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Article: Substrate-binding reactions of the 3[dσ*pσ] excited state of binuclear gold(I) complexes with bridging bis(dicyclohexylphosphino)methane ligands: Emission and time-resolved absorption spectroscopic studies

TitleSubstrate-binding reactions of the 3[dσ*pσ] excited state of binuclear gold(I) complexes with bridging bis(dicyclohexylphosphino)methane ligands: Emission and time-resolved absorption spectroscopic studies
Authors
KeywordsBinuclear Complexes
Exciplexes
Gold
Luminescence
Quenching
Issue Date2001
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, 2001, v. 7 n. 21, p. 4656-4664 How to Cite?
AbstractThe complexes [Au 2(dcpm) 2]-Y 2 (dcpm = bis(dicyclohexylphosphino)-methane; Y = ClO 4 - (1), PF 6 - (2), CF 3SO 3 - (3), Au(CN) 2 - (4), Cl - (5), SCN - (6) and I - (7)) were prepared, and the structures of 1 and 4-7 were determined by X-ray crystallography. Complexes 1-4 display intense phosphorescence with λ max at 360-368 nm in the solid state at room temperature as well as in glassy solutions at 77 K. The solid-state emission quantum yields of the powdered samples are 0.37 (1), 0.74 (2), 0.53 (3) and 0.12 (4). Crystalline solid 5 displays both high-energy UV (λ max = 366 nm) and low-energy visible emissions (λ max = 505 nm) at room temperature, whereas either 6 or 7 shows only an intense emission with λ max at 465 or 473 nm, respectively. All the complexes in degassed acetonitrile solutions exhibit an intense phosphorescence with λ max ranging from 490 to 530 nm. The high-energy UV emission is assigned to the intrinsic emission of the 3[dσ*pσ] excited state of [Au 2(dcpm) 2] 2+, whereas the visible emission is attributed to the adduct formation of the triplet excited state with the solvent/counterion. The quenching rate constants of the visible emission of [Au 2(dcpm) 2] 2+ in acetonitrile by various anions are 6.08 × 10 5 (ClO 4 -), 9.18 × 10 5 (PF 6 -), 1.55 × 10 7 (Cl -) and 4.06 × 10 9 (I -) mol -1dm 3s -1. The triplet-state difference absorption spectra of 1-4 in acetonitrile show an absorption band with λ max at 350 nm and a shoulder/absorption maxima at 395-420 nm; their relative intensities are dependent upon the halide ion present in solution. Substrate binding reactions of the 3[dσ*pσ] excited state with halide (X -) to give [Au 2(dcpm) 2X] +* would account for the lower energy absorption maxima in the triplet-state difference absorption spectra. With iodide as the counterion, complex 7 undergoes a photoinduced electron-transfer reaction with I - to give the radical anion I 2 -. © Wiley-VCH Verlag GmbH, 2001.
Persistent Identifierhttp://hdl.handle.net/10722/167697
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorFu, WFen_US
dc.contributor.authorChan, KCen_US
dc.contributor.authorCheung, KKen_US
dc.contributor.authorChe, CMen_US
dc.date.accessioned2012-10-08T03:10:10Z-
dc.date.available2012-10-08T03:10:10Z-
dc.date.issued2001en_US
dc.identifier.citationChemistry - A European Journal, 2001, v. 7 n. 21, p. 4656-4664en_US
dc.identifier.issn0947-6539en_US
dc.identifier.urihttp://hdl.handle.net/10722/167697-
dc.description.abstractThe complexes [Au 2(dcpm) 2]-Y 2 (dcpm = bis(dicyclohexylphosphino)-methane; Y = ClO 4 - (1), PF 6 - (2), CF 3SO 3 - (3), Au(CN) 2 - (4), Cl - (5), SCN - (6) and I - (7)) were prepared, and the structures of 1 and 4-7 were determined by X-ray crystallography. Complexes 1-4 display intense phosphorescence with λ max at 360-368 nm in the solid state at room temperature as well as in glassy solutions at 77 K. The solid-state emission quantum yields of the powdered samples are 0.37 (1), 0.74 (2), 0.53 (3) and 0.12 (4). Crystalline solid 5 displays both high-energy UV (λ max = 366 nm) and low-energy visible emissions (λ max = 505 nm) at room temperature, whereas either 6 or 7 shows only an intense emission with λ max at 465 or 473 nm, respectively. All the complexes in degassed acetonitrile solutions exhibit an intense phosphorescence with λ max ranging from 490 to 530 nm. The high-energy UV emission is assigned to the intrinsic emission of the 3[dσ*pσ] excited state of [Au 2(dcpm) 2] 2+, whereas the visible emission is attributed to the adduct formation of the triplet excited state with the solvent/counterion. The quenching rate constants of the visible emission of [Au 2(dcpm) 2] 2+ in acetonitrile by various anions are 6.08 × 10 5 (ClO 4 -), 9.18 × 10 5 (PF 6 -), 1.55 × 10 7 (Cl -) and 4.06 × 10 9 (I -) mol -1dm 3s -1. The triplet-state difference absorption spectra of 1-4 in acetonitrile show an absorption band with λ max at 350 nm and a shoulder/absorption maxima at 395-420 nm; their relative intensities are dependent upon the halide ion present in solution. Substrate binding reactions of the 3[dσ*pσ] excited state with halide (X -) to give [Au 2(dcpm) 2X] +* would account for the lower energy absorption maxima in the triplet-state difference absorption spectra. With iodide as the counterion, complex 7 undergoes a photoinduced electron-transfer reaction with I - to give the radical anion I 2 -. © Wiley-VCH Verlag GmbH, 2001.en_US
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_US
dc.relation.ispartofChemistry - A European Journalen_US
dc.subjectBinuclear Complexesen_US
dc.subjectExciplexesen_US
dc.subjectGolden_US
dc.subjectLuminescenceen_US
dc.subjectQuenchingen_US
dc.titleSubstrate-binding reactions of the 3[dσ*pσ] excited state of binuclear gold(I) complexes with bridging bis(dicyclohexylphosphino)methane ligands: Emission and time-resolved absorption spectroscopic studiesen_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1002/1521-3765(20011105)7:21<4656::AID-CHEM4656>3.0.CO;2-D-
dc.identifier.pmid11757658-
dc.identifier.scopuseid_2-s2.0-0035813668en_US
dc.identifier.hkuros72361-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0035813668&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume7en_US
dc.identifier.issue21en_US
dc.identifier.spage4656en_US
dc.identifier.epage4664en_US
dc.identifier.isiWOS:000172133300015-
dc.publisher.placeGermanyen_US
dc.identifier.scopusauthoridFu, WF=7202947315en_US
dc.identifier.scopusauthoridChan, KC=13609968400en_US
dc.identifier.scopusauthoridCheung, KK=7402406613en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US

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