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Article: 3[(dx2-y2, dxy)(pz)] excited states of binuclear copper(I) phosphine complexes: Effect of copper - ligand and copper - copper interactions on excited state properties and photocatalytic reductions of the 4,4′-dimethyl-2,2′-bipyridinium ion in alcohols

Title3[(dx2-y2, dxy)(pz)] excited states of binuclear copper(I) phosphine complexes: Effect of copper - ligand and copper - copper interactions on excited state properties and photocatalytic reductions of the 4,4′-dimethyl-2,2′-bipyridinium ion in alcohols
Authors
KeywordsCopper
Luminescence
Metal-metal interactions
Phosphanes
Photochemistry
Issue Date2003
PublisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry
Citation
Chemistry - A European Journal, 2003, v. 9 n. 12, p. 2885-2894 How to Cite?
AbstractA comprehensive study of the structural and spectroscopic properties of two-, three-, and four-coordinate copper(I) complexes with aliphatic phosphine ligands is presented. All complexes described in this work are characterized by X-ray crystallography. The intramolecular Cu⋯Cu separations in [Cu2(dcpm)2]X2, [Cu2(dcpm)2-(CH3CN)2] X2, and [Cu2(dmpm)3]-(ClO4)2 (dcpm=bis(dicyclohexylphosphino)methane; dmpm=bis(dimethylphosphino)methane; X=ClO4 - and PF6 -) are in the range 2.639(2)-3.021(2) Å. The anion⋯CuI interaction is weak, as evidenced by the nearest O⋯Cu separation of 2.558(6) Å in [Cu2(dcpm)2](ClO4)2 and the closest Cu⋯F separation of 2.79(1) Å in [Cu2(dcpm)2](PF6)2. The absorption bands of [Cu2(dcpm)2]X2 and [Cu2(dcpm)2(CH3CN)2]X2 (X=ClO4 - and PF6 -) at λmax 307-311 nm in CH2Cl2 are assigned as 1[3dσ* → 4pσ] transitions; this has been confirmed by resonance Raman spectroscopy. The triplet emissions in the visible region from these complexes exhibit long lifetimes and are sensitive to the environment. The lowest emissive excited state is tentatively ascribed as 3[(dx2-y2, dxy)(pz)] in nature. For [Cu2(dcpm)2]2+ salts in CH3CN, the emissive species is postulated to be [Cu2(dcpm)2(CH3CN)n]2+ (n≥3). Efficient photocatalytic reduction of MV2+ (4,4′-dimethyl-2,2′-bipyridinium) to MV+ in alcoholic solutions by using [Cu2(dcpm)2](PF6)2 or [Cu2(dppm)2(CH3CN)4] (ClO4)2 (dppm= bis(diphenylphosphino)methane) as a catalyst has been observed. The addition of CH3CN or use of [Cu2(dmpm)3]-(ClO4)2 as a catalyst did not allow photocatalytic reduction processes to occur.
Persistent Identifierhttp://hdl.handle.net/10722/167805
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorMao, Zen_HK
dc.contributor.authorChao, HYen_HK
dc.contributor.authorHui, Zen_HK
dc.contributor.authorChe, CMen_HK
dc.contributor.authorFu, WFen_HK
dc.contributor.authorCheung, KKen_HK
dc.contributor.authorZhu, Nen_HK
dc.date.accessioned2012-10-08T03:11:51Z-
dc.date.available2012-10-08T03:11:51Z-
dc.date.issued2003en_HK
dc.identifier.citationChemistry - A European Journal, 2003, v. 9 n. 12, p. 2885-2894en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167805-
dc.description.abstractA comprehensive study of the structural and spectroscopic properties of two-, three-, and four-coordinate copper(I) complexes with aliphatic phosphine ligands is presented. All complexes described in this work are characterized by X-ray crystallography. The intramolecular Cu⋯Cu separations in [Cu2(dcpm)2]X2, [Cu2(dcpm)2-(CH3CN)2] X2, and [Cu2(dmpm)3]-(ClO4)2 (dcpm=bis(dicyclohexylphosphino)methane; dmpm=bis(dimethylphosphino)methane; X=ClO4 - and PF6 -) are in the range 2.639(2)-3.021(2) Å. The anion⋯CuI interaction is weak, as evidenced by the nearest O⋯Cu separation of 2.558(6) Å in [Cu2(dcpm)2](ClO4)2 and the closest Cu⋯F separation of 2.79(1) Å in [Cu2(dcpm)2](PF6)2. The absorption bands of [Cu2(dcpm)2]X2 and [Cu2(dcpm)2(CH3CN)2]X2 (X=ClO4 - and PF6 -) at λmax 307-311 nm in CH2Cl2 are assigned as 1[3dσ* → 4pσ] transitions; this has been confirmed by resonance Raman spectroscopy. The triplet emissions in the visible region from these complexes exhibit long lifetimes and are sensitive to the environment. The lowest emissive excited state is tentatively ascribed as 3[(dx2-y2, dxy)(pz)] in nature. For [Cu2(dcpm)2]2+ salts in CH3CN, the emissive species is postulated to be [Cu2(dcpm)2(CH3CN)n]2+ (n≥3). Efficient photocatalytic reduction of MV2+ (4,4′-dimethyl-2,2′-bipyridinium) to MV+ in alcoholic solutions by using [Cu2(dcpm)2](PF6)2 or [Cu2(dppm)2(CH3CN)4] (ClO4)2 (dppm= bis(diphenylphosphino)methane) as a catalyst has been observed. The addition of CH3CN or use of [Cu2(dmpm)3]-(ClO4)2 as a catalyst did not allow photocatalytic reduction processes to occur.en_HK
dc.languageengen_US
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistryen_HK
dc.relation.ispartofChemistry - A European Journalen_HK
dc.subjectCopperen_HK
dc.subjectLuminescenceen_HK
dc.subjectMetal-metal interactionsen_HK
dc.subjectPhosphanesen_HK
dc.subjectPhotochemistryen_HK
dc.title3[(dx2-y2, dxy)(pz)] excited states of binuclear copper(I) phosphine complexes: Effect of copper - ligand and copper - copper interactions on excited state properties and photocatalytic reductions of the 4,4′-dimethyl-2,2′-bipyridinium ion in alcoholsen_HK
dc.typeArticleen_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1002/chem.200204610en_HK
dc.identifier.pmid12868420-
dc.identifier.scopuseid_2-s2.0-0038789203en_HK
dc.identifier.hkuros83822-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0038789203&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume9en_HK
dc.identifier.issue12en_HK
dc.identifier.spage2885en_HK
dc.identifier.epage2894en_HK
dc.identifier.isiWOS:000183712300024-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridMao, Z=7202633924en_HK
dc.identifier.scopusauthoridChao, HY=7202973715en_HK
dc.identifier.scopusauthoridHui, Z=7005565139en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridFu, WF=7202947315en_HK
dc.identifier.scopusauthoridCheung, KK=7402406613en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK

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