Title:
PHOTOLUMINESCENT METAL-(BIS)LIGAND COMPLEXES HAVING DIFFERENT LIGANDS
Document Type and Number:
WIPO Patent Application WO/2000/050534
Kind Code:
A2
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 O¿2?, NH¿3? and NO¿x?, in dye sensitization for photovoltaic devices/solar cells, in producing visible TiO¿2? photosensitization and in H¿2? 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:
August 31, 2000
Filing Date:
February 23, 2000
Export Citation:
Assignee:
UNIV CALIFORNIA (US)
International Classes:
C07F1/00; C09K11/06; (IPC1-7): C09K11/00
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 [2Ü- 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: ÄCu(bfp)2Ü+ (bfp = 2,9-bis(trifluoromethyl)-1,10-phenanthroli ne)" 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 [2Ü- 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: ÄCu(bfp)2Ü+ (bfp = 2,9-bis(trifluoromethyl)-1,10-phenanthroli ne)" 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
Attorney, Agent or Firm:
Mcclain, James W. (Martin Haller & McClain 1660 Union Street
San Diego, CA, US)
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Claims:
CLAIMS
| 1. | A complex being heteroleptic and comprising a metal bound to a first ligand and a second ligands, each ligand having a pair of substituents with said substituents on said first ligand being different from the substituents on said second ligand, one of said ligands being of a size and shape which prevents two of that ligand from forming a homoleptic complex with said metal, and said different ligands not interfering sterically with each other. |
| 2. | A complex as in Claim 1 wherein said metal comprises copper, silver, zinc or lithium or an analog thereof. |
| 3. | A complex as in Claim 1 wherein each said ligand comprises a hydrocarbon or substituted hydrocarbon compound. |
| 4. | A complex as in Claim 3 wherein substituents on said substituted hydrocarbon compound are disposed terminally of said substituted hydrocarbon compound. |
| 5. | A complex as in Claim 3 wherein said substituted hydrocarbon comprises a hydrocarbon compound containing at least one alkyl, aryl, or alkaryl or halogen, chalcogen, nitrogenor phosphoruscontaining moiety or a heteroatom. |
| 6. | A complex as in Claim 3 wherein at least one of said ligands comprises phenanthroline or a substituted phenanthroline compound. |
| 7. | A complex as in Claim 1 having the property of photoluminescence. |
| 8. | A method for preparation of a heteroleptic complex of a metal bound to a first ligand and a second ligand, each ligand having a pair of substituents with said substituents on said first ligand being different from the substituents on said second ligand, one of said ligands being of a size and shape which prevents two of that ligand from forming a homoleptic complex with said metal, and said different ligands not interfering sterically with each other, which method comprises reacting said metal and each of said ligands in solution in equal molar amounts, such that formation of said heteroleptic complex proceeds to the substantial exclusion of formation of any homoleptic complexes of said metal and either ligand. |
| 9. | A method as in Claim 8 wherein said metal comprises copper, silver, zinc or lithium or an analog thereof. |
| 10. | A method as in Claim 8 further comprising using as each said ligand a hydrocarbon or substituted hydrocarbon compound. |
| 11. | A method as in Claim 10 further comprising having substituents on said substituted hydrocarbon compound disposed terminally of said substituted hydrocarbon compound. |
| 12. | A method as in Claim 10 further comprising using as said substituted hydrocarbon a hydrocarbon compound containing at least one alkyl, aryl, or alkaryl or halogen, chalcogen, nitrogenor phosphoruscontaining moiety or a heteroatom. |
| 13. | A method as in Claim 10 further comprising using as at least one of said ligands a phenanthroline or substituted phenanthroline compound. |
| 14. | A method as in Claim 1 further comprising said method producing a heteroleptic complex having the property of photoluminescence. |
| 15. | A method for the detection of molecules in a gas comprising contacting said gas with a complex as in Claim 1 and quantifying quenching of photoluminescence of said complex by said gas, wherein the degree of quantification of said quenching is indicative of the concentration of said molecules in said gas. |
| 16. | A method as in Claim 15 wherein said molecules comprise oxygen, ammonia, nitric oxide and nitrogen dioxide molecules. |
| 17. | A method as in Claim 16 wherein said molecules comprise oxygen molecules. |
| 18. | A method as in Claim 15 wherein said complex is attached to a solid support. |
| 19. | A method for the detection of molecules in a liquid comprising contacting said liquid with a complex as in Claim 1 and quantifying quenching of photoluminescence of said complex by said liquid, wherein the degree of quantification of said quenching being indicative of the concentration of said molecules in said liquid. |
| 20. | A method as in Claim 19 wherein said molecules comprise oxygen, ammonia, nitric oxide and nitrogen dioxide molecules. |
| 21. | A method as in Claim 20 wherein said molecules comprise oxygen molecules. |
| 22. | A method as in Claim 19 wherein said complex is attached to a solid support. |
| 23. | A method for the visible photosensitization of titanium dioxide comprising contacting said titanium dioxide with a complex as in Claim 1. |
| 24. | A method for the production of hydrogen comprising photochemically splitting water by contact of said water with a complex as in Claim 1. |
| 25. | A method for the sensitization of dyes for photovoltaic devices/solar cells comprising contacting said dyes with a complex as in Claim 1. |
Description:
INTERNATIONALSEARCHREPORT PCT/US00/04622 C.(Continua n)DOCUMENTSCONSIDEREDTOBERELEVANT Category° Citation ofdocument,with indicabon, where appropnate,ofthe relevantpassagesRelevanttodaimNo. XSCHNITTEL M ET AL :"SYNTHESIS OF 1-14 STERICALLYENCUMBERED2,9-DIARYL SUBSTITUTEDPHENANTHROLINESKEYBUILDING BLOCKSFORTHEPREPARATIONOFMIXED (BIS-HETEROLEPTIC)PHENANTHROLINE COPPER(I)CMPLEXES(1)" HETEROCYCLICCOMMUNICATIONS,IL,FREUND PUBLISHINGHOUSE,TELAVIV, vol.3,no.6,1997,pages493-498, XP000872155 ISSN:0793-0283 Ythewholedocument15-25 XNIERENGARTEN,JEANFRANCOISETAL:1-14 "Synthesisofadoublyinterlocked'2!- catenane" J.AM.CHEM.SOC.(1994),116(1),375-6, XP002146766 Yfigure315-25 YBLASKIE,MARCUSW.ETAL:"Photostudies15-22 ofcopper(I)systems.6.Room -temperatureemissionandquenching studiesof bis copper(I)" INORG.CHEM.(1980),19(11),3519-22, XP002146767 page3519-page3520 YISHIJITETAL:"Microenvironmental15-18 studiesofanRu(bpy)31uminescentprobe incorporatedintoNafionfilmandits applicationtoanoxygensensor" SENSORSANDACTUATORSB,CH,ELSEVIER SEQUOIAS.A.,LAUSANNE, vol.22,no.3, 1December1994(1994-12-01),pages 205-210,XP004011066 ISSN:0925-4005 page205-page207 YMCMURRAYHNETAL:"OXYGENQUENCHINGOF19-22 TRIS(2,2'-BIPYRIDINE)RUTHENIUM(II) COMPLEXESINTHINORGANICFILMS" JOURNALOFPHOTOCHEMISTRYAND PHOTOBIOLOGY,A:CHEMISTRY,CH,ELSEVIER SEQUOIA,LAUSANNE, vol.80,no.1/03,1994,pages283-288, XP000872207 ISSN:1010-6030 page283-page284 2 2 INTERNATIONALSEARCHREPORT InterxialApplicationNo PCT/US00/04622 C.(Continuatlon) DOCUMENTS CONSIDEREDTOBERELEVANT CategoryCitabonofdocument,withindication, where appropnate,ofterelevantpassagesRelevanttodaimNo. YTENNAKONEKETAL:"SOLID-STATE23,25 PHOTOVOLTAICCELLSENSITIZEDWITHA RUTHENIUMBIPYRIDYLCOMPLEX" JOURNALOFPHYSICSD.APPLIED PHYSICS,GB,IOPPUBLISHING,BRISTOL, vol.31,no.12, 21June1998(1998-06-21),pages 1492-1496,XP000869122 ISSN:0022-3727 figure1 YMILLER,MARKT.ETAL:"A 24 photoluminescentcopper(I)complexwith anexceptionallyhighCuII/CuIredox potential:'Cu (bfp)2!+(bfp= 2,9-bis (trifluoromethyl)-1, 10-phenanthroli ne)" ANGEW.CHEM.,INT.ED.(1998),37(11), 1556-1558, XP002146768 page1557,column2 APALLENBERG,ALEXANDERJ.ETAL:1-14 "SynthesisandCharacterizationofSome Copper(I)PhenanthrolineComplexes" INORG.CHEM.(1995),34(11),2833-40, XP000900904 table1 2