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Article: Gold(III) photooxidants. Photophysical, photochemical properties, and crystal structure of a luminescent cyclometalated gold(III) complex of 2,9-diphenyl-1,10-phenanthroline

TitleGold(III) photooxidants. Photophysical, photochemical properties, and crystal structure of a luminescent cyclometalated gold(III) complex of 2,9-diphenyl-1,10-phenanthroline
Authors
Issue Date1994
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1994, v. 33 n. 7, p. 1266-1272 How to Cite?
AbstractA luminescent cyclometalated gold(III) complex [Au(C∧N∧N-dpp)Cl](X) (1a, X = C7H7SO3; 1b, X = ClO4; where C∧N∧N = C-anion of 2,9-diphenyl-1,10-phenanthroline) was prepared and characterized by X-ray crystal analysis. Crystal data for [Au(C24H15N2)Cl](C7H 7SO3)·1/2CH3OH: mol wt 950.97, triclinic, space group P1 (No. 2), a = 9.690(3) Å, b = 10.799(2) Å, c = 15.934(3) Å, α = 74.20(1)°, β = 85.59(2)°, γ = 68.72(2)°, V = 1494.6 Å3, Z = 2. In the solid state, two [Au(C∧N∧N-dpp)Cl]+ cations stack on each other with an intermolecular Au⋯Au separation of 3.6 Å. Complexes 1a and 1b are emissive in fluid solutions with quantum yields of ∼10-4 and lifetimes of 0.4-0.7 μs. The emission spectra of 1a and 1b are quite insensitive to solvents (521-670 nm) and display vibrational progression of ∼1400 cm-1. The small spectral red-shift (1400 cm-1) of the emission of 1a from that of free ligand (dpp) suggests a metal-perturbed intraligand emissive state. The estimated excited state reduction potential E°*(AuIII/II) of 2.2 V (vs NHE) suggests that [Au(C∧N∧N-dpp)Cl]+is a strong photo-oxidant. This photooxidizing property has been demonstrated with the formation of the 1,4-dimethoxybenzene cation radical (DMB•+) upon UV-vis irradiation of an acetonitrile solution of [Au(C∧N∧N-dpp)Cl]+ and DMB and visible light (λ = 406 nm) induced reduction of the gold(III) complex by tetrahydrofuran. © 1994 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167258
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChan, CWen_HK
dc.contributor.authorWong, WTen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2012-10-08T03:04:57Z-
dc.date.available2012-10-08T03:04:57Z-
dc.date.issued1994en_HK
dc.identifier.citationInorganic Chemistry, 1994, v. 33 n. 7, p. 1266-1272en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167258-
dc.description.abstractA luminescent cyclometalated gold(III) complex [Au(C∧N∧N-dpp)Cl](X) (1a, X = C7H7SO3; 1b, X = ClO4; where C∧N∧N = C-anion of 2,9-diphenyl-1,10-phenanthroline) was prepared and characterized by X-ray crystal analysis. Crystal data for [Au(C24H15N2)Cl](C7H 7SO3)·1/2CH3OH: mol wt 950.97, triclinic, space group P1 (No. 2), a = 9.690(3) Å, b = 10.799(2) Å, c = 15.934(3) Å, α = 74.20(1)°, β = 85.59(2)°, γ = 68.72(2)°, V = 1494.6 Å3, Z = 2. In the solid state, two [Au(C∧N∧N-dpp)Cl]+ cations stack on each other with an intermolecular Au⋯Au separation of 3.6 Å. Complexes 1a and 1b are emissive in fluid solutions with quantum yields of ∼10-4 and lifetimes of 0.4-0.7 μs. The emission spectra of 1a and 1b are quite insensitive to solvents (521-670 nm) and display vibrational progression of ∼1400 cm-1. The small spectral red-shift (1400 cm-1) of the emission of 1a from that of free ligand (dpp) suggests a metal-perturbed intraligand emissive state. The estimated excited state reduction potential E°*(AuIII/II) of 2.2 V (vs NHE) suggests that [Au(C∧N∧N-dpp)Cl]+is a strong photo-oxidant. This photooxidizing property has been demonstrated with the formation of the 1,4-dimethoxybenzene cation radical (DMB•+) upon UV-vis irradiation of an acetonitrile solution of [Au(C∧N∧N-dpp)Cl]+ and DMB and visible light (λ = 406 nm) induced reduction of the gold(III) complex by tetrahydrofuran. © 1994 American Chemical Society.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleGold(III) photooxidants. Photophysical, photochemical properties, and crystal structure of a luminescent cyclometalated gold(III) complex of 2,9-diphenyl-1,10-phenanthrolineen_HK
dc.typeArticleen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ic00085a010-
dc.identifier.scopuseid_2-s2.0-0000196374en_HK
dc.identifier.volume33en_HK
dc.identifier.issue7en_HK
dc.identifier.spage1266en_HK
dc.identifier.epage1272en_HK
dc.identifier.isiWOS:A1994NE10200010-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridChan, CW=7404814723en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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