Title:
PHOTOLUMINESCENT METAL-(BIS)LIGAND COMPLEXES HAVING DIFFERENT LIGANDS
Document Type and Number:
WIPO Patent Application WO2000050534
Kind Code:
A3
Abstract:
Photoluminescent complexes of copper, silver, zinc, lithium or similar metals are described, being (bis)ligand, with two different ligands. A variety of ligands may be used, the larger ligand being of a size or shape such that a pair of such ligand are prevented by steric properties from forming a (bis)ligand complex with the metal. Preferred substituents may be alkyl, aryl or alkaryl hydrocarbons, or halogen, chalcogen, nitrogen or phosphorus moieties, or included heteroatoms. Formulation of the (bis)ligand complex is accomplished by maintaining the molar ratios of reactants at that which is equivalent to the (bis)ligand complex composition. The complexes are useful as optical sensors for O2, NH3 and NOx, in dye sensitization for photovoltaic devices/solar cells, in producing visible TiO2 photosensitization and in H2 production from the photochemically splitting water. These heteroleptic complexes exhibit photoluminescence equal to or better than ruthenium homoleptic complexes.
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Inventors:
KARPISHIN TIMOTHY B
MILLER MARK T
MILLER MARK T
Application Number:
PCT/US2000/004622
Publication Date:
December 21, 2000
Filing Date:
February 23, 2000
Export Citation:
Assignee:
UNIV CALIFORNIA (US)
International Classes:
C07F1/00; C09K11/06
Other References:
SCHMITTEL, MICHAEL ET AL: "New building blocks for sensors and supramolecular arrays. 4. Stable mixed phenanthroline copper (I) complexes. Key building blocks for supramolecular coordination chemistry", CHEM. COMMUN. (CAMBRIDGE) (1997), (11), 999-1000, XP002146765
SCHNITTEL M ET AL: "SYNTHESIS OF STERICALLY ENCUMBERED 2,9-DIARYL SUBSTITUTED PHENANTHROLINES KEY BUILDING BLOCKS FOR THE PREPARATION OF MIXED (BIS-HETEROLEPTIC) PHENANTHROLINE COPPER(I) CMPLEXES (1)", HETEROCYCLIC COMMUNICATIONS,IL,FREUND PUBLISHING HOUSE, TEL AVIV, vol. 3, no. 6, 1997, pages 493 - 498, XP000872155, ISSN: 0793-0283
NIERENGARTEN, JEAN FRANCOIS ET AL: "Synthesis of a doubly interlocked [2]- catenane", J. AM. CHEM. SOC. (1994), 116(1), 375-6, XP002146766
BLASKIE, MARCUS W. ET AL: "Photostudies of copper (I) systems. 6. Room -temperature emission and quenching studies of bis(2,9-dimethyl-1,10-phenanthroline) copper (I)", INORG. CHEM. (1980), 19(11), 3519-22, XP002146767
ISHIJI T ET AL: "Microenvironmental studies of an Ru(bpy)3luminescent probe incorporated into Nafion film and its application to an oxygen sensor", SENSORS AND ACTUATORS B,CH,ELSEVIER SEQUOIA S.A., LAUSANNE, vol. 22, no. 3, 1 December 1994 (1994-12-01), pages 205 - 210, XP004011066, ISSN: 0925-4005
MCMURRAY H N ET AL: "OXYGEN QUENCHING OF TRIS(2,2'-BIPYRIDINE) RUTHENIUM(II) COMPLEXES IN THIN ORGANIC FILMS", JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY, A: CHEMISTRY,CH,ELSEVIER SEQUOIA, LAUSANNE, vol. 80, no. 1/03, 1994, pages 283 - 288, XP000872207, ISSN: 1010-6030
TENNAKONE K ET AL: "SOLID-STATE PHOTOVOLTAIC CELL SENSITIZED WITH A RUTHENIUM BIPYRIDYL COMPLEX", JOURNAL OF PHYSICS D. APPLIED PHYSICS,GB,IOP PUBLISHING, BRISTOL, vol. 31, no. 12, 21 June 1998 (1998-06-21), pages 1492 - 1496, XP000869122, ISSN: 0022-3727
MILLER, MARK T. ET AL: "A photoluminescent copper (I) complex with an exceptionally high CuII/CuI redox potential: [Cu(bfp)2]+ (bfp = 2,9-bis(trifluoromethyl)-1,10-phenanthroline)", ANGEW. CHEM., INT. ED. (1998), 37(11), 1556-1558, XP002146768
PALLENBERG, ALEXANDER J. ET AL: "Synthesis and Characterization of Some Copper (I) Phenanthroline Complexes", INORG. CHEM. (1995), 34(11), 2833-40, XP000900904
SCHNITTEL M ET AL: "SYNTHESIS OF STERICALLY ENCUMBERED 2,9-DIARYL SUBSTITUTED PHENANTHROLINES KEY BUILDING BLOCKS FOR THE PREPARATION OF MIXED (BIS-HETEROLEPTIC) PHENANTHROLINE COPPER(I) CMPLEXES (1)", HETEROCYCLIC COMMUNICATIONS,IL,FREUND PUBLISHING HOUSE, TEL AVIV, vol. 3, no. 6, 1997, pages 493 - 498, XP000872155, ISSN: 0793-0283
NIERENGARTEN, JEAN FRANCOIS ET AL: "Synthesis of a doubly interlocked [2]- catenane", J. AM. CHEM. SOC. (1994), 116(1), 375-6, XP002146766
BLASKIE, MARCUS W. ET AL: "Photostudies of copper (I) systems. 6. Room -temperature emission and quenching studies of bis(2,9-dimethyl-1,10-phenanthroline) copper (I)", INORG. CHEM. (1980), 19(11), 3519-22, XP002146767
ISHIJI T ET AL: "Microenvironmental studies of an Ru(bpy)3luminescent probe incorporated into Nafion film and its application to an oxygen sensor", SENSORS AND ACTUATORS B,CH,ELSEVIER SEQUOIA S.A., LAUSANNE, vol. 22, no. 3, 1 December 1994 (1994-12-01), pages 205 - 210, XP004011066, ISSN: 0925-4005
MCMURRAY H N ET AL: "OXYGEN QUENCHING OF TRIS(2,2'-BIPYRIDINE) RUTHENIUM(II) COMPLEXES IN THIN ORGANIC FILMS", JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY, A: CHEMISTRY,CH,ELSEVIER SEQUOIA, LAUSANNE, vol. 80, no. 1/03, 1994, pages 283 - 288, XP000872207, ISSN: 1010-6030
TENNAKONE K ET AL: "SOLID-STATE PHOTOVOLTAIC CELL SENSITIZED WITH A RUTHENIUM BIPYRIDYL COMPLEX", JOURNAL OF PHYSICS D. APPLIED PHYSICS,GB,IOP PUBLISHING, BRISTOL, vol. 31, no. 12, 21 June 1998 (1998-06-21), pages 1492 - 1496, XP000869122, ISSN: 0022-3727
MILLER, MARK T. ET AL: "A photoluminescent copper (I) complex with an exceptionally high CuII/CuI redox potential: [Cu(bfp)2]+ (bfp = 2,9-bis(trifluoromethyl)-1,10-phenanthroline)", ANGEW. CHEM., INT. ED. (1998), 37(11), 1556-1558, XP002146768
PALLENBERG, ALEXANDER J. ET AL: "Synthesis and Characterization of Some Copper (I) Phenanthroline Complexes", INORG. CHEM. (1995), 34(11), 2833-40, XP000900904
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