounds may comprise an azadibenzofuran, azadibenzothiophene, or azadibenzose- lenophene joined directly or indirectly to an anthracene.
  • the compounds may be used in the electron transport layer of organic light emitting devices.
  • WO2013038650 relates to compounds relates to compounds represented by formula
  • US2013119353 relates to aryl silicon and aryl germanium host materials.
  • host materials containing triphenylene and pyrene fragments are described.
  • WO2011160758 relates to compounds according to formula
  • Ar 1 and Ar 2 may be the same or different and x-x
  • US2012298966 relates to aryl silicon and aryl germanium host materials, which may be used as hosts in the emissive layer of OLEDs.
  • the host materials contain a -Si(Ar)(Ar 1 )-, or -Ge(Ar)(Ar 1 )- group, wherein Ar and Ar 1 contains a group selected from the group consisting of dibenzofuran, dibenzothiophene, azadibenzofuran, azadibenzothiophene, dibenzose- lenophene and azadibenzoselenophene, which are optionally further substituted, and wherein the substitution is optionally fused to at least one benzo ring.
  • WO12153780A1 organic EL material having a meta-phenylene skeleton in the molecular skeleton and an organic electroluminescence device that employs this material.
  • WO13069242A1 relates to compounds represented by formula (1), wherein each of Ci and C2 represents a carbon atom; each of X1-X4 represents N, CH or C(Ri); and L represents a group that is represented by formula (2), -l_i-(A) n , wherein Li represents
  • A represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, an arylthio group, a heteroaryl group, a heteroaryloxy group, an amino group, a silyl group, a diaryloxy phosphinyl group, a divalent group corresponding to one of these groups, a fluoro group or a cyano group.
  • US2013293094A relates to novel asymmetric host compounds containing an electron- transport moiety, a hole-transport moiety, an aromatic spacer, and a triaryl silane group are provided. These compounds are useful materials that can be incorporated into OLED devices. None of the above references disclose triphenylsilyl substituted azadibenzofurans and aza- dibenzothiophenes.
  • organic light emitting devices comprising new electron transport materials to provide improved efficiency, stability, manufacturability, and/or spectral characteristics of electroluminescent devices.
  • 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 electron transport materi- als, hole/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 volt- age of the OLEDs.
  • triphenylsilyl substituted azadibenzofurans and azadibenzothiophenes are found to be suitable for use in organo-electroluminescent devices.
  • said derivatives are suitable electron transporting materials, hole blocking materials or host materials for phos- phorescent emitters with good efficiency and durability.
  • the present invention relates to compounds of formula
  • R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 are independently of each other H, CN, F, a Ci- C25alkyl group, which can optionally be interupted by D; a Cs-Cearyl group, which can optionally be substituted by G; a C2-Csheteroaryl group, which can optionally be substituted
  • o 0, or 1
  • p is 0, or 1
  • a 1 and A 2 are independently of each other a group of formula or
  • Y' and Y" are independently of each other O, or S,
  • B i ' is N, or CR 81 ' ,
  • B2 ' is N, or CR 82' ,
  • B 3' is N, or CR 83' ,
  • B 4' is N, or CR 84' ,
  • B 6' is N, or CR 86' ,
  • B 7' is N, or CR 87' ,
  • B 8' is N, or CR 88' ,
  • R 8 ' , R 82' , R 83' , R 84' , R 85 ' , R 86' , R 87' and R 88' are independently of each other H, CN, F, a Ci- C25alkyl group, which can optionally be interupted by D;
  • R 9 2 a re independently of each other a phenyl group, which may optionally be substituted by one, or more d-Csalkyl groups,
  • R 93 and R 94 are independently of each other H, or a Ci-C2salkyl group
  • E is -OR 69 , -SR 69 , -NR 65 R 66 , -COR 68 , -COOR 67 , -CONR 65 R 66 , -CN, or F,
  • G is E, or a C-i-C-isalkyl group, a C6-C2 4 aryl group, a C6-C2 4 aryl group, which is substituted by F, Ci-Ci8alkyl, or Ci-Cisalkyl which is interrupted by O; a C2-C3oheteroaryl group, or a C2-C3oheteroaryl group, which is substituted by F, C-i-C-isalkyl, or C-i-C-isalkyl which is interrupted by O;
  • R 63 and R 64 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 -O-;
  • R 65 and R 66 are independently of each other a C6-Cisaryl group; a C6-Cisaryl which is sub- stituted by C-i-C-isalkyl, or Ci-Cisalkoxy; a Ci-Cisalkyl group; or a C-i-C-isalkyl group, which is interrupted by -0-; or
  • R 65 and R 66 together form a five or six membered ring
  • R 67 is a C6-Ci8aryl group; a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, or Ci- Ciealkoxy; a Ci-Cisalkyl group; or a C-i-C-isalkyl group, which is interrupted by -O-,
  • R 68 is H; a C6-Cisaryl group; a C6-Cisaryl group, which is substituted by C-i-C-isalkyl, or Ci- Cisalkoxy; a Ci-Cisalkyl group; or a Ci-Cisalkyl group, which is interrupted by -O-,
  • R 69 is a C6-Ciearyl; a C6-Cisaryl, which is substituted by Ci-Cisalkyl, or Ci-Cisalkoxy; a Ci- Ciealkyl group; or a Ci-Cisalkoxy; a Ci- Ciealkyl group; or
  • R 70 and R 71 are independently of each other a Ci-Cisalkyl group, a C6-Cisaryl group, or a Ce-Cisaryl group, which is substituted by Ci-Cisalkyl, and
  • R 72 is a Ci-Cisalkyl group, a C6-Cisaryl group, or a C6-Cisaryl group, which is substituted by Ci-Cisalkyl, with the provisos that
  • At least one of the substituents B , B 2 , B 3 , B 4 , B 5 , B 6 , B 7 and B 8 represents N;
  • At least one of the substituents R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 represents a group of formula (II).
  • Certain compounds of the present invention show, when used as host and/or hole blocker in combination with phosphorescent emitters, excellent power efficiencies, in particular.
  • Electroluminescent (EL) devices comprising the compounds of the present invention exhibit reduced drive voltage while maintaining excellent luminance properties. Furthermore, the colour and EQE can be improved and the roll-off may be reduced by use of the inventive compounds.
  • the compounds of the present invention may be used for electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaics), switching elements, such as organic transistors, for example, organic FETs and organic TFTs, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers and electrolumi- nescent devices, such as, for example, organic light-emitting diodes (OLEDs).
  • organic solar cells organic photovoltaics
  • switching elements such as organic transistors, for example, organic FETs and organic TFTs, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers and electrolumi- nescent devices, such as, for example, organic light-emitting diodes (OLEDs).
  • a further subject of the present invention is directed to an electronic device, comprising a compound according to the present invention.
  • the electronic device is preferably an electroluminescent device.
  • the compounds of formula I can in principal be used in any layer of an EL device, but are preferably used as host, electron transport and/or hole blocking material.
  • a further subject of the present invention is directed to an electron transport layer and/or a hole blocking 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.
  • D is preferably -CO-, -COO-, -S-, -SO-, -SO2-, -0-, -N R 65 -, wherein R 65 is Ci-Ci 8 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl, or sec-butyl, or C6-Ci 4 aryl, such as phenyl, tolyl, naphthyl, or biphenylyl, or C2-C3oheteroaryl, such as, for example,
  • E is preferably -OR 69 ; -SR 69 ; -N RssRss; -COR 68 ; -COOR 67 ; -CON RssRss; or -CN; wherein R 65 , R 67 , R 68 and R 69 are independently of each other Ci-Cisalkyl, such as methyl, ethyl, n- propyl, iso-propyl, n-butyl, isobutyl, tert-butyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C6- Ci 4 aryl, such as phenyl, tolyl, naphthyl, or biphenylyl.
  • Ci-Cisalkyl such as methyl, ethyl, n- propyl, iso-propyl, n-butyl, isobutyl, tert-butyl,
  • At least one of the substituents B ' , B 2' , B 3' , B 4' , B 5' , B 6' , B 7' and B 8' represents N; not more than two of the groups B 1 ' , B 2' , B 3 ' and B 4' represent N; and not more than two of the groups B 5' , B 6' , B 7' and B 8' represent N.
  • the number of nitrogen atoms in the basic skeleton of the compound of formula ( ⁇ ) is preferably 1 (B 6 is CR 86 and B 4 is CR 84 ), or 2 (B 6 is N and B 4 is CR 84 , or B 6 is CR 86 and B 4 is N). If B 4 is N, B 6 is preferably CH. If B 6 is N, B 4 is preferably CH. I the present invention is directed to compounds of formula
  • the present invention is directed to compounds of formula (la), (lb), (lc), (Id), (le), or (If), wherein Y is S.
  • the present invention is directed to compounds of formula (la), (lb), (lc), (Id), (le), or (If), wherein Y is O.
  • R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 may be a C 5 -C 6 aryl group, which can optionally be substituted by G; or a C2-Csheteroaryl group, which can optionally be substituted by G.
  • the C5-C6aryl group, which optionally can be substituted by G, is typically phenyl, 4- methylphenyl, or 4-methoxyphenyl.
  • the C2-Csheteroaryl group which optionally can be substituted by G, represent an aromatic ring with five to seven ring atoms, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically, furyl, furfuryl, 2H-pyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, or indazol- yl, which can be unsubstituted or substituted.
  • the C5-C6aryl and C2-Csheteroaryl groups may be substituted by G.
  • G has the same preferences as E, or is Ci-Cisalkyl, such as methyl, ethyl, n-propyl, iso- propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or is Ci-Ci8perfluoroalkyl, such, for example, -CF3.
  • Ci-Cisalkyl such as methyl, ethyl, n-propyl, iso- propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl
  • Ci-Ci8perfluoroalkyl such, for example, -CF3.
  • R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 are independently of each other H, CN, F, a Ci- C25alkyl group, which can optionally be interupted by D; a Cs-Cearyl group, which can optionally be substituted by G, or a group of formula (II).
  • the present invention is directed to compounds of formula (la), wherein R 83 is a group of formula (II) and
  • R 87 is a group of formula (II), H, or Ci-C2salkyl
  • R 83 is a group of formula (II), H, or Ci-C2salkyl
  • R 85 is a group of formula (II), H, or Ci-C 25 alkyl; compounds of formula (Ic), wherein R 83 is a group of formula (II) and
  • R 87 is a group of formula (II), H, or Ci-C25alkyl
  • R 83 is a group of formula (II), H, or Ci-C25alkyl
  • R 86 is a group of formula (II), H, or Ci-C25alkyl
  • R 83 is a group of formula (II), H, or Ci-C2salkyl
  • R 85 and R 87 are a group of formula (II), H, or Ci-C 25 alkyl;
  • R 83 and R 87 are a group of formula (II), H, or Ci-C 25 alkyl;
  • R 83 and R 85 are a group of formula (II), H, or Ci-C 2 5alkyl;
  • R 83 and R 87 are a group of formula (II), H, or Ci-C 25 alkyl;
  • R 8 and R 87 are a group of formula (II), H, or Ci-C 2 5alkyl; or
  • R 81 and R 83 are a group of formula (II), H, or Ci-C2salkyl.
  • the compounds of formula (I) especially (la), (lb), (Ic), (Id), (le), or (If), at least one group of formula (II) is present.
  • R 83 is a group of formula (II) and R 85 and R 87 are H.
  • compounds of formula (If) compounds are more preferred, wherein R 83 and R 87 are a group of formula (II) and R 81 is H; or wherein R 81 and R 87 are a group of formula (II) and R 83 is H.
  • o 0, or 1
  • p is 0, or 1 ;
  • R 89 is H, a group of formula
  • R 89 is H.
  • a 1 and A 2 are independently of each other a
  • the group of formula (II) is more preferably a group of formula
  • Examples of preferred compounds are compounds C-1 to C-12, C-49 and C-50 as shown i
  • Ci-C25alkyl (Ci-Cisalkyl) is typically linear or branched, where possible. Examples are me- thyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3- pentyl, 2,2-dimethylpropyl, 1 ,1 ,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1 ,1 ,3,3,5,5- hexa methyl hexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyl- heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl,
  • d-Csalkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2- ethylhexyl.
  • Ci-C4alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl.
  • Ci-C25alkoxy groups are straight-chain or branched alkoxy groups, e.g.
  • Examples of d-Csalkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2- dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1 ,1 ,3,3-tetramethylbutoxy and 2- ethylhexyloxy, preferably Ci-C4alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy.
  • C6-C2 4 aryl which optionally can be substituted, is typically phenyl, 4- methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, or anthryl, which may be unsubstituted or substituted.
  • Phenyl, 1-naphthyl and 2-naphthyl are examples of a C6-Cioaryl group.
  • C2-C3oheteroaryl represents a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically a heterocyclic group with five to 30 atoms having at least six conjugated ⁇ -electrons such as thienyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzo- furanyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl,
  • Benzimidazo[1 ,2- a]benzimidazo-5-yl, benzimidazo[1 ,2-a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are examples of a C2-Ci 4 heteroaryl group.
  • substituted by G means that one, or more, especially one to three substitu- ents G might be present. If a substituent occurs more than one time in a group, it can be different in each occurrence.
  • the aforementioned groups may be 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.
  • Ci-Cisalkyl interrupted by one or more units D is, for example, (CH2CH 2 0)i-9-R x , where R x is H or Ci-Cioalkyl or C2-Cioalkanoyl (e.g.
  • R y is Ci-Ci 8 alkyl, C 5 -Ci 2 cycloalkyl, phe- nyl, 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 z is H, Ci-Cisalkyl, (CH2CH20)i-9-R x , and R x embraces the definitions indicated above;
  • the present invention is also directed to a process for the production of a compound of
  • a solvent such as, for example, dimethylformamide
  • elevated temperature such as, for example, at 80 to 153 °C, for 3 to 72 hours, to obtain a
  • Ci-C25alkyl group which can optionally be interupted by D;
  • Cioalkyl group and Y 2 is a C2-Cioalkylene group, Y 13 and Y 14 are independently of each other hydrogen, or a Ci-Cioalkyl group;
  • R 83" is a C5-C6aryl group, which can optionally be substituted by G; a C 2 -Csheteroaryl group, which can optionally be substituted by G; or a group of formula
  • R 87 is H, a Ci-C25alkyl group, which can optionally be interupted by D; a group of formula (II), and
  • the organic solvent is an aromatic hydrocarbon or a usual polar organic solvent, such as, for example benzene, toluene, xylene, tetrahydrofurane (TH F), N ,N-dimethyformamide
  • DM F dimethoxyethane
  • DME dimethoxyethane
  • dioxane or mixtures thereof, or mixtures of an aromatic hydrocarbon and an alcohol, such as, for example, toluene/ethanol.
  • the organic solvent may be used in admixture with water.
  • Suitable palladium catalysts are, for example, Pd(PPh 3 )4, Pd(OAc) 2 , Pd(PPh 3 )2CI 2 ,
  • a palladi- um/ligand system comprising selected from the group con
  • Suitable bases are, for example, alkali and alkaline earth metal hydroxides, carboxylates, carbonates, fluorides and phosphates such as sodium and potassium hydroxide, acetate, carbonate, fluoride and phosphate or also metal alcoholates. It is also possible to use a mixture of bases.
  • the reaction is preferably carried out in the presence of an aqueous base, such as, for example, an alkali metal hydroxide or carbonate such as NaOH, KOH, Na2C03, K2CO3 and CS2CO3, more preferably an aqueous K2CO3 solution is chosen.
  • Organic bases such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example tetrabutylammoniumbromide (TBAB), can promote the activity of the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein).
  • phase transfer catalysts such as, for example tetrabutylammoniumbromide (TBAB)
  • reaction temperature is chosen in the range of from 40 to 180°C, preferably under reflux conditions.
  • reaction time is chosen in the range of from 1 to 80 hours, more preferably from 20 to 24 hours.
  • 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 (II) 2,8 positions (dibenzofuran and dibenzothiophene) or 3,6 positions (carbazole).
  • Optionally substituted dibenzofurans, dibenzothiophenes and carbazoles can be dibromin- ated in the 2,8 positions (dibenzofuran and dibenzothiophene) or 3,6 positions (carbazole) with bromine or NBS in glacial acetic acid or in chloroform.
  • the bromination with Br2 can be effected in glacial acetic acid or chloroform at low temperatures, e.g. 0°C.
  • Dibenzofuran (dibenzothiophene) 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.
  • Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles 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,
  • a catalyst such as, for example, [1 ,1'- bis(diphenylphosphino)ferrocene]dichloropalladium(ll), complex (Pd(CI)2(dppf)
  • a base such as, for example, potassium acetate
  • a solvent such as, for example, dimethyl formamide, dimethyl sulfoxide, diox
  • Y 1 is independently in each occurrence a Ci-Ci8alkylgroup and Y 2 is independently in each occurrence a C2-Cioalkylene group, such as -CY 3 Y 4 -CY 5 Y 6 -, or -CY 7 Y 8 -CY 9 Y 10 - CY Y 12 -, wherein Y 3 , Y 4 , Ys, ⁇ ⁇ , ⁇ ?, ⁇ ⁇ _ ⁇ ⁇ .
  • ⁇ and Y ⁇ are independently of each other hydrogen, or a Ci-Ci8alkylgroup, especially -C(CH3)2C(CH3)2-, - C(CH3)2CH 2 C(CH 3 )2-, or -CH 2 C(CH 3 )2CH 2 -, and Y 13 and Y 14 are independently of each other hydrogen, or a Ci-Ci8alkylgroup.
  • Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and car- apeloles 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 by reaction with boronic esters, such as, for example, B(isopropoxy)3,
  • Diboronic acid or diboronate group containing dibenzofurans, dibenzothiophenes and carbazoles can also be prepared by reacting dibenzofurans, dibenzothiophenes and carbazoles with lithium amides, such as, for example, lithium diisopropylamide (LDA) followed by esters such as, for example, B(isopropoxy)3, B(methoxy)3, or
  • lithium amides such as, for example, lithium diisopropylamide (LDA) followed by esters such as, for example, B(isopropoxy)3, B(methoxy)3, or
  • the Suzuki reaction is carried out in the presence of an organic solvent, such as an aromatic hydrocarbon or a usual polar organic solvent, such as benzene, toluene, xylene, tetrahydrofurane, or dioxane, or mixtures thereof, most preferred toluene.
  • an organic solvent such as an aromatic hydrocarbon or a usual polar organic solvent, such as benzene, toluene, xylene, tetrahydrofurane, or dioxane, or mixtures thereof, most preferred toluene.
  • the amount of the solvent is chosen in the range of from 1 to 10 I per mol of boronic acid derivative.
  • the reaction is carried out under an inert atmosphere such as nitrogen, or argon.
  • an aqueous base such as an alkali metal hydroxide or carbonate such as NaOH, KOH, Na2C03, K2CO3, Cs2C03 and the like, preferably an aqueous K2CO3 solution is chosen.
  • the molar ratio of the base to boronic acid or boronic ester derivative is chosen in the range of from 0.5: 1 to 50:1 , very especially 1 :1.
  • the reaction temperature is chosen in the range of from 40 to 180°C, preferably under reflux conditions.
  • the reaction time is chosen in the range of from 1 to 80 hours, more preferably from 20 to 72 hours.
  • a usual catalyst for coupling reactions or for polycondensation reactions is used, preferably Pd-based, which is described in WO2007/101820.
  • the palladium compound is added in a ratio of from 1 :10000 to 1 :50, preferably from 1 :5000 to 1 :200, based on the number of bonds to be closed. Preference is given, for example, to the use of palla- dium(ll) salts such as PdAc2 or Pd2dba3 d from the
  • the ligand is added in a ratio of from 1 : 1 to 1 :10, based on Pd.
  • the catalyst is added as in solution or suspension.
  • an appropriate organic solvent such as the ones described above, preferably benzene, toluene, xylene, THF, dioxane, more preferably toluene, or mixtures thereof, is used.
  • the amount of solvent usually is chosen in the range of from 1 to 10 I per mol of boronic acid derivative.
  • Organic bases such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Lead- beater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein).
  • phase transfer catalysts such as, for example TBAB
  • Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252 and G. A. Molander und B. Canturk, Angew. Chem. , 121 (2009) 9404 - 9425.
  • JP2011084531 describes, for example, the synthesis of benzofuro[3,2-b]pyridine in two steps starting from 2-bromopyridin-3-ol using a base catalyzed cyclisation. The brominated ation with bromine in the presence of silver sulfate.
  • US2010/0187984 describes, for example, the synthesis of 3,6-dichloro-benzofuro[2,3- b]pyridine in three steps starting from 2-amino-5-chloropyridine using a cyclisation of a dia- zoniumion salt.
  • JP2002284862 describes the syntheses of 2,7-dibromo-furo[3,2-b:4,5-b]dipyridine starting from 2-(3-amino-5-bromo-2-pyridyl)-5-bromo-pyridin-3-amine using an acid catalyzed cyclisation of a diazoniumion salt.
  • the synthesis of the starting material is described by Y. Fort, T
  • halogen/metal exchange is done with nBuLi/THF at -78°C, or tBuLi/THF at -78°C.
  • WO2010/079051 where the synthesis conditions are described in more detail.
  • the inventive organic light-emitting diode thus generally has the following structure:
  • the inventive OLED may, for example - in a preferred embodiment - be formed from the following layers:
  • Layer sequences different than the aforementioned structure are also possible, and are known to those skilled in the art.
  • the OLED does not have all of the layers mentioned; for example, an OLED with layers (a) (anode), (e) (light-emitting layer) and (i) (cathode) is likewise suitable, in which case the functions of the layers (c) (hole transport layer) and (f) (blocking layer for holes/excitons) and (g) (electron transport layer) are assumed by the adjacent layers.
  • OLEDs which have layers (a), (c), (e) and (i), or layers (a), (e), (f), (g) and (i), are likewise suitable.
  • the OLEDs may have a blocking layer for electrons/excitons (d) between the hole transport layer (c) and the Light- emitting layer (e).
  • a plurality of the aforementioned functions are combined in one layer and are assumed, for example, by a single material present in this layer.
  • a material used in the hole transport layer, in one 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. 1 11 (2000) 421 (in- dolocarbazoles), WO2010002850 (substituted phenylamine compounds) and
  • WO2012/16601 in particular the hole transport materials mentioned on pages 16 and 17 of WO2012/16601. Combination of different hole transport material may be used.
  • Customarily used hole-transporting molecules are selected from the group consisting of
  • 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 copol- ymers 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- diy
  • 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- aazatriphe mentioned as host below, such as, for
  • (SH-1 ) may be used as hole transport material and exciton blocker material.
  • 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,
  • bene complex is lr(DPBIC)3 with the formula: (HTM-1).
  • Another exa carbene complex is lr(ABIC)3 with the
  • the hole-transporting layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device.
  • Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, 2003, 359 (p-doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No.
  • mixtures may, for example, be the following mixtures: mixtures of the abovementioned hole transport materials with at least one metal oxide, for example M0O2, M0O3, WO x , ReCb and/or V2O5, preferably M0O3 and/or ReCb, more preferably 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
  • the hole transport layer comprises from 0.1 to 10 wt % of M0O3 and 90 to 99.9 wt % carbene com- plex, 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, W02006/056418 A2, WO2005/113704, WO2007/115970, WO2007/115981 , WO2008/000727 and WO2014147134. 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.
  • suitable carbene complexes are compounds 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 2006/1 15301 A1 , WO 2006/067074 A1 , WO 2006/056418, WO 2006121811 A1 , WO 2007095118 A2, WO 2007/1 15970, WO 2007/115981 ,
  • metal complexes are the commercially available metal complexes tris(2- phenylpyridine)iridium(lll), iridium(lll) tris(2-(4-tolyl)pyridinato-N,C 2 '), bis(2- phenylpyridine)(acetylacetonato)iridium(lll), iridium(lll) tris(l-phenylisoquinoline), iridium(lll) bis(2,2'-benzothienyl)pyridinato-N,C 3 ')(acetylacetonate), tris(2-phenylquinoline)iridium(lll), iridium(lll) bis(2-(4,6-difluorophenyl)pyridinato-N,C 2 )picolinate, iridium(lll) bis(1- phenylisoquinoline)(acetylacetonate), bis(2-phenylquinoline)(acett
  • Preferred phosphorescence emitters are carbine complexes. Suitable phosphorescent blue emitters are specified in the following publications: WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981 , WO2008/000727, WO2009050281 , WO2009050290, WO2011051404, US201 1/057559 WO2011/073149, WO2012/121936A2,
  • the light emitting layer (e) comprises at least one carbine complex as phosphorescence emitter.
  • Suitable carbine complexes are, for example, compounds of the
  • M is a metal atom selected from the group consisting of Co, Rh, Ir, Nb, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re, Cu, Ag and Au in any oxidation state possible for the respective metal atom;
  • Carbene is a carbene ligand which may be uncharged or monoanionic and monodentate, bidentate or tridentate, with the carbene ligand also being able to be a biscarbene or triscarbene ligand;
  • L is a monoanionic or dianionic ligand, which may be monodentate or bidentate
  • K is an uncharged monodentate or bidentate ligand selected from the group consisting of phosphines; phosphonates and derivatives thereof, arsenates and derivatives thereof; phosphites; CO; pyridines; nitriles and conjugated dienes which form a ⁇ complex with M 1
  • n1 is the number of carbene ligands, where n1 is at least 1 and when n1 > 1 the carbene ligands in the complex of the formula I can be identical or different;
  • nl is the number of ligands L, where ml can be 0 or ⁇ 1 and when ml > 1 the ligands L can be identical or different;
  • o is the number of ligands K, where o can be 0 or ⁇ 1 and when o > 1 the ligands K can be identical or different;
  • n1 + ml + o is dependent on the oxidation state and coordination number of the metal atom and on the denticity of the ligands carbene, L and K and also on the charge on the ligands, carbene and L, with the proviso that n1 is at least 1.
  • M, n1 , Y, A 2 ', A3', A A ⁇ , Rsi , R52, RSS, R54, RSS, Rse, RS?, RSS, R59, ⁇ , L, ml and o1 are each defined as follows:
  • M is Ir, or Pt
  • n1 is an integer selected from 1 , 2 and 3,
  • Y is NRs i , 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,
  • R5s are eac h, jf A 2 ', A 3 ', A 4 ' and/or A 5 ' is N, a free electron pair, or, if A 2 ', A 3' , A 4' and/or A 5' is C, each independently hydrogen, linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 1 to 20 carbon atoms, cycloalkyi radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one 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 accept
  • R 53 and R 54 together with A 3' and A 4' form an optionally substituted, unsaturated ring op- tionally 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 unsubstituted aryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms, group with donor or acceptor action, or
  • R 56 and R 57 , R 57 and R 58 or R 58 and R 59 together with the carbon atoms to which they are bonded, form a saturated, unsaturated or aromatic, optionally substituted ring optionally interrupted by at least one heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms, and/or
  • R 55 and R 56 together form a saturated or unsaturated, linear or branched bridge optionally comprising heteroatoms, an aromatic unit, heteroaromatic unit and/or functional groups and having a total of 1 to 30 carbon atoms and/or heteroatoms, to which is optional- ly 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 WO201 1/073149.
  • the compounds of the present invention can also be used as host for phosphorescent green emitters.
  • Suitable phosphorescent green emitters are, for example, specified in the following publications: WO2006014599, WO20080220265, WO2009073245, WO2010027583, WO2010028151 , US20110227049, WO201 1090535, WO2012/08881 , WO20100056669, WO20100118029, WO20100244004, WO201 1109042, WO2012166608, US20120292600, EP2551933A1 ; US6687266, US20070190359, US20070190359, US20060008670; WO2006098460, US20110210316, WO 2012053627; US6921915, US20090039776; 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 especially a compound of the formula la, lb, lc, Id, le, or If is used as matrix material.
  • Examples of preferred compounds of formula I are compounds C-1 to C-50.
  • 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.
  • 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 2005/1 13704 WO 2007/1 15970
  • WO 2007/1 15981 WO 2008/000727
  • WO2014147134 WO2014147134
  • 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.
  • WO20081401 14 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 poly- mers of monomers 1-1 to 1-9, preferably of 1-3, 1-7, and 1-9, WO2008029729 the (polymers 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, JP2009182298 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 1-1-1
  • 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, WO2014/009317 (in particular compound A-24), WO2014/044722 and WO2014/072320 (in particular page 25 to 29 of WO2014/072320).
  • the above-mentioned small molecules are more preferred than the above-mentioned (co)polymers of the small molecules.
  • X is NR, S, O or PR
  • R is aryl, heteroaryl, alkyl, cycloalkyl, or heterocycloalkyi;
  • R221 R222 anc are independently of each other aryl, heteroaryl, alkyl, cycloalkyl, 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 R208 i R209 i R2io_ R2i i _ R212_ R213_ R214 u nc
  • R215 are independently of each other aryl, heteroaryl, alkyl,
  • Additional host materials on basis of dibenzofurane are, for example, described in US2009066226, EP1885818B1 , EP1970976, EP1998388 and EP2034538. Examples of particularly preferred host materials are shown below:
  • T is O, or S, preferably O. If T occurs more than one time in a molecule, all groups T have the same meaning.
  • Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer.
  • the hole blocking layer may be disposed between the emitting layer (e) and electron transport layer (g), to block holes from leaving layer (e) in the direction of electron transport layer (g).
  • Blocking layers may also be used to block excitons from diffusing out of the emissive layer.
  • At least one compound of the formula I especially a compound of the formula la, lb, lc, Id, le, or If is used as hole/exciton blocking material.
  • Examples of preferred compounds of formula I are compounds C-1 to C-50.
  • Additional hole blocker materials typically used in OLEDs are 2,6-bis(N-carbazolyl)pyridine (mCPy), 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline (bathocuproin, (BCP)), bis(2- methyl-8-quinolinato)-4-phenylphenylato)aluminum(lll) (BAIq), phenothiazine S,S-dioxide derivates and 1 ,3,5-tris(N-phenyl-2-benzylimidazolyl)benzene) (TPBI), TPBI also being suitable as electron-transport material.
  • mCPy 2,6-bis(N-carbazolyl)pyridine
  • BCP 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline
  • BAIq bis(2- methyl-8-quinolinato)-4-phenylphenylato)aluminum(lll)
  • BAIq bis(
  • hole blockers and/or electron conductor materials are 2,2',2"-(1 ,3,5-benzenetriyl)tris(1-phenyl-1-H-benzimidazole), 2-(4- biphenylyl)-5-(4-tert-butylphenyl)-1 ,3,4-oxadiazole, 8-hydroxyquinolinolatolithium, 4- (naphthalen-1-yl)-3,5-diphenyl-4H-1 ,2,4-triazole, 1 ,3-bis[2-(2,2'-bipyridin-6-yl)-1 ,3,4- oxadiazo-5-yl] benzene, 4,7-diphenyl-1 ,10-phenanthroline, 3-(4-biphenylyl)-4-phenyl-5-tert- butylphenyl-1 ,2,4-triazole, 6,6'-bis[5-(biphenyl-4-yl)-1 ,3,4
  • disilyl compounds selected from the group consisting of disilylcarbazoles, disilylbenzofurans, dis- ilylbenzothiophenes, disilylbenzophospholes, disilylbenzothiophene S-oxides and dis- ilylbenzothiophene S,S-dioxides, as specified, for example, in PCT applications
  • 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 compound of the formula I especially a compound of the formula la, lb, lc, Id, le, or If is used as electron transport material.
  • Examples of preferred compounds of formula I are compounds C-1 to C-50.
  • 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 WO201 1/157779.
  • the electron-transport layer may also be electronically doped in order to improve the transport properties of the materials used, in order firstly to make the layer thicknesses more generous (avoidance of pinholes/short circuits) and in order secondly to minimize the operating voltage of the device.
  • Electronic doping is known to those skilled in the art and is disclosed, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1 , 1 July 2003 (p- doped organic layers); A. G. Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No.
  • n-Doping is achieved by the addition of reducing materials.
  • mixtures may, for example, be mixtures of the abovementioned electron transport materials with alkali/alkaline earth metals or alkali/alkaline earth metal salts, for example Li, Cs, Ca, Sr, CS2CO3, with alkali metal complexes, for example 8-hydroxyquinolatolithium (Liq), and with Y, Ce, Sm, Gd, Tb, Er, Tm, Yb, Li 3 N, Rb 2 C0 3 , dipotassium phthalate, W(hpp) 4 from
  • EP1786050 or with compounds described in EP1837926B1 , EP1837927, EP2246862 and WO2010132236.
  • the electron-transport layer comprises at least one compound of the general formula (VII)
  • R 32 and R 33 are each independently F, d-Cs-alkyl, or C6-Ci 4 -aryl, which is optionally substituted by one or more d-Cs-alkyl groups, or two R 32 and/or R 33 substituents together form a fused benzene ring which is optionally substituted by one or more d-Cs-alkyl groups;
  • a and b are each independently 0, or 1 , 2 or 3,
  • M 1 is an alkaline metal atom or alkaline earth metal atom
  • p is 1 when M 1 is an alkali metal atom, p is 2 when M 1 is an earth alkali metal atom.
  • a very particularly preferred compound of the formula (VII) is (Liq), which may be present as a single species, or in other forms such as Li g Q g in which g is an integer, for example LkQe- Q is an 8-hydroxyquinolate ligand or an 8-hydroxyquinolate derivative.
  • the electron-transport layer comprises at least one compound of the formul
  • R37 are each independently H, Ci-Cie-alkyl, Ci-Cie- 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;
  • E is -OR 44 ; -SR 44 ; -NR 4 oR 4i ; -COR 43 ; -COOR 42 ; -CONR 40 R 4i ; -CN; or F;
  • G is E, Ci-Cie-alkyl, Ci-Cie-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-Cie-aryl; C6-Cis-aryl which is substituted by Ci-Cie-alkyl or Ci-Cis-alkoxy; Ci-Cie-alkyl; or Ci-Cie-alkyl which is interrupted by -0-; R 40 and R 41 are each independently C6-Cie-aryl; C6-Cis-aryl which is substituted by C1-C18- alkyl or Ci-Cis-alkoxy; Ci-Cie-alkyl; or Ci-Cie-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-Cie-aryl; C6-Cis-aryl which is substituted by C1-C18- alkyl or Ci-Cis-alkoxy; Ci-Cie-alkyl; or Ci-Cie-alkyl which is interrupted by -0-,
  • R 44 is C6-Ci8-aryl; C6-Cis-aryl which is substituted by Ci-Cie-alkyl or Ci-Cis-alkoxy; C1-C18- alkyl; or Ci-Cie-alkyl which is interrupted by -0-,
  • R 45 and R 46 are each independently Ci-Cie-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cie-alkyl,
  • R 47 is Ci-Cie-alkyl, C6-Cis-aryl or C6-Cis-aryl which is substituted by Ci-Cie-alkyl.
  • Preferred compounds of the formula (VIII) are compounds of the formula (Villa)
  • the electron-transport layer comprises a compound Liq and a compound ETM-2.
  • the electron-transport layer comprises the compound of the formula (VII) in an amount of 99 to 1 % by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, where the amount of the compounds of the formulae (VII) and the amount of the compounds of the formulae (VIII) adds up to a total of 100% by weight.
  • the electron-transport layer comprises Liq in an amount of 99 to 1 % by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, where the amount of Liq and the amount of the dibenzofuran compound(s), especially ETM-1 , adds up to a total of 100% by weight.
  • the electron-transport layer comprises at least one phenanthro- line derivative and/or pyridine derivative.
  • the electron-transport layer comprises at least one phe- nanthroline derivative and/or pyridine derivative and at least one alkali metal hydroxyquino- late complex.
  • the electron-transport layer comprises at least one of the dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described in WO2011/157790, especially ETM-1.
  • the electron-transport layer comprises a compound described in WO2012/11 1462, WO2012/147397, WO2012014621 , such as, for example, a
  • the electron injection layer may be any layer that improves the injection of electrons into an adjacent organic layer.
  • Lithium-comprising organometallic compounds such as 8- hydroxyquinolatolithium (Liq), CsF, NaF, KF, CS2CO3 or LiF may be applied between the electron transport layer (g) and the cathode (i) as an electron injection layer (h) in order to reduce the operating voltage.
  • the cathode (i) is an electrode which serves to introduce electrons or negative charge carriers.
  • the cathode may be any metal or nonmetal which has a lower work function than the anode. Suitable materials for the cathode are selected from the group consisting of alkali metals of group 1 , for example Li, Cs, alkaline earth metals of group 2, metals of group 12 of the Periodic Table of the Elements, comprising the rare earth metals and the lanthanides and actinides.
  • metals such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof, may be used.
  • the different layers, if present have the following thicknesses:
  • anode 500 to 5000 A (angstrom), preferably 1000 to 2000 A;
  • Suitable materials for the individual layers are known to those skilled in the art and are disclosed, for example, in WO 00/70655.
  • the 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 techniques, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others.
  • the organic layers of the OLED can be applied from solutions or dispersions in suitable solvents, employing coating techniques known to those skilled in the art.
  • the compounds of the formula I in at least one layer of the OLED preferably in the light-emitting layer (preferably as a matrix material), charge transport layer and/or in the charge/exciton blocking layer makes it possible to obtain OLEDs with high efficiency and with low use and operating voltage.
  • the OLEDs obtained by the use of the compounds of the formula I additionally have high lifetimes.
  • the efficiency of the OLEDs can additionally be improved by optimizing the other layers of the OLEDs.
  • high-efficiency cathodes such as Ca or Ba, if appropriate in combination with an intermedi- ate 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; illumi- nation 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
  • illumi- nation units keyboards
  • items of clothing furniture
  • wallpaper comprising at least one inventive organic light-emitting diode or at least one inventive light-emitting layer.
  • BB-1 (3-bromophenyl)triphenylsilane
  • BB-3 (1 g, 3.7 mmol) is dissolved in acetonitrile (40 ml) under nitrogen. Iodine monochlo- ride (0.2 ml, 3.7 mmol, 0.6 g) is added dropwise. Stirring is continued at room temperature for 45 min (until TLC shows complete consumption of the starting material).
  • the reaction mixture is poured into water (150 ml) and is extracted with methyl ferf-butyl ether (MTBE) (3 x 100 ml). The organic layer is washed with 10% aqueous Na2S203 solution (100 ml) and brine (100 ml). It is dried over Na2S0 4 and the solvent is removed in vacuo.
  • the crude product is recrystallized from 2-propanol.
  • BB-4 (0.83 g, 3.2 mmol, 87%) is obtained as white crystalline solid.
  • BB-8 (500 mg, 1.9 mmol) is dissolved in ethanol (20 ml) under argon.
  • Formamidine hydrochloride (171 mg, 2.1 mmol) is added at room temperature with stirring.
  • An aqueous solution of KOH (108 mg, 1.9 mmol, in 8 ml) is added.
  • Stirring is continued for 30 min and another portion of KOH in water (108 mg, 1.9 mmol, in 8 ml) is added. Stirring is continued at room temperature until the GC shows complete consumption of the starting material and the intermediate (1 h).
  • the reaction mixture is poured into water (50 ml) and it is extracted with ethyl acetate (2 x 100 ml). The combined organic layers are washed with water (50 ml) and brine (50 ml). It was dried over Na2S0 4 and the solvent is removed in vacuo.
  • the crude product is purified by silica column chromatography using heptane/ethyl acetate (4: 1 ) as eluent. BB-9 (340 mg, 1.4 mmol, 71 %) is obtained as white solid.
  • BB-10 8-bromo-2-tert-butylbenzofuro[3,2-d]pyrimidine (BB-10): The compound is synthesized using the method described for BB-5 applying BB-4 (1 .90 g, 7.34 mmol), tert- butylformamidine hydrochloride (1 .10 g, 8.07 mmol), DBU (2.6 ml, 16.14 mmol, 2.46 g) and DMF (130 ml). BB-10 (2.06 g, 6.75 mmol, 92%) is obtained as white solid.
  • BB-12 3-triphenylsilylbenzamidine hydrochloride
  • BB-15 (8-bromodibenzofuran-2-yl)triphenylsilane
  • BB-16 (8-cyanodibenzofuran-2-yl)triphenylsilane
  • BB-15 (8.6 g, 17 mmol) and CuCN (2.29 g, 25.5 mmol) are suspended in DMF (170 ml) under argon and heated up to 145 °C with stirring. TLC shows complete consumption of the starting material after 48 h.
  • the reaction mixture is diluted with aqueous 1 % NaCN solution (255 ml) and stirring is continued at 100 °C for 1 h. It is cooled to room temperature, the mixture is diluted with ethyl acetate (100 ml) and the layers are separated. The aqueous layer is extracted with ethyl acetate.
  • BB-17 8-triphenylsilyldibenzofuran-2-carboxamidine hydrochloride
  • Pd(P i3) 4 (15 mg, 0.013 mmol) is added and it is heated up to 40 °C with stirring for 8.5 h (until TLC shows complete consumption of the starting material).
  • the reaction mixture is poured into water (100 ml) and ethyl acetate (100 ml). The layers were separated and the aqueous layer is extracted with ethyl acetate (2 x 75 ml). The combined or- ganic layers are washed with brine (75 ml) and dried over Na2S0 4 . The solvent is removed in vacuo.
  • the crude product is purified via alumina (bas. act. II) column chromatography using heptane/DCM (1 :1) as eluent. BB-18 (226 mg, 0.389 mmol, 90%) is obtained as white solid.
  • Pd(P i3) 4 (175 mg, 0.15 mmol) is added and it is heated up to 80 °C with stirring for 17 h (until TLC shows complete consumption of the starting material).
  • the reaction mixture is cooled to room temperature and is poured into water (150 ml) and ethyl acetate (200 ml). The layers are separated and the aqueous layer is extracted with ethyl acetate (2 x 100 ml). The combined organic layers are washed with water (100 ml) and dried over Na2S0 4 . The solvent is removed in vacuo.
  • the crude product is dissolved in chloro- form (100 ml) and 3% aqueous NaCN solution (100 ml) is added.
  • the compound is synthesized using the method described for C-1 applying BB-9 (1.83 g, 6.0 mmol), BB-2 (2.77 g, 6.0 mmol), toluene (120 ml), ethanol (60 ml), water (30 ml), K 2 C0 3 (4.45 g, 32 mmol) and Pd(PPh 3 ) 4 (208 mg, 0.18 mmol).
  • C-4 (2.9 g, 5.2 mmol, 86%) is ob- tained as white solid. It is distilled at 240 °C / 3.4 x10- 6 mbar.
  • the compound is synthesized using the method described for C-1 applying BB-15 (3.1 g,
  • the residue is poured into chloroform (200 ml) and water (200 ml). The layers are separated and the aqueous layer is extracted with chloroform (3 x 150 ml). The combined organic layers are washed with brine (100 ml) and dried over MgS0 4 . The solvent is removed in vacuo.
  • the crude product is purified via filtration over a short alumina (bas. act. II) column and silica column chromatography using heptane/DCM as eluent (1 :1 , 1 :2). C-7 (2.15 g, 3.62 mmol, 83%) is obtained as white solid. It is further purified via recrystallization from xylene/cyclohexane.
  • the phases are separated and the aqueous phase extracted twice with tolu- ene (250 ml each).
  • the combined organic phases are washed three times with water (100 ml each), dried with magnesium sulfate, filtered and the solvent is evaporated on the rota- vap.
  • the crude product (16.8 g) is purified by flash chromatography with heptane/ethyl acetate as eluent yielding 12.4 g (74%) of 5-bromo-3-(5-bromo-2-methoxy-phenyl)pyridin-2- amine.
  • the yellow suspension is filtered, washed twice with 30 ml of ice water each, twice with 30 ml of methanol each and dried at high vacuum.
  • the crude product (8.57 g) is purified by flash chromatography with ethyl acetate/toluene as eluent yielding 8.19 g of product.
  • the light yellow crystals are refluxed in 80 ml of chloroform, cooled to room temperature, filtered and dried to yield 7.33 g (62 %) of 3,6-dibromobenzofuro[2,3- b]pyridine.
  • the clear solution is stirred for 1 hour at room temperature, then poured on 250 ml of water and extracted twice with 150 ml of ethyl acetate each.
  • the water phase is extracted again with 150 ml of ethyl acetate.
  • the combined organic phases are washed with 250 ml of brine, dried over Na2S0 4 , filtered and the solvent is evaporated at high vacuum.
  • the crude product is purified by flash chromatography with heptane/toluene as eluent yielding 4.13 g of yellow crystals.
  • the water phase is extracted with 250 ml of toluene, the combined organic phases are washed with 250 ml of water and 250 ml of brine, dried over Na2S0 4 , filtered and the solvent is evaporated on the rotavap.
  • the crude product is recrystallized in hot acetonitrile, then recrystallized a sec- ond time in toluene/isopropanol 2:5 to yield 16.50 g (80%) of [3,5-bis(4,4,5,5-tetramethyl-
  • This solution is added in one portion at 50°C to the reac- tion mixture prepared above, then the brown emulsion is heated to 75°C and stirred at this temperature for 1.5 hours.
  • the reaction mixture is filtered through hyflo into a separation funnel, then 50 ml of water and 500 ml of toluene are added and the phases are separated.
  • the water phase is extracted with 25 ml of toluene.
  • the combined organic phases are washed with 50 ml of water, 50 ml of brine, dried over Na2S0 4 , filtered and the solvent is evaporated on the rotavap.
  • the crude product is purified by flash chromatography with ethyl acetate/toluene as eluent.
  • All thin films are prepared by dissolving the materials in dichloromethane according intended concentrations, followed by stirring it for few minutes until dissolution.
  • the solutions are casted by doctor-blading with a film applicator (Model 360 2082, Erichsen) with a 60 ⁇ gap onto quartz substrates providing thin doped polymer films (thickness ca. 5-6 ⁇ ).
  • the triplet energy of the host materials is extracted from phosphorescence spectrum of a neat host film.
  • the phosphorescence spectra are measured from neat films at 4K by time- gated spectroscopy using FLS920 spectrometer system (Edinburgh Instruments) with excitation by Xe flash pulses and a detection delay-time of 0.18 ms.
  • the photoluminescence (PL) of emitter in the corresponding host systems are measured for hostemitter (96:4) films where 4% of reference emitter is doped into the corresponding host.
  • the PL spectra and quantum-yields (Q.Y.) of these films are measured with the integrating- sphere method using the Absolute PL Quantum Yield Measurement System (Hamamatsu, Model C9920-02) (excitation wavelength: 370 nm).
  • the ITO substrate used as the anode is first cleaned with an acetone/isopropanol mixture in an ultrasonic bath. To eliminate any possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for further 25 minutes. This treatment also improves the hole injection properties of the ITO. Then Plexcore ® OC AJ20-1000 (commercially available from Plextronics Inc.) is spin-coated and dried to form a hole injection layer (-40 nm).
  • transport and exciton blocker dpbic)3; HTM-1 is applied to the substrate with a thickness of 20 nm, wherein the first 10 nm are doped with MoO x (-10%) to improve the conductivity.
  • SH-1 is applied by vapor deposition in a thickness of 40 nm. Subsequently, material SH-1 is applied by vapour deposition with a thickness of 5 nm as blocker. Thereafter, a 20 nm thick electron transport layer is deposited consisting of
  • EQE External quantum efficiency
  • the devices are fabricated and characterized as in Comparative Application Example 2 except for the following:
  • a hole transport and exciton blocker material SH-1 is applied to the substrate with a thickness of 20 nm, wherein the first 10 nm are doped with MoO x (-10%) to improve the conductivity.
  • a mixture of 10% by weight of emitter compound BE-1 and 90% of compound SH-1 is deposited followed by 5 nm compound SH- 1 as hole blocking layer (HBL).
  • C-49 is synthesized using the method described for C-1 applying 2- bromobenzothiopheno[2,3-b]pyridine (2.0 g, 7.57 mmol), BB-2 (3.68 g, 7.95 mmol), toluene (100 ml), ethanol (50 ml), water (25 ml), K 2 C0 3 (5.65 g, 41 mmol) and Pd(PPh 3 ) 4 (219 mg, 0.19 mmol).
  • C-49 (3.40 g, 6.54 mmol, 86%) is obtained as white solid. It is distilled at 260 °C / 1.6x10-6 mbar.
  • the LDA solution prepared as described above is now added drop by drop within 15 minutes and the reaction mixture is stirred at -78°C for 20 minutes.
  • 9.132 g (32.4 mmol) of diiodoethan are added; the reaction mixture is stirred for 5 minutes at -78°C and then warmed to room temperature.
  • the solution is poured on 200 ml of a 5% solution of Na 2 S03, the phases are separated and the water phase is extracted with 200 ml of ethyl acetate.
  • the organic phases are washed twice with 200 ml of brine each, dried over Na 2 S03, filtered and the solvent is removed in vacuo.
  • the crude product is purified by flash chromatography using toluene as eluent yielding 2.99 g (53%) of 4- iodobenzothiopheno[3,2-b]pyridine.
  • the crude product is purified by flash chromatography using toluene as eluent.
  • Two addi- tional purifications by flash chromatography using chloroform/heptane in a ratio 1 :1 as eluent and finally decocting in heptane give benzothiopheno[3,2-b]pyridin-4- yl(tr phenyl)silane (C-50) in a HPLC purity of 100%.

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  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

La présente invention concerne des composés de formule (I), qui sont caractérisés en ce qu'ils sont substitués par au moins un groupe de formule (II) et en ce qu'au moins un des substituants B1, B2, B3, B4, B5, B6, B7 et B8 représente N ; un procédé pour leur production, et leur utilisation dans des dispositifs électroniques, notamment des dispositifs électroluminescents. Lorsqu'ils sont utilisés comme matière de transport d'électrons, matière de blocage de trous et/ou matière hôte pour émetteurs phosphorescents dans des dispositifs électroluminescents, les composés de formule I peuvent fournir un rendement, une stabilité, une aptitude à la fabrication meilleurs ou des caractéristiques spectrales accrues de dispositifs électroluminescents.
PCT/EP2015/051953 2014-02-03 2015-01-30 Azadibenzofuranes substitués par silyle et azadibenzothiophènes WO2015114102A1 (fr)

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KR20170023388A (ko) * 2015-08-21 2017-03-03 삼성디스플레이 주식회사 유기 발광 소자
US9960361B2 (en) * 2015-08-21 2018-05-01 Samsung Display Co., Ltd. Organic light-emitting device
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JP2017041636A (ja) * 2015-08-21 2017-02-23 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． 有機発光素子
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EP3133666A1 (fr) * 2015-08-21 2017-02-22 Samsung Display Co., Ltd. Dispositif électroluminescent organique
US11211564B2 (en) 2015-08-21 2021-12-28 Samsung Display Co., Ltd. Organic light-emitting device
WO2019059577A1 (fr) * 2017-09-20 2019-03-28 삼성에스디아이(주) Composé organique, composition, élément photoélectronique organique et dispositif d'affichage
KR20200131858A (ko) * 2018-03-16 2020-11-24 닛산 가가쿠 가부시키가이샤 아닐린 유도체 및 그 이용
KR102786862B1 (ko) 2018-03-16 2025-03-26 닛산 가가쿠 가부시키가이샤 아닐린 유도체 및 그 이용
CN108752237A (zh) * 2018-07-05 2018-11-06 四川青木制药有限公司 一种对氨基苯甲脒盐酸盐的新制备方法
US20210028376A1 (en) * 2019-07-22 2021-01-28 Universal Display Corporation Organic electroluminescent materials and devices

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