WO2015053292A1 - Complexe d'iridium - Google Patents

Complexe d'iridium Download PDF

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WO2015053292A1
WO2015053292A1 PCT/JP2014/076862 JP2014076862W WO2015053292A1 WO 2015053292 A1 WO2015053292 A1 WO 2015053292A1 JP 2014076862 W JP2014076862 W JP 2014076862W WO 2015053292 A1 WO2015053292 A1 WO 2015053292A1
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carbon atoms
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alkyl group
represented
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直田健
小宮成義
川守田創一郎
今田泰嗣
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国立大学法人大阪大学
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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    • 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
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
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    • 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 an iridium complex.
  • the phosphorescent light emission by the organometallic complex can achieve a theoretically higher quantum efficiency than the fluorescent light emission in organic EL (electroluminescence).
  • the said organometallic complex is anticipated as a material of functional elements, such as an organic light emitting element which is a next generation technique, specifically, a material of an organic EL display, etc.
  • Non-Patent Document 1 a compound that generates phosphorescent light is easily quenched in a high concentration solution or a solid state.
  • a compound represented by the following formula (X) generates strong phosphorescent light emission in a solution state (quantum yield 97%), but quenches in an amorphous solid state (quantum yield 0.6%). It is known (for example, Non-Patent Document 1).
  • Non-Patent Documents 2 and 3 Recently, phosphorescent gold complexes having gelling ability (see, for example, Non-Patent Documents 2 and 3) and platinum complexes (for example, see Non-Patent Documents 4 to 7) have been reported.
  • these gold complexes and platinum complexes have a gelling ability as a whole compound by containing a structure having a gelling ability in the complex itself.
  • an object of the present invention is to provide a luminescent material having improved luminescence intensity in a gel state than in a solution state.
  • the present invention is an iridium complex represented by the formula (I).
  • Any one of hydrogens in the group represented by any one of the formulas (1) to (10) is substituted with a group represented by the formula —OX; and Any one or more of the remaining hydrogens in the group represented by any one of the formulas (1) to (10) is optionally a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 2 to 12 carbon atoms.
  • R 100 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms
  • M is 2 to 1,000
  • phenyl group, phenoxy group, nitrile group, nitro group, or thiol group substituent R may be substituted
  • X is a group represented by the formula (a)
  • n1, n2, n3 and n4 are each independently 1 to 20, R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, — (OCH 2 CH 2 ) m —OR 100 (R 100 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m is 2 to 1,000), —NH 2 , —N (alkyl having 1 to 6 carbon atoms) Group) 2 , —OH, —COOH, —C ( ⁇ O) O— (alkyl group having 1 to 6 carbon atoms), phenyl group, phenoxy group, nitrile group, nitro group, or thiol group, Two
  • Any one or more of hydrogens in the group represented by any one of the formulas (11) to (74) is optionally a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.
  • R 100 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m Is 2 to 1,000), —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C ( ⁇ O) O— (alkyl having 1 to 6 carbon atoms) Group), phenyl group, phenoxy group, nitrile group, nitro group, or thiol group substituent R ′.
  • the present invention also provides the iridium complex, It is a composition for luminescent materials containing a supramolecular gelling agent.
  • the present invention is a gel-like luminescent material obtained from the luminescent material composition. Moreover, this invention is a luminescent material containing a supramolecular gel and the iridium complex of this invention covalently bonded to the said supramolecular gel.
  • the gel-like luminescent material obtained from the composition for luminescent material containing the iridium complex of the present invention and the supramolecular gelling agent has an advantage that the luminescence intensity is improved in the gel state as compared with the solution state.
  • the inventors of the present invention have provided a novel iridium complex (I) in which an amino acid side chain moiety represented by the formula (a) is bound to an iridium compound known to have phosphorescence emission performance, and a supramolecular gelling agent. It was unexpectedly found that the gel-like material obtained from the above showed stronger emission intensity than the solution state of the novel iridium complex (I) alone. On the other hand, the iridium compound represented by the following formula (IV) having no amino acid side chain moiety represented by the formula (a) was obtained from a supramolecular gelling agent even in a single solution state. It has also been found that there is almost no change in emission intensity even in the state of a gel material. Based on these findings, the present inventors have completed the present invention.
  • Any one of hydrogens in the group represented by any one of the formulas (1) to (10) is substituted with a group represented by the formula —O— (CH 2 ) n1 —COOR 21 (R 21 is an alkyl group having 1 to 12 carbon atoms), and Any one or more of the remaining hydrogens in the group represented by any one of the formulas (1) to (10) is optionally a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 2 to 12 carbon atoms.
  • An alkenyl group, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, — (OCH 2 CH 2 ) m —OR 100 (R 100 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms) , M is 2 to 1,000), —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C ( ⁇ O) O— (1 to 6 carbon atoms) Alkyl group), phenyl group, phenoxy group, nitrile group, nitro group, or thiol group.
  • n1 are as defined in formula (I).
  • the iridium platinum complex of the present invention is represented by the following formula (I).
  • Any one of hydrogens in the group represented by any one of the formulas (1) to (10) is substituted with a group represented by the formula —OX; and Any one or more of the remaining hydrogens in the group represented by any one of the formulas (1) to (10) is optionally a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 2 to 12 carbon atoms.
  • R 100 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms
  • M is 2 to 1,000
  • phenyl group, phenoxy group, nitrile group, nitro group, or thiol group substituent R may be substituted
  • X is a group represented by the formula (a)
  • n1, n2, n3 and n4 are each independently 1 to 20, R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, — (OCH 2 CH 2 ) m —OR 100 (R 100 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m is 2 to 1,000), —NH 2 , —N (alkyl having 1 to 6 carbon atoms) Group) 2 , —OH, —COOH, —C ( ⁇ O) O— (alkyl group having 1 to 6 carbon atoms), phenyl group, phenoxy group, nitrile group, nitro group, or thiol group, Two
  • Any one or more of hydrogens in the group represented by any one of the formulas (11) to (74) is optionally a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.
  • R 100 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m Is 2 to 1,000), —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C ( ⁇ O) O— (alkyl having 1 to 6 carbon atoms) Group), phenyl group, phenoxy group, nitrile group, nitro group, or thiol group substituent R ′.
  • any one or more of the remaining hydrogens in the group represented by any one of the formulas (1) to (10) is optionally a halogen atom, an alkyl group having 1 to 12 carbon atoms, or 2 to 2 carbon atoms.
  • any one or more of the hydrogen atoms in the group represented by any one of the above formulas (11) to (74) is optionally a halogen atom, an alkyl group having 1 to 12 carbon atoms, or 2 to 12 carbon atoms.
  • An alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, — (OCH 2 CH 2 ) m —OR 100 (R 100 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms) M is from 2 to 1,000), —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C ( ⁇ O) O— (from 1 to carbon atoms) 6 alkyl group), a phenyl group, a phenoxy group, a nitrile group, a nitro group, or a substituent group R ′ of a thiol group, which is represented by any one of the formulas (11) to (74). Any two or more of the hydrogens in the group are replaced by the substituent R ′ If it is, even though each of the substituents R 'are different, may be identical.
  • N1, n2, n3 and n4 are each independently 1 to 20.
  • the n1 is preferably 1 to 10, and more preferably 3 to 8.
  • the n2 is preferably 1 to 10, and more preferably 1 to 5.
  • N3 is preferably 5 to 20, and more preferably 5 to 10.
  • the n4 is preferably 5 to 20, and more preferably 5 to 10.
  • the iridium complex of the present invention is
  • N1, n2, n3 and n4 in formula (a) are each independently 1 to 6, R 1 and R 2 are hydrogen atoms, Two
  • Any one or more of hydrogens in the group represented by any one of the formulas (11), (15), and (27) may be optionally replaced with a halogen atom.
  • the iridium complex of the present invention is
  • N1, n2, n3 and n4 in formula (a) are each independently 1 to 6, R 1 and R 2 are hydrogen atoms, Two
  • Any one or more of hydrogens in the group represented by the formula (11) or (27) may be optionally replaced with a halogen atom.
  • the iridium complex of the present invention is more preferably a compound represented by formula (I-1), formula (I-2), or formula (I-3).
  • the present invention is also a composition for a luminescent material comprising the iridium complex of the present invention and a supramolecular gelling agent.
  • the supramolecular gelling agent is preferably a gelling agent that causes gelation by hydrogen bonding, and more preferably a gelling agent that is soluble in an organic solvent.
  • Examples of the supramolecular gelling agent include compounds represented by the following formula (XI).
  • n12, n13 and n14 are each independently 0 to 20, n11 is 6 to 20, R 11 , R 12 and R 13 are each independently a hydrogen atom, a halogen atom, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms,-( OCH 2 CH 2 ) m —OR 100 (R 100 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m is 2 to 1,000), —NH 2 , —N (1 to 6 alkyl group) 2 , —OH, —COOH, —C ( ⁇ O) O— (alkyl group having 1 to 6 carbon atoms), phenyl group, phenoxy group, nitrile group, nitro group, or thiol group.
  • n12, n13 and n14 are each independently 1 to 6, n11 is 6 to 15, R11, R12 and R13 are preferably hydrogen atoms.
  • the compound represented by the formula (XI) is, for example, a compound represented by the formula (XI-1).
  • a compound represented by the formula (XII) and a compound represented by the formula (XIII) can be used.
  • the compound represented by the formula (XII) see Hanabusa et al., Angew. Chem. Int. Ed., 1996, 35, p.1949-1951.
  • the compound represented by the formula (XIII) see Suzuki et al., Langumuir, 2003, 19, p.8623-8624.
  • alkyl group having 1 to 12 carbon atoms includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like.
  • the alkyl group may be linear or branched.
  • the alkyl group having 1 to 12 carbon atoms is, for example, an alkyl group having 1 to 10 carbon atoms, preferably 5 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms.
  • C2-C12 alkenyl group includes, for example, ethylenyl, propylenyl, butenyl, pentenyl, hexenyl and the like.
  • the alkenyl group may be linear or branched.
  • Examples of the alkenyl group having 2 to 12 carbon atoms include alkenyl groups having 2 to 10 carbon atoms, preferably 5 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms.
  • alkynyl group having 2 to 12 carbon atoms includes, for example, acetylenyl, propenyl and the like.
  • the alkynyl group may be linear or branched.
  • the alkynyl group having 2 to 12 carbon atoms is, for example, an alkynyl group having 2 to 10 carbon atoms, preferably 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms.
  • alkoxy group having 1 to 12 carbon atoms is an alkyloxy group.
  • the alkyl part of the alkyloxy group is the same as the alkyl group having 1 to 12 carbon atoms.
  • Examples of the alkoxyl group include methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy and the like.
  • the alkoxy group having 1 to 12 carbon atoms is, for example, an alkoxy group having 1 to 10 carbon atoms, preferably 5 to 10 carbon atoms, and more preferably 5 to 8 carbon atoms.
  • the alkyl group moiety of the term “—N (C 1-6 alkyl group) 2 ” is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl and the like.
  • the alkyl moieties may be the same as or different from each other.
  • Examples of —N (C 1-6 alkyl group) 2 include dimethylamino, diethylamino, methylethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino and the like.
  • the alkyl group moiety may be linear or branched.
  • —N (alkyl group having 1 to 6 carbon atoms) 2 is, for example, —N (alkyl group having 1 to 5 carbon atoms) 2 , preferably —N (alkyl group having 1 to 4 carbon atoms) 2 , more preferably Is —N (an alkyl group having 1 to 3 carbon atoms) 2 .
  • the alkyl group moiety of the term “—C ( ⁇ O) O— (C 1-6 alkyl group)” is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl and the like.
  • Examples of —C ( ⁇ O) O— (an alkyl group having 1 to 6 carbon atoms) include —C ( ⁇ O) O-methyl, —C ( ⁇ O) O-ethyl, —C ( ⁇ O) O.
  • Examples of —C ( ⁇ O) O— include —C ( ⁇ O) O— (alkyl group having 1 to 5 carbon atoms), preferably —C ( ⁇ O).
  • O— an alkyl group having 1 to 4 carbon atoms
  • more preferably —C ( ⁇ O) O— an alkyl group having 1 to 3 carbon atoms.
  • the iridium complex of the present invention can be produced, for example, as follows.
  • Any one of hydrogens in the group represented by any one of the formulas (1) to (10) is substituted with a group represented by the formula —O— (CH 2 ) n1 —COOH; and Any one or more of the remaining hydrogens in the group represented by any one of the formulas (1) to (10) is optionally a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 2 to 12 carbon atoms.
  • An alkenyl group, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, — (OCH 2 CH 2 ) m —OR 100 (R 100 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms) , M is 2 to 1,000), —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C ( ⁇ O) O— (1 to 6 carbon atoms) Alkyl group), phenyl group, phenoxy group, nitrile group, nitro group, or thiol group.
  • n1 is the same as defined in formula (I).
  • n2, n3, n4, R 1 and R 2 are the same as defined in the formula (I).
  • the compound of formula (I) is reacted with the compound of formula (III) in the presence of a condensing agent to obtain a compound of formula (I).
  • a condensing agent examples include EDCI (1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride), DCC (dicyclohexylcarbodiimide) and the like.
  • DMAP dimethylaminopropylcarbodiimide
  • DMAP dimethylaminopropylcarbodiimide
  • This reaction is performed, for example, at room temperature to 100 ° C. for 3 hours to 24 hours.
  • the solvent for this reaction is not limited, and for example, 1,2-dichloroethane, 1, 1? And dichloromethane.
  • the compound represented by the formula (II) and the compound represented by the formula (III) may be obtained commercially, or may be made in-house with reference to known literatures.
  • the compound represented by the formula (II) can be produced, for example, as follows.
  • Any one of hydrogens in the group represented by any one of the formulas (101) to (110) is substituted with a group represented by the formula —O— (CH 2 ) n1 —COOR 21 (R 21 is an alkyl group having 1 to 12 carbon atoms), and Any one or more of the remaining hydrogens in the group represented by any one of the formulas (101) to (110) is optionally a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 2 to 12 carbon atoms.
  • An alkenyl group, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, — (OCH 2 CH 2 ) m —OR 100 (R 100 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms) , M is 2 to 1,000), —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C ( ⁇ O) O— (1 to 6 carbon atoms) Alkyl group), phenyl group, phenoxy group, nitrile group, nitro group, or thiol group.
  • Any one of hydrogens in the group represented by any one of the formulas (1) to (10) is substituted with a group represented by the formula —O— (CH 2 ) n1 —COOR 21 (R 21 is an alkyl group having 1 to 12 carbon atoms), and Any one or more of the remaining hydrogens in the group represented by any one of the formulas (1) to (10) is optionally a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 2 to 12 carbon atoms.
  • An alkenyl group, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, — (OCH 2 CH 2 ) m —OR 100 (R 100 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms) , M is 2 to 1,000), —NH 2 , —N (alkyl group having 1 to 6 carbon atoms) 2 , —OH, —COOH, —C ( ⁇ O) O— (1 to 6 carbon atoms) Alkyl group), phenyl group, phenoxy group, nitrile group, nitro group, or thiol group.
  • the compound represented by the formula (IV) is obtained by heating the compound of the formula (V) and the compound of the formula (VI) in a solvent.
  • This reaction may be performed in the presence of silver trifluoromethanesulfonate, silver trifluoroacetate, or the like.
  • This reaction is performed, for example, at the reflux temperature of the solvent for the necessary time.
  • a solvent of this reaction For example, toluene, benzene, etc. are mentioned.
  • the compound of formula (II) can be obtained by subjecting the obtained compound of formula (IV) to ester decomposition by heating in the presence of an alkali.
  • the alkali in the ester decomposition include lithium hydroxide.
  • This ester decomposition is performed, for example, at a reflux temperature of the solvent for a necessary time.
  • the ester decomposition solvent include, but are not limited to, THF, methanol, water, a mixture thereof, and the like.
  • the luminescent material of the present invention is a gel luminescent material obtained from the composition for luminescent material of the present invention. Specifically, for example, an iridium complex solution and a supramolecular gelling agent solution included in the composition for a luminescent material of the present invention are prepared, mixed, heated, and then cooled to room temperature. By doing so, a gel-like luminescent material can be obtained.
  • the heating temperature is, for example, 40 to 100 ° C., preferably 80 to 100 ° C.
  • the concentration of the iridium complex solution is, for example, 1.0 ⁇ 10 ⁇ 5 to 4.0 ⁇ 10 ⁇ 4 mol / L, preferably 1.0 ⁇ 10 ⁇ 4 to 2.0 ⁇ 10 ⁇ 4 mol / L.
  • the concentration of the supramolecular gelling agent solution is, for example, 2.0 ⁇ 10 ⁇ 2 to 2.0 ⁇ 10 ⁇ 1 mol / L, preferably 2.0 ⁇ 10 ⁇ 2 to 5.0 ⁇ 10 ⁇ 2 mol / L. .
  • the luminescent material of the present invention is a luminescent material containing a supramolecular gel and the iridium complex of the present invention covalently bonded to the supramolecular gel.
  • the supramolecular gel is produced from the supramolecular gelling agent.
  • the luminescent material of the present invention has an effect that the emission intensity is improved in the gel state than in the solution state. Therefore, the light-emitting material of the present invention can be used as a high-luminance light-emitting material and a light-emitting material of an organic EL element, specifically, a material of a light-emitting layer.
  • an organic EL element for example, a substrate, an anode, a hole transport layer, a light emitting layer containing the light emitting material of the present invention, an electron transport layer, and a cathode are laminated in this order.
  • the substrate, the anode, the hole transport layer, the electron transport layer, and the cathode may be formed by a conventionally known manufacturing method using a conventionally known material.
  • the light emitting layer may contain a host material in addition to the light emitting material of the present invention.
  • the host material include those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton.
  • Mass spectrometry was measured using a mass spectrometer (model number JMS-DX303HF) manufactured by JEOL Ltd.
  • the IR analysis was performed using a Fourier transform infrared spectrophotometer (model number FTIR-4100) manufactured by JASCO Corporation.
  • the melting point was measured using a melting point measuring device (model MP-21) manufactured by Yamato Scientific Co., Ltd.
  • the quantum yield was measured using a fluorometer FP-6500N, a low-temperature medium integrating sphere system INK-533 for phosphorescence measurement, and a liquid sample cell LPH-120 (all manufactured by JASCO Corporation).
  • EDCI 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride
  • DMAP N, N-dimethyl-4-aminopyridine
  • the emission quantum yield ⁇ (%) of the compound (I-1) and the compound (IV-1) in a solution state (296K) was measured. Specifically, a 2-MeTHF solution (2.0 ⁇ 10 ⁇ 4 M) of each compound was obtained by an absolute method. The measuring method is as follows.
  • each sample was measured in an argon atmosphere as it was by removing the oxygen by passing an argon stream through the solution for 1 minute. All emission spectra were corrected by using a standard light source. The measurement results are shown in Table 1.
  • novel iridium complex (I) of the present invention exhibits the effects as described above is unclear, the present inventors presume the following mechanism.
  • the novel iridium complex (I) of the present invention is considered to be incorporated and immobilized in the gel fiber formed by the supramolecular gelling agent. In that case, the possibility of interaction between iridiums is reduced, and quenching is suppressed. Therefore, it is conceivable that the novel iridium complex (I) of the present invention exhibits a stronger luminescence intensity in a gel material obtained from a supramolecular gelling agent than in a single solution state.
  • the iridium compound of the formula (IV) is not incorporated into the gel fiber but only confined between the gel fibers in the gel material from the supramolecular gelling agent. In that case, the possibility of interaction between iridium is equivalent to that in the solution state, and therefore, it is considered that there is no significant change in the emission intensity.
  • the luminescent material of the present invention Since the luminescent material of the present invention has a higher emission intensity in the gel state than in the solution state, the emission intensity sufficient for practical use can be obtained. Therefore, the luminescent material of the present invention is useful as a material for an organic light-emitting device or the like that is a next-generation technology. Moreover, the luminescent material of the present invention is excellent in coatability and can emit light under UV light. Therefore, the luminescent material of the present invention is useful as a material for a luminescent paint sensitive to UV light.

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Abstract

Le problème de la présente invention concerne une substance luminescente qui présente une intensité de luminescence augmentée dans un état de gel par rapport à un état de solution. Selon l'invention, une substance luminescente de type gel est obtenue à partir d'une composition de substance luminescente comprenant : un complexe d'iridium représenté par la formule (I); et un gélifiant supramoléculaire. Dans la formule, AA représente respectivement un groupe exprimé par l'une quelconque des formules (1) à (10) et un groupe exprimé par l'une quelconque des formules (11) à (74).
PCT/JP2014/076862 2013-10-11 2014-10-07 Complexe d'iridium WO2015053292A1 (fr)

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CN110862547A (zh) * 2019-11-13 2020-03-06 华中科技大学 一种稀土超分子凝胶发光材料、其制备和应用

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