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WO2007086505A1 - Compose de complexe de metal de transition et dispositif electroluminescent organique l’utilisant - Google Patents

Compose de complexe de metal de transition et dispositif electroluminescent organique l’utilisant Download PDF

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Publication number
WO2007086505A1
WO2007086505A1 PCT/JP2007/051263 JP2007051263W WO2007086505A1 WO 2007086505 A1 WO2007086505 A1 WO 2007086505A1 JP 2007051263 W JP2007051263 W JP 2007051263W WO 2007086505 A1 WO2007086505 A1 WO 2007086505A1
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group
substituent
carbon atoms
atom
transition metal
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Japanese (ja)
Inventor
Masami Watanabe
Toshikazu Hirao
Toshiyuki Moriuchi
Lisheng Mao
Hsyueh-Liang Wu
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Idemitsu Kosan Co Ltd
University of Osaka NUC
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Idemitsu Kosan Co Ltd
Osaka University NUC
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Priority claimed from US11/516,585 external-priority patent/US7759489B2/en
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Priority to JP2007556013A priority Critical patent/JPWO2007086505A1/ja
Publication of WO2007086505A1 publication Critical patent/WO2007086505A1/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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • 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
    • 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

Definitions

  • the present invention relates to a transition metal complex compound and an organic electroluminescent device using the same, and in particular, an organic electroluminescent device that emits blue light with high luminous efficiency and a novel device that realizes the organic electroluminescent device.
  • the present invention relates to a transition metal complex compound.
  • Organic electoluminescence (EL) devices use the principle that a fluorescent substance emits light by recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field. Self-luminous element. Report of low-voltage driven organic EL devices using stacked devices by Eastman Kodak's CW Tang et al. (CW Tang, SA Vanslyke, Applied Physics Letters, 51 ⁇ , 913, 1987, etc.) ) Since then, research on organic EL devices using organic materials as constituent materials has been actively conducted. Tang et al. Used tris (8-hydroxyquinolinol aluminum) for the light-emitting layer and triphenyldiamine derivative for the hole-transporting layer.
  • the advantages of the stacked structure are that it increases the efficiency of hole injection into the light-emitting layer, blocks the electrons injected from the cathode, and increases the generation efficiency of excitons generated by recombination. For example, confining excitons.
  • the device structure of the organic EL device includes a hole transport (injection) layer, a two-layer type of an electron transport light-emitting layer, or a hole transport (injection) layer, a light-emitting layer, and an electron transport (injection).
  • the three-layer type is well known.
  • the structure of the element and the formation method have been devised.
  • the light-emitting material of the organic EL element is a tris (8-quinolinolato) aluminum complex.
  • Luminescent materials such as chelate complexes, coumarin derivatives, tetraphenylbutadiene derivatives, distyrylarylene derivatives, oxadiazole derivatives, etc. are known, and it has been reported that they can emit light in the visible region from blue to red. Therefore, it is expected to realize a color display element (for example, see Patent Document 1).
  • Patent Document 1 In recent years, it has also been proposed to use a phosphorescent material in addition to a fluorescent material for the light emitting layer of an organic EL element (see, for example, Non-Patent Document 1 and Non-Patent Document 2).
  • the triplet excited state or triplet exciton is not sequentially quenched so that the anode, the hole transport layer, the organic light emitting layer, the electron transport layer (hole blocking layer),
  • a structure in which layers are stacked such as an electron transport layer and a cathode has been used, and a host compound and a phosphorescent compound have been used for an organic light emitting layer (see, for example, Patent Document 2 and Patent Document 3).
  • These patent documents are technologies related to phosphorescent materials that emit red to green light.
  • techniques relating to a light emitting material having a blue emission color have been disclosed (see, for example, Patent Document 4, Patent Document 5, and Patent Document 6).
  • Patent Documents 7 and 8 describe a ligand skeleton in which an Ir metal and a phosphorus atom are bonded, and these emit light blue but have weak bonds. The heat resistance is extremely poor.
  • Patent Document 7 similarly describes a complex in which an oxygen atom and a nitrogen atom are bonded to the central metal, but there is no description about the specific effect of the group bonded to the oxygen atom, and it is unclear.
  • Patent Document 8 discloses a complex in which nitrogen atomic energy contained in different ring structures is bonded to a central metal, and a device using the same emits blue light, but the external quantum efficiency is as low as about 5%. It has become.
  • a carbene is a two-coordinate carbon that has two electrons in the sp 2 hybrid orbit and the 2p orbit, and the combined force of the orbit into which the two electrons enter and the direction of the spin. It is usually a singlet carbene, consisting of a sp 2 hybrid occupied orbit and an empty 2p orbit.
  • carbene complexes are short-lived 'unstable, and are intermediates or organic intermediates in organic synthesis reactions. Power that has been used as a synthetic conversion reagent such as addition to refin Around 1991, stable carbene complexes consisting of aromatic heterocyclic structures and stable carbene complexes consisting of non-aromatic cyclic structures were discovered.
  • the acyclic carbene complex was stably obtained by stabilizing with nitrogen and phosphorus.
  • the catalytic performance is improved by combining it with a transition metal as a ligand, in recent years, expectations for a stable carbene complex have increased in the catalytic reaction in organic synthesis.
  • complexes having a carbene iridium bond include the following non-patent document 12 (tris (carbene) iridium complex that also has a non-heterocyclic carbene ligand force) and non-patent document 13 (monodentate coordination type mono-). Carbene iridium complex), but the application to the organic EL device field is described.
  • Patent Document 9 discloses the synthesis of an iridium complex having a carbene bond, its emission wavelength, and device performance. Power energy efficiency, external quantum efficiency are low, and the emission wavelength is distributed in the ultraviolet region. The visual efficiency is poor. Therefore, it is not suitable for light-emitting devices in the visual wavelength range such as organic EL. Also, there was a problem in that impurities could be mixed during device fabrication because vacuum deposition could not be performed because the decomposition temperature was low or the molecular weight was high, and the complex was decomposed during the deposition.
  • Patent Documents 10 to 18 have descriptions relating to complexes having various carbene bonds, and blue light emitting complexes are disclosed. However, energy efficiency and external quantum efficiency are low, and neither of them mentions the extension of the light emission lifetime.
  • Patent Documents 19 and 20 describe three 3-phenylpyridine-N, C 2 group sites as a method for extending the lifetime of tris (2-phenylpyridine-N, C 2 ) iridium complex. Although it is disclosed that a leg-shaped bridge is used, only a tripod-type cross-linking site having a benzene ring skeleton has been reported. Guidelines Is not shown.
  • Patent Document 1 Japanese Patent Laid-Open No. 8-239655
  • Patent Document 2 U.S. Pat.No. 6,097,147
  • Patent Document 3 International Publication WO01Z41512
  • Patent Document 4 US2001Z0025108 Publication
  • Patent Document 5 US 2002/0182441 Publication
  • Patent Document 6 Japanese Patent Laid-Open No. 2002-170684
  • Patent Document 7 Japanese Unexamined Patent Publication No. 2003-123982
  • Patent Document 8 Japanese Patent Laid-Open No. 2003-133074
  • Patent Document 9 International Publication WO05Z019373
  • Patent Document 10 US2005Z0258433 Publication
  • Patent Document 11 US2005Z0258742 Publication
  • Patent Document 12 US2005Z0260441 Publication
  • Patent Document 13 US2005Z0260444 Publication
  • Patent Document 14 US2005Z0260445 Publication
  • Patent Document 15 US2005Z0260446 Publication
  • Patent Document 16 US2005Z0260447 Publication
  • Patent Document 17 US2005Z0260448 Publication
  • Patent Document 18 US2005Z0260449 Publication
  • Patent Document 19 US2005Z0170206 Publication
  • Patent Document 20 US 2005Z0170207 Publication
  • Non-Patent Document 1 D. F. OBrien and M. A. Baldo et al "lmproved energy tr ansferin electrophosphorescent devices" Vol. 74 No. 3, pp 442-444, Januaryl8, 1999
  • Non-Patent Document 2 M. A. Baldo et al Very high-efficiency green organic li ght -emitting devices based on electrophosphorescence "Applied Phys ics letters Vol. 75 No. 1, pp4-6, July 5, 1999
  • Non-Patent Document 3 Chem. Rev. 2000, 100, p39
  • Non-Patent Document 4 Am. Chem. Soc., 1991, 113, ⁇ 361
  • Non-Patent Document 5 Angew. Chem. Int. Ed., 2002, 41, pi 290
  • Non-Patent Document 6 Am. Chem. Soc., 1999, 121, p2674
  • Non-Patent Document 7 Organometallics, 1999, 18, p2370
  • Non-Patent Document 8 Angew. Chem. Int. Ed., 2002, 41, pl363
  • Non-Patent Document 9 Angew. Chem. Int. Ed., 2002, 41, pi 745
  • Non-Patent Document 10 Organometallics, 2000, 19, p3459
  • Non-patent literature ll TetrahedronAymmetry, 2003, 14, p951
  • Non-Patent Document 12 Organomet. Chem., 1982, 239, C26-C30
  • Non-Patent Document 13 Chem. Commun., 2002, ⁇ 2518
  • the present invention has been made to solve the above-mentioned problems, and is an organic EL device having a high luminous efficiency and a long luminescent lifetime, and a blue luminescent organic EL having a high luminescent efficiency and a long luminescent lifetime. It is an object to provide a device and a novel transition metal complex compound that realizes the device.
  • the present inventors have found that an iridium obtained by crosslinking three ligands in a tripod shape with a bridging group having a saturated cyclic structure or a saturated polycyclic structure.
  • organic EL devices with a high emission efficiency and a long emission lifetime can be produced by using a complex (transition metal complex compound), and that the emission efficiency can be achieved by using an iridium complex having a metal carbene bond as a ligand.
  • the present inventors have found that an organic EL element that emits blue light with a long emission lifetime can be produced, and the present invention has been completed.
  • the present invention provides a transition metal complex compound represented by the following general formula (1).
  • A is a bridged bidentate group consisting of ⁇ — (Z 1 ) —L 2
  • B is L 3 — (d
  • Z 2 ) — a group of bridged bidentate ligands with L 4 force
  • C is a bridged bidentate of L 5 — (Z 3 ) —L 6 ef
  • L 1 , L 3 — and L 5 — denote covalent bonds to Ir (iridium) (L 1 — Ir, L 3 — Ir and L 5 — Ir), respectively, L 2 ⁇ , L 4 ⁇ and L 6 ⁇ represents coordination bonds to Ir (L 2 ⁇ Ir, L 4 ⁇ Ir and L 6 ⁇ Ir), respectively.
  • X is a bridging group having a saturated cyclic structure or saturated polycyclic structure having 3 to 18 atoms, and is a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, or a boron atom. It is a trivalent residue of a compound composed of atoms selected from the group, and may have a substituent.
  • Y 1 is X and A
  • Y 2 is X and B
  • Y 3 is a bridging group that bonds X and C
  • Y 1 is ⁇ L 2 or ⁇ 1 ⁇ 2 is L 3 , L 4 or Z 2
  • Y 3 is bound to L 5 , L 6 or Z 3
  • ⁇ 2 and ⁇ 3 are independently a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a boron atom. It is a residue and may have a substituent.
  • a, b and c each independently represent an integer of 0 to 0. When a, b or c is plural, a plurality of Y 1 Y 2 or Y 3 may be the same or different.
  • Z 1 represents L 1 and L 2
  • Z 2 represents L 3 and L 4
  • Z 3 represents a bridging group that links L 5 and L 6
  • Z 2 and Z 3 are independently hydrogen atoms.
  • Z 1 is directly bonded to Y 1
  • Z 2 is directly bonded to Y 2
  • Z 3 is directly bonded to Y 3
  • Z 2 and Z 3 are each a corresponding trivalent group.
  • d, e and f each independently represent an integer of 0 to 0.
  • the plurality of z Z 2 or Z 3 may be the same or different.
  • ⁇ L 3 and L 5 are each independently a divalent aromatic hydrocarbon group having 6-30 nuclear carbon atoms which may have a substituent, or a nuclear atom number having 3-30 which may have a substituent. It may have a divalent heterocyclic group or a substituent, or it may have a divalent carboxyl-containing group or substituent having 1 to 30 carbon atoms!
  • Divalent amino group ⁇ contains a hydroxyl group A hydrocarbon group, a cycloalkylene group having 3 to 50 carbon atoms, a cycloalkylene group having 3 to 50 carbon atoms, an alkylene group having 1 to 30 carbon atoms that may have a substituent, and a substituent group; Alkylene group having 2 to 30 carbon atoms or a substituent, but it is an aralkylene group having 7 to 40 carbon atoms, and when L 1 is directly bonded to ⁇ 1 , L 3 is directly bonded to ⁇ 2 When L 5 is directly bonded to ⁇ 3 , ⁇ L 3 and L 5 are respectively equivalent trivalent groups.
  • L 2 , L 4 and L 6 are each independently a monovalent group having a carbene carbon which may have a substituent, or a monovalent group having 3 to 30 nuclear atoms which may have a substituent.
  • L 2 is directly bonded to Y 1
  • L 4 is directly bonded to Y 2
  • L 6 is directly bonded to Y 3
  • L 2 , L 4 and L 6 are , Each corresponding to a divalent group.
  • the present invention provides an organic EL element in which an organic thin film layer comprising at least one light emitting layer or a plurality of layers is sandwiched between an anode and a cathode, and at least one of the organic thin film layers is An organic EL device containing a transition metal complex compound is provided. The invention's effect
  • the organic EL device using the transition metal complex compound of the present invention has a high luminous efficiency and a long luminous lifetime.
  • the organic EL device using the transition metal complex compound having a metal carbene bond of the present invention emits blue light, has high emission efficiency, and has a long emission lifetime.
  • FIG. 1 is a diagram showing 1 H-NMR spectral data of transition metal complex compound 8 obtained in Example 1.
  • FIG. 2 is a diagram showing 13 C-NMR spectrum data of transition metal complex compound 8 obtained in Example 1.
  • FIG. 3 is a diagram showing an emission spectrum of transition metal complex compound 8.
  • FIG. 5 is a diagram showing 1 H-NMR ⁇ vector data of transition metal complex compound 15 obtained in Example 2.
  • FIG. 6 is a diagram showing 13 C-NMR spectrum data of transition metal complex compound 15 obtained in Example 2.
  • FIG. 7 is a graph showing an emission spectrum of transition metal complex compound 15.
  • FIG. 8 is a diagram showing 1 H-NMR vector data of the transition metal complex compound 20 obtained in Example 3.
  • FIG. 9 is a diagram showing 13 C-NMR spectrum data of transition metal complex compound 20 obtained in Example 3.
  • FIG. 10 is a graph showing an emission spectrum of transition metal complex compound 20.
  • FIG. 11 is a diagram showing an EL spectrum of the organic EL device obtained in Example 4.
  • the transition metal complex compound of the present invention is an iridium complex in which three ligands are crosslinked in a tripod shape with a bridging group having a saturated cyclic structure or a saturated polycyclic structure, and a metal carbene bond is formed on these three ligands.
  • Such a transition metal complex compound of the present invention is represented by the following general formula (1).
  • A is a bridged bidentate ligand group consisting of L 1 — (Z 1 ) — L 2 , and B is L 3 — (
  • Z 2 ) — a group of bridged bidentate ligands with L 4 force
  • C is a bidentate bridge consisting of L 5 — (Z 3 ) —L 6 ef
  • L 1 , L 3 — and L 5 — denote covalent bonds to Ir (iridium) (L 1 — Ir, L 3 — Ir and L 5 — Ir), respectively, L 2 ⁇ , L 4 ⁇ and L 6 ⁇ represents coordination bonds to Ir (L 2 ⁇ Ir, L 4 ⁇ Ir and L 6 ⁇ Ir), respectively.
  • X is a bridging group having a saturated cyclic structure or a saturated polycyclic structure having 3 to 18 atoms, and is a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, sulfur.
  • saturated cyclic structure or saturated polycyclic structure examples include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cycloundecane ring, adamantane ring.
  • one of the carbon atoms constituting these rings or one of a carbon atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a boron atom may be substituted.
  • the bridging group X is more preferably the following structure (2) (inside the broken line), which is preferably a cyclohexane residue.
  • the alkyl group is preferably one having 1 to LO carbon atoms.
  • methyl, ethyl, propyl, isopropyl, n-butyl, sbutyl, isobutyl, tbutyl, n-pentyl, n-hexyl, and n- are preferred.
  • Ptyl group Ptyl group, n-octyl group, n-nor group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n —Heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 1 pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, cyclohexyl group, cyclooctyl group, 3,5-tetramethylcyclo Hexyl group.
  • halogenated alkyl group those having 1 to 10 carbon atoms are preferred, for example, chloromethyl group, 1-chloroethyl ethyl group, 2-chlorodiethyl group, 2-chlorodiisobutyl group, 1,2-dichloro.
  • a fluoromethyl group preferred are a trifluoromethyl group, a pentafluoroethyl group, a perfluoroisopropyl group, a perfluorobutyl group, and a perfluorocyclohexyl group.
  • the aromatic hydrocarbon group is preferably one having a nuclear carbon number of 6 to 18, for example, a phenol group, 1 naphthyl group, 2 naphthyl group, 1 anthryl group, 2 anthryl group, 9-a Enthryl group, 1 phenanthryl group, 2 phenanthryl group, 3 phenanthryl group, 4 phenanthryl group, 9 phenanthryl group, 1 naphthacene group, 2 naphthacetyl group, 9-naphthaphthalyl group, 1-pyrole group , 2 pyreyl group, 4 pyreyl group, 2 biphenyl group, 3—biphenyl group, 4-biphenyl group, p terferyl group 4 —yl group, p terferlu group 3— P-group, p-Terfer-Lu 2-yl group, m-Ter-Fel-Lu 4-Yel group, m-Ter-Fel-L
  • a phenyl group 1 naphthyl group, 2 naphthyl group, 9 phenanthryl group, 2 biphenylyl group, 3 biphenylyl group, 4 biphenylyl group, p-tolyl group, 3, 4-Xylylenyl group.
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, and 2- And a norbornyl group.
  • the aralkyl group is preferably one having 7 to 18 carbon atoms, for example, benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group.
  • the alkenyl group is preferably one having 2 to 16 carbon atoms, for example, a bur group, a allyl group, a 1-butur group, a 2-butyl group, a 3-butyl group, a 1,3-butane angel group.
  • the heterocyclic group preferably has 3 to 18 nuclear atoms.
  • 2-pyridyl group 1-indolidyl group, 2-indolidyl group, 3-indolidyl group, 5-indolidyl group, 6-indolidyl group, 7 —Indolizyl group, 8 Indolizyl group, 2 Imidazopyridyl group, 3 Imidazopyridinyl group, 5 Imidazopyridinyl group, 6—Imidazopyridyl group, 7—Imidazopyridyl group, 8—Imidazopyridyl group Group, 3-pyridyl group, 4 pyridyl group, 1 indolyl group, 2 indolyl group, 3—indolyl group, 4 indolyl group, 5—indolyl group, 6—indolyl group, 7—indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoin
  • the alkoxy group and Ariruokishi group is a group represented by OX 1, is an example of X 1, same examples as those described for the alkyl group and Nono Rogeni spoon alkyl and Ariru group Is mentioned.
  • the alkylamino group and the arylamino group are groups represented by —NX 1 X 2 , and examples of X 1 and X 2 are those described for the alkyl group, the halogenated alkyl group, and the aryl group, respectively. The same example is given.
  • Examples of the carboxyl-containing group include methyl ester, ethyl ester, and butyester.
  • alkylsilyl group examples include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a butyldimethylsilyl group, and a propyldimethylsilyl group.
  • arylsilyl group examples include a triphenylsilyl group, a phenyldimethylsilyl group, and a t-butyldiphenylsilyl group.
  • Examples of the ring structure formed by crosslinking of R a to Ri include the same examples as those given for the heterocyclic group and the aromatic hydrocarbon group.
  • R a to Ri forces are all hydrogen atoms.
  • a specific example of the general formula (2) is shown below.
  • Y 1 represents X and A
  • Y 2 represents X and B
  • Y 3 represents a bridging group that binds X and C
  • Y 1 represents ⁇ L 2 or ⁇ represents L 3
  • L 4 or Z 2 and Y 3 are bonded to L 5 , L 6 or Z 3 .
  • ⁇ ⁇ 2 and ⁇ 3 are each independently a hydrogen atom, a carbon atom, a key atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, and a boron atom. And may have a substituent.
  • a, b and c each independently represent an integer of 0 to 0, preferably 0 to 3.
  • the plurality of Y ⁇ 2 or ⁇ 3 may be the same or different.
  • ⁇ ⁇ 2 and ⁇ 3 are: —CI ⁇ R 2 —, -SiR'R 2- , — NR 1 —, _0—,-
  • R 1 and R 2 are the same as in the above-described R a to R f, may be the same or different in their respective independent.
  • R 1 and R 2 may be cross-linked with X or may be cross-linked with R 1 and R 2 .
  • each Y 1 each Y 2 and each Y 3 is the same as one CR 2- , one SiR 2- , one NR 1- , one O-, one S-, one PR 1 - and single BR 1 - can be optionally selected from.
  • R 1 and R 2 between each Y 1 and each Y 2 and each Y 3 may be cross-linked with R 1 and R 2 that cross-links with X.
  • Z 1 represents L 1 and L 2
  • Z 2 represents L 3 and L 4
  • Z 3 represents a bridging group that binds L 5 and L 6
  • z Z 2 and Z 3 are each a divalent residue of a compound composed of an atom selected from the group consisting of a hydrogen atom, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom and a boron atom. , May have a substituent.
  • Z 1 is directly bonded to Y 1
  • Z 2 is directly bonded to Y 2
  • Z 3 is directly bonded to Y 3
  • z Z 2 and Z 3 are each a corresponding trivalent group and Become.
  • d, e and f each independently represent an integer of 0 to 0, preferably 0 to 3.
  • Z 2 or Z 3 may be the same or different.
  • zz 2 and z 3 are the same as those of Y 1 Y 2 and Y 3 and groups in which they are trivalent.
  • ⁇ ⁇ ⁇ L 3 and L 5 each independently have a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms and a substituent which may have a substituent. Yes, it may have a bivalent heterocyclic group or substituent having 3 to 30 heteronuclear atoms, or it may have a divalent carboxyl-containing group or substituent having 1 to 30 carbon atoms.
  • Good Divalent amino group or hydroxyl group-containing hydrocarbon group may have a substituent, may be a cycloalkylene group having 3 to 50 nuclear carbon atoms, or may have a substituent, an alkylene group having 1 to 30 carbon atoms , Aruke good 2 to 30 carbon atoms which may have a substituent - alkylene group, a Ararukiren group to carbon atoms which may be 7 to 40 have a substituent, and when L 1 is bonded directly Upsilon 1, L 3 When Y 2 is directly bonded, or when L 5 is directly bonded to ⁇ 3 , ⁇ L 3 and L 5 are the corresponding trivalent groups.
  • divalent aromatic hydrocarbon groups divalent heterocyclic groups, divalent carboxyl-containing groups, cycloalkylene groups, alkylene groups, alkylene groups and aralkylene groups
  • Preferred examples include the divalent examples of the aromatic hydrocarbon group, heterocyclic group, carboxyl-containing group, cycloalkyl group, alkyl group, alkenyl group and aralkyl group described above. The same can be mentioned.
  • Examples of the divalent amino group or the hydroxyl group-containing hydrocarbon group include an amino group having each hydrocarbon group represented by ⁇ L 3 and L 5 , and a hydrogen atom of the hydrocarbon group is a hydroxyl group. Something that has been replaced.
  • ⁇ L 3 and L 5 aromatic hydrocarbon group or a heterocyclic there when it example preferred instrument Examples group, phenyl group and substituted phenyl group among structures of these preferred tool shown below Is preferred.
  • ⁇ represents an adjacent linking group, that is, L 2 , L 4 or L 6 .
  • L 2 , L 4 and L 6 are each independently a monovalent group having a rubene carbon which may have a substituent, or a nuclear atom which may have a substituent
  • L 2, L 4 of ⁇ Pi L 6, further preferably at least when one is a group having a carbene carbon preferably fixture L 2
  • L 4 ⁇ Pi L 6 is a group having a carbene carbon.
  • the monovalent group having a carbene carbon is usually preferably one that forms a stable carbene together with a metal.
  • imidazole-2-ylidene 1,2,4_triazole-1-ylidene and cyclic diaminocarbene, and more preferred are imidazole-2-ylidene and 1,2,4tritriazole-1.
  • Iridene its specific structure is listed below.
  • the A ring represents an adjacent linking group, that is, ⁇ L 3 or L 5 .
  • R j is the same as described above.
  • L 2 , L 4 and L 6 are groups having no carbene carbon
  • a substituted or unsubstituted aryl group having 5 to 50 nuclear carbon atoms a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon
  • An alkoxy group having 1 to 50 carbon atoms a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 carbon atoms, a substituted or unsubstituted carbon atom number 5
  • Examples thereof include an arylothio group of ⁇ 50, a substituted or unsubstituted alkoxycarbon group having 1 to 50 carbon atoms, an amino group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, and a carboxyl group.
  • an alkyl group having 1 to 10 carbon atoms a cycloalkyl group having 5 to 7 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkyl group having 1 to 6 carbon atoms, and 5 to 7 carbon atoms are preferable.
  • the organic EL device of the present invention is an organic EL device in which an organic thin film layer having at least one light emitting layer or a multi-layer force is sandwiched between a pair of electrodes having an anode and a cathode force. However, it contains a transition metal complex compound represented by the general formula (1) of the present invention.
  • the content of the metal complex compound of the present invention in the organic thin film layer is usually 0.1 to LOO% by weight and preferably 1 to 30% by weight with respect to the total mass of the light emitting layer. .
  • the light emitting layer preferably contains the transition metal complex compound of the present invention as a light emitting material or a dopant.
  • the light emitting layer can be made thin by vacuum deposition or coating. Since the coating process can simplify the manufacturing process, the layer containing the transition metal complex compound of the present invention is formed by coating. This is preferable.
  • the organic thin film layer is of a single layer type, the organic thin film layer is a light emitting layer, and this light emitting layer contains the transition metal complex compound of the present invention.
  • Multi-layer organic EL devices include (Anode Z hole injection layer (Hole transport layer) Z Light emitting layer Z cathode), (Anode Z Light emitting layer Z Electron injection layer (Electron transport layer) Z cathode), (Anode Z hole injection layer (hole transport layer) Z light emitting layer Z electron injection layer (electron transport layer) Z cathode) and the like.
  • the anode of the organic EL device of the present invention supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like, and it is effective to have a work function of 4.5 eV or more. is there.
  • a material for the anode a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used.
  • Specific examples of the material of the anode include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), or metals such as gold, silver, chromium, nickel, and conductive materials thereof. Mixture or laminate of conductive metal oxide and metal
  • Inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyarlin, polythiophene and polypyrrole, and laminates of these with ITO, preferably conductive metal oxide
  • ITO inorganic conductive materials
  • the film thickness of the anode can be appropriately selected depending on the material.
  • the cathode of the organic EL device of the present invention supplies electrons to an electron injection layer, an electron transport layer, a light emitting layer, and the like.
  • the cathode material include metals, alloys, metal halides, metal oxides. , Electrically conductive compounds, or mixtures thereof.
  • Specific examples of cathode materials include alkali metals (eg, Li, Na, K, etc.) and their fluorides or oxides, alkaline earth metals (eg, Mg, Ca, etc.), and their fluorides or oxides.
  • aluminum and lithium-aluminum are preferable.
  • the cathode may have a single layer structure of the material or a laminated structure of layers containing the material.
  • a laminated structure of aluminum Z lithium fluoride and aluminum / lithium oxide is preferable.
  • the film thickness of the cathode can be appropriately selected depending on the material.
  • the hole injection layer and the hole transport layer of the organic EL device of the present invention have a function of injecting holes from the anode cover, a function of transporting holes, and a barrier from electrons injected from the cathode cover.
  • Any device having any of the functions may be used. Specific examples thereof include strength rubazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine amines, amino substituted chalcone derivatives, styrylanthracene.
  • the hole injection layer and the hole transport layer may have a single layer structure composed of one or more of the materials, or a multilayer structure having a multi-layer force of the same composition or different compositions. It may be.
  • the electron injection layer and the electron transport layer of the organic EL device of the present invention have any one of a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. What is necessary is just to have. Specific examples thereof include triazole derivatives, oxazol derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carpositimide derivatives, fluorenylidenemethane derivatives.
  • the electron injection layer and the electron transport layer may have a single-layer structure composed of one or more of the materials, or a multilayer structure having a multi-layer force of the same composition or different compositions. Moyo.
  • examples of the electron transport material used for the electron injection layer and the electron transport layer include the following compounds.
  • the electron injection layer and / or the electron transport layer contain a ⁇ electron deficient nitrogen-containing heterocyclic derivative as a main component.
  • ⁇ electron deficient nitrogen-containing heterocyclic derivatives include benzimidazole ring, benztria Nitrogen-containing 5-membered ring selected from sol ring, pyridinoimidazole ring, pyrimidinoimidazole ring, pyridazinoimidazole ring, and nitrogen-containing nitrogen composed of pyridine ring, pyrimidine ring, pyrazine ring, triazine ring Preferred examples include 6-membered ring derivatives.
  • Preferred examples of the nitrogen-containing 5-membered ring derivative include structures represented by the following general formula B—I.
  • Examples of the nitrogen-containing 6-membered ring derivative include the following general formula C— Preferred examples include structures represented by I, cn, cm, C-IV, Ji and Hide ⁇ , and particularly preferred are structures represented by the general formulas CI and C-II.
  • L D represents a divalent or higher linking group, preferably a linking group formed of carbon, silicon, nitrogen, boron, oxygen, sulfur, metal, metal ion, or the like. More preferably a carbon atom, a nitrogen atom, a carbon atom, a boron atom, an oxygen atom, a sulfur atom, an aromatic hydrocarbon ring or an aromatic heterocycle, and still more preferably a carbon atom, a carbon atom or an aromatic. It is a hydrocarbon ring or an aromatic hetero ring.
  • L B is preferably an alkyl group as Yogu substituent may have a substituent, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, an amino group, an alkoxy group, Ariruokishi group, ⁇ sill group, an alkoxy Carbon group, aryloxycarbol group, acyloxy group, acylamino group, alkoxy carbolumino group, aryloxycarbolamino group, sulfo-lumino group, sulfamoyl group, rubamoyl group, alkylthio Group, aryl group, sulfonyl group, halogen atom, cyano group and aromatic heterocyclic group, more preferably alkyl group, aryl group, alkoxy group, aryloxy group, halogen atom, cyan group and aromatic heterocyclic group. More preferably, alkyl group, aryl group, alkoxy group, aryloxy group, halogen atom,
  • linking group represented by Table B in LB include the following.
  • R B2 represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group.
  • the aliphatic hydrocarbon group represented by R B2 is a linear, branched or cyclic alkyl group (preferably, An alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a tert butyl group, and an n-octyl group. N-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.
  • alkyl group preferably an alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a bur group, a allyl group, a 2 butyr group, 3 pentyl groups, etc.
  • alkyl groups preferably alkynyl groups having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl. Group, 3 pentynyl group, etc.
  • alkyl group preferably an alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a bur group, a allyl group, a 2 butyr group, 3 pentyl groups, etc.
  • alkyl groups preferably alkynyl groups having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to
  • the aryl group represented by R B2 is a monocyclic or condensed aryl group, preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • aryl group 2-methylphenyl group, 3-methylphenyl group, 4-methylphenol group, 2-methoxyphenyl group, 3-trifluoromethylphenyl group, pentafluorophenyl group, 1-naphthyl group Group, 2-naphthyl group and the like.
  • the heterocyclic group represented by R B2 is a monocyclic or condensed heterocyclic group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 2 to 10 carbon atoms).
  • Ring group preferably an aromatic heterocyclic group containing at least one of a nitrogen atom, an oxygen atom, a sulfur atom, and a selenium atom, such as pyrrolidine, piperidine, piperazine, morpholine, Thiophene, selenophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, pyrimidine, triazole, triazine, indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine , Naphthy
  • R B2 is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, more preferably an aryl group or an aromatic heterocyclic group, and still more preferably an aryl group.
  • Z B2 represents an atomic group necessary for forming an aromatic ring.
  • the aromatic ring formed by z B 2 may further form a condensed ring with another ring or may have a substituent.
  • a substituent preferably an alkyl group, an alkyl group, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, an acyloxy group.
  • acylamino group alkoxy carbo-lumino group, aryloxy carbo-lumino group, sulfo-lumino group, sulfamoyl group, strong rubamoyl group, alkylthio group, arylothio group, sulfol group, halogen atom, cyano group
  • a heterocyclic group more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, a cyano group, or a heterocyclic group, and even more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group.
  • aromatic heterocyclic group particularly preferably alkyl group, aryl group, alkoxy group.
  • Ru heterocyclic group der aromatic.
  • n B is an integer of 1 to 4, preferably 2 to 3.
  • R B71 , R B72 and R B73 are the same as R B2 in general formula (BI), respectively, and the preferred ranges are also the same.
  • Z B71, Z B72 and Zeta Beta73 are similar to Zeta B2 in the general formula (Beta iota) respectively, also are similar ranges have preferred.
  • L B71, L B72 and L B73 each represent a linking group
  • the general formula (B- I) can be mentioned those divalent examples of L B in, preferably, a single bond, a divalent aromatic hydrocarbon A hydrogen ring group, a divalent aromatic heterocyclic group, and a linking group having a combination force thereof, more preferably a single bond.
  • L m , L B72 and L B73 may have a substituent. Examples of the substituent may be the same as L B in the general formula (BI).
  • Y represents a nitrogen atom, a 1, 3, 5-benzenetriyl group or a 2, 4, 6-triazine triyl group.
  • the 1, 3, 5-benzenetriyl group may have a substituent at the 2, 4, 6-position, and examples thereof include an alkyl group, an aromatic hydrocarbon ring group, and a halogen atom. It is possible.
  • Cz is a substituted or unsubstituted carbazolyl group, aryl carbazolyl group or force rubazolylalkylene group
  • A is a group formed from a site represented by the following general formula (A).
  • n and m are integers from 1 to 3, respectively.
  • M and M ′ are each independently a nitrogen-containing heterocycle having 2 to 40 carbon atoms to form a ring. It is an aromatic ring, and the ring may or may not have a substituent. M and M ′ may be the same or different.
  • L is a single bond, an arylene group having 6 to 30 carbon atoms, a cycloalkylene group having 5 to 30 carbon atoms, or a heteroaromatic ring having 2 to 30 carbon atoms, and having a substituent bonded to the ring. May not be included.
  • p is an integer from 0 to 2
  • q is an integer from 1 to 2
  • r is an integer from 0 to 2. However, p + r is 1 or more.
  • the bonding mode of the group represented by the general formula (A) depends on the number of parameters p, q, r, specifically, the forms described in (1) to (16) in the following table. It is.
  • Ar to Ar each represent the same group as R B2 in the general formula (B—I), and specific examples thereof are also the same.
  • Ar to Ar are divalent groups similar to R B2 in the general formula (B—I).
  • the example is similar. )
  • R to R each represent the same group as R B2 in the general formula (B—I), and specific examples thereof are also the same.
  • Ar ⁇ Ar 4 represents the same group as R B2 in the general formula (BI), and the specific examples are also the same.
  • an insulator or a semiconductor inorganic compound as a substance constituting the electron injection / transport layer. Electron injection 'transport layer If it is composed of an edge body or a semiconductor, current leakage can be effectively prevented and electron injection properties can be improved.
  • an insulator it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkali earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides. . If the electron injecting / transporting layer is composed of these alkali metal chalcogenides or the like, it is preferable in that the electron injecting property can be further improved.
  • alkali metal chalcogenides include, for example, Li 0, LiO, Na
  • alkaline earth metal chalcogenides include
  • alkali metal halide examples include LiF, NaF, KF, LiCl, KC1, and NaCl.
  • alkaline earth metal halides examples include fluorides such as Ca F, BaF, SrF, MgF and BeF, and halides other than fluorides.
  • the electron injection 'transport layer at least one of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn is used.
  • the inorganic compound constituting the electron transport layer is preferably a microcrystalline or amorphous insulating thin film. If the electron transport layer is composed of these insulating thin films, a more uniform thin film is formed, and pixel defects such as dark spots can be reduced. Examples of such inorganic compounds include the alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides described above.
  • the electron injection layer and / or the electron transport layer may contain a reducing dopant having a work function of 2.9 eV or less.
  • the reducing dopant is a compound that increases the electron injection efficiency.
  • reducing dopants include alkali metals and alkaline earth metals. Oxides, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metal halides, rare earth metal oxides or rare earth metal halides, alkali metal complexes, alkalis Group power of earth metal complex and rare earth metal complex At least one compound selected.
  • preferable reducing dopants include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV) and Cs (work function: 1.
  • At least one selected alkaline earth metal, with a work function of 2.9 eV is particularly preferred.
  • a more preferable reducing dopant is at least one alkali metal selected from the group consisting of K, Rb and Cs, more preferably Rb or Cs, and most preferably Cs.
  • alkaline earth metal oxide examples include BaO, SrO, CaO and Ba Sr O (0 ⁇ x ⁇ 1) mixed with these, Ba Ca O (0 ⁇ x ⁇ 1). are listed as preferred
  • alkali oxides or fluorides examples include LiF, Li 0
  • the alkali metal complex, alkaline earth metal complex, and rare earth metal complex are not particularly limited as long as they contain at least one of alkali metal ions, alkaline earth metal ions, and rare earth metal ions as metal ions.
  • the ligand include quinolinol, benzoquinolinol, ataridinol, phenanthridinol, hydroxyphenylazole, hydroxyphenylthiazole, hydroxydiaryloxadiazole, hydroxydiarylthiadiazole, Hydroxyphenyl lysine, hydroxy phenyl benzimidazole, hydroxy benzotriazole, hydroxy fulborane, bipyridyl, phenanthorin, phthalocyanine, porphyrin, cyclopentagen, 13-diketones, azomethines, their derivatives, etc.
  • the powers listed are not limited to these.
  • the reducing dopant it is formed in a layered or island shape.
  • the preferred film thickness is 0.05 to 8 nm.
  • an organic substance that is a light-emitting material or an electron injecting material that forms an interface region is simultaneously deposited while a reducing dopant is deposited by resistance heating vapor deposition.
  • a method in which a reducing dopant is dispersed therein is preferred.
  • the dispersion concentration is 100: 1 to 1: 100, preferably 5: 1 to 1: 5, as a molar ratio.
  • the reducing dopant When forming the reducing dopant in layers, after forming the light emitting material or electron injecting material, which is an organic layer at the interface, into layers, the reducing dopant is vapor-deposited alone by resistance heating evaporation, preferably 0.5 nm in thickness. ⁇ ! Form at ⁇ 15nm.
  • the reducing dopant When forming the reducing dopant in the form of an island, after forming the light emitting material or electron injecting material which is the organic layer at the interface, the reducing dopant is vapor-deposited by resistance heating evaporation method, preferably 0.05 to ln. Form with m.
  • the light-emitting layer of the organic EL device of the present invention can inject holes from the anode or the hole injection layer when an electric field is applied, and can inject electrons from the cathode or the electron injection layer. It provides a function to move the generated charges (electrons and holes) by the force of an electric field, a field for recombination of electrons and holes, and a function to connect this to light emission.
  • the light emitting layer of the organic EL device of the present invention may contain a host material using the transition metal complex compound as a guest material, which preferably contains at least the transition metal complex compound of the present invention.
  • the host material examples include those having a force rubazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an allylsilane skeleton. . It is preferable that the T1 (minimum triplet excited state energy level) of the host material is larger than the T1 level of the guest material.
  • the host material may be a low molecular compound or a high molecular compound.
  • the light emitting material such as the transition metal complex compound
  • a method for forming each layer is not particularly limited, but a vacuum deposition method, an LB method, a resistance heating deposition method, an electron beam method, a sputtering method, a molecular lamination method, and the like.
  • Various methods such as a coating method (spin coating method, casting method, dip coating method, etc.), inkjet method, printing method, etc. can be used.
  • the coating method is preferred.
  • the organic thin film layer containing the transition metal complex compound of the present invention can be prepared by vacuum deposition, molecular beam deposition (MBE), solution dating, solvent coating, spin coating, casting, bar coating. It can be formed by a known method using a coating method such as a coating method or a roll coating method.
  • MBE molecular beam deposition
  • the coating method can be formed by dissolving the transition metal complex compound of the present invention in a solvent to prepare a coating solution, and coating and drying the coating solution on a desired layer (or electrode). .
  • rosin which may contain rosin can be dissolved in a solvent or dispersed.
  • a non-conjugated polymer for example, polyvinyl carbazole
  • a conjugated polymer for example, a polyolefin polymer
  • each organic layer of the organic EL element of the present invention is not particularly limited, but generally, if the film thickness is too thin, defects such as pinholes are generated, and conversely, if it is too thick, a high applied voltage is required and efficiency increases. Usually, the range of several nm to 1 ⁇ m is preferable because of worsening.
  • Compound 3 was synthesized by the following steps.
  • Compound 5 was synthesized by the following steps.
  • Compound 7 was synthesized by the following steps.
  • Compound 8 was synthesized by the following steps.
  • the measurement conditions for FD-MS measurement were as follows.
  • Measuring solvent Solvent CD C1 (deuterated methylene chloride), standard 0 OOppm (tetomethylsilane)
  • Compound 10 was synthesized by the following steps.
  • the compound 9 1.07 g was added to 20 ml of dry 1-propanol and suspended. Hydrogen chloride gas was published for 2 hours. While continuing publishing, this reaction solution was heated to reflux for 1 hour to be reacted. After completion of the reaction, this was returned to room temperature and evaporated under reduced pressure.
  • Compound 11 was synthesized by the following steps.
  • reaction was carried out under an inert gas stream.
  • Compound 11 was synthesized by the following steps.
  • reaction was carried out under an inert gas stream.
  • LiAIH lithium aluminum hydride
  • Compound 12 was synthesized by the following steps.
  • reaction was carried out under an inert gas stream.
  • Compound 14 was synthesized by the following steps.
  • reaction was carried out under an inert gas stream.
  • Compound 15 was synthesized by the following steps.
  • the measurement conditions for the FD-MS measurement were as follows.
  • HX110 manufactured by JEOL Ltd.
  • Compound 17 was synthesized by the following steps.
  • a potassium aqueous solution of 28 milliliters (molecular weight: 99.11, 5.45 g, 55 millimonole) was added and refluxed for 48 hours. After cooling, the aqueous layer was separated from this reaction solution with a separatory funnel, and extracted with methylene chloride three times. The oil layer was dried over anhydrous magnesium sulfate, and volatiles were distilled off under reduced pressure to obtain a crude product. Further, this was purified by silica gel column chromatography (hexane Z ethyl acetate mixed solvent) to obtain 2.48 g (molecular weight: 187.21, 13.2 midimonore, yield: 53%) of the target compound 17.
  • Compound 18 was synthesized by the following steps.
  • NBS N-bromosuccinimide
  • Compound 19 was synthesized by the following steps.
  • Compound 20 was synthesized by the following steps.
  • reaction mixture was passed through celite, and further purified by silica gel column chromatography with hexane / ethyl acetate mixture, methylene chloride Z hexane mixture, and the target compound 20 (yellow solid, molecular weight 876 95, 1.4 mg, yield 2.2%).
  • the measurement conditions for FD-MS measurement were as follows.
  • NMR measurements 1 H—NMR, 13 C—NMR, H—H COZY (homogeneous nuclear correlation two-dimensional NMR spectrum), HMQC (heteronuclear multiquantum correlation two-dimensional NMR spectrum), HMBC (heteronuclear remote multiquantum) Correlated two-dimensional NMR spectra) and NOESY (nuclear overhauser effect correlated two-dimensional NMR spectra) were assigned as follows (Fig. 8: 'H-NMR, Fig. 9: 13C NMR).
  • NMR device name JEOL JNM-ECP 400 (— NMR: 400MHz ⁇ 13 C—NMR: 100 MHz)
  • Compound 20 was synthesized by the following steps.
  • the reaction mixture was passed through Celite, and further purified by silica gel column chromatography using a mixture of hexane and ethyl acetate, or methylene chloride and hexane to obtain the target compound 20 (yellow solid, molecular weight 876). 95, 8.0 milligrams, 11% yield).
  • an organic EL device having a glass substrate, a Z anode, a Z hole injection layer, a Z light emitting layer, a Z hole blocking layer, a Z electron transport layer, and an electron injection layer was prepared.
  • a 1 mm thick glass substrate with an ITO transparent electrode was ultrasonically cleaned in isopropyl alcohol for 5 minutes, followed by UV ozone cleaning for 5 minutes to prepare an electrode-glass substrate assembly.
  • PEDO T polystyrene sulfonic acid
  • a light emitting layer was formed by spin coating on a PEDOT: PSS hole injection layer using a 1:20) black mouth benzene solution to obtain a light emitting layer.
  • the thickness of this light emitting layer was 70 nm.
  • the substrate was deposited on the substrate holder of the vacuum deposition system, bathocuproine (BCP) with a film pressure of 20 nm, and then tris (8-hydroxyquinoline) aluminum (Alq) with a film thickness of 20 nm. ) was formed by vacuum evaporation.
  • BCP bathocuproine
  • Alq (8-hydroxyquinoline) aluminum
  • This BCP film functions as a hole blocking layer.
  • the Alq film functions as an electron transport layer. Furthermore, vacuum evaporation of lnm thick lithium fluoride
  • the film was formed by the method to form an electron injection layer. Finally, an aluminum (A1) cathode with a film thickness of 150 nm was formed by vacuum evaporation to produce an organic EL device.
  • Fig. 11 shows the EL spectrum of the obtained organic EL device.
  • the organic EL device using the transition metal complex compound of the present invention has high emission efficiency and long emission lifetime. Moreover, it has a metal carbene bond of the present invention Organic EL devices using transition metal complex compounds emit blue light, have high luminous efficiency, and have a long emission lifetime. Therefore, it is extremely useful as a material for organic EL devices that require blue light emission.

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Abstract

L’invention concerne un composé de complexe de métal de transition, trois ligands étant réticulés en une configuration de tripode par un groupement de pontage ayant une structure cyclique saturée ou une structure polycyclique saturée. L’invention concerne également un dispositif électroluminescent organique, un film mince organique composé d’une ou de plusieurs couches comprenant au moins une couche émettrice de lumière étant interposé entre une paire d’électrodes. Au moins une couche du film mince organique contenant un tel composé de complexe de métal de transition, le dispositif électroluminescent organique est capable de présenter une efficacité lumineuse élevée, tout en ayant une longue durée de vie d’émission. Le composé de complexe de métal de transition permet de réaliser un tel dispositif électroluminescent organique.
PCT/JP2007/051263 2006-01-27 2007-01-26 Compose de complexe de metal de transition et dispositif electroluminescent organique l’utilisant Ceased WO2007086505A1 (fr)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008096609A1 (fr) * 2007-02-05 2008-08-14 Idemitsu Kosan Co., Ltd. Composé complexe en métal de transition et dispositif électroluminescent organique l'utilisant
JP2009076509A (ja) * 2007-09-18 2009-04-09 Fujifilm Corp 有機電界発光素子
CN101643479B (zh) * 2008-08-07 2012-07-18 通用电气公司 含苯吡啶单元的化合物
JP2013247174A (ja) * 2012-05-24 2013-12-09 Konica Minolta Inc 有機エレクトロルミネッセンス素子及び照明装置
JP2015053493A (ja) * 2008-10-01 2015-03-19 エルジー・ケム・リミテッド 有機発光素子およびその製造方法
JP2019523262A (ja) * 2016-07-25 2019-08-22 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ 金属錯体の、有機エレクトロルミネッセンス素子における発光体としての使用
JP2019527684A (ja) * 2016-07-14 2019-10-03 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ 金属錯体
JP2019529349A (ja) * 2016-07-25 2019-10-17 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ 三脚型二座副配位子を含む、二核およびオリゴ核の金属錯体、並びにその電子デバイスにおける使用
JP2019534244A (ja) * 2016-08-30 2019-11-28 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ 金属錯体
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WO2008096609A1 (fr) * 2007-02-05 2008-08-14 Idemitsu Kosan Co., Ltd. Composé complexe en métal de transition et dispositif électroluminescent organique l'utilisant
JP2009076509A (ja) * 2007-09-18 2009-04-09 Fujifilm Corp 有機電界発光素子
CN101643479B (zh) * 2008-08-07 2012-07-18 通用电气公司 含苯吡啶单元的化合物
JP2015053493A (ja) * 2008-10-01 2015-03-19 エルジー・ケム・リミテッド 有機発光素子およびその製造方法
JP2013247174A (ja) * 2012-05-24 2013-12-09 Konica Minolta Inc 有機エレクトロルミネッセンス素子及び照明装置
US10840468B2 (en) 2013-07-11 2020-11-17 Joled Inc. Organic EL element and method for manufacturing organic EL element
JP7039549B2 (ja) 2016-07-14 2022-03-22 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 金属錯体
JP2019527684A (ja) * 2016-07-14 2019-10-03 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ 金属錯体
US12479873B2 (en) 2016-07-14 2025-11-25 UDC Ireland Metal complexes
US11713332B2 (en) 2016-07-14 2023-08-01 Merck Patent Gmbh Metal complexes
US10720587B2 (en) 2016-07-19 2020-07-21 Universal Display Corporation Organic electroluminescent materials and devices
JP2019523262A (ja) * 2016-07-25 2019-08-22 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ 金属錯体の、有機エレクトロルミネッセンス素子における発光体としての使用
JP7030780B2 (ja) 2016-07-25 2022-03-07 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 三脚型二座副配位子を含む、二核およびオリゴ核の金属錯体、並びにその電子デバイスにおける使用
JP7030781B2 (ja) 2016-07-25 2022-03-07 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 金属錯体の、有機エレクトロルミネッセンス素子における発光体としての使用
US11437592B2 (en) 2016-07-25 2022-09-06 Merck Patent Gmbh Dinuclear and oligonuclear metal complexes containing tripodal bidentate part ligands and their use in electronic devices
US11932659B2 (en) 2016-07-25 2024-03-19 Udc Ireland Limited Metal complexes for use as emitters in organic electroluminescence devices
JP2019529349A (ja) * 2016-07-25 2019-10-17 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ 三脚型二座副配位子を含む、二核およびオリゴ核の金属錯体、並びにその電子デバイスにおける使用
JP7039566B2 (ja) 2016-08-30 2022-03-22 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 金属錯体
JP2019534244A (ja) * 2016-08-30 2019-11-28 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ 金属錯体
US11370809B2 (en) 2019-02-08 2022-06-28 Universal Display Corporation Organic electroluminescent materials and devices
US12137605B2 (en) 2019-02-08 2024-11-05 Universal Display Corporation Organic electroluminescent materials and devices
JP2023504723A (ja) * 2019-12-04 2023-02-06 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 金属錯体
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