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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
Title | Gold(III) photooxidants. Photophysical, photochemical properties, and crystal structure of a luminescent cyclometalated gold(III) complex of 2,9-diphenyl-1,10-phenanthroline |
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Authors | |
Issue Date | 1994 |
Publisher | American 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? |
Abstract | A 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 Identifier | http://hdl.handle.net/10722/167258 |
ISSN | 2023 Impact Factor: 4.3 2023 SCImago Journal Rankings: 0.928 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Chan, CW | en_HK |
dc.contributor.author | Wong, WT | en_HK |
dc.contributor.author | Che, CM | en_HK |
dc.date.accessioned | 2012-10-08T03:04:57Z | - |
dc.date.available | 2012-10-08T03:04:57Z | - |
dc.date.issued | 1994 | en_HK |
dc.identifier.citation | Inorganic Chemistry, 1994, v. 33 n. 7, p. 1266-1272 | en_HK |
dc.identifier.issn | 0020-1669 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/167258 | - |
dc.description.abstract | A 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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic | en_HK |
dc.relation.ispartof | Inorganic Chemistry | en_HK |
dc.title | Gold(III) photooxidants. Photophysical, photochemical properties, and crystal structure of a luminescent cyclometalated gold(III) complex of 2,9-diphenyl-1,10-phenanthroline | en_HK |
dc.type | Article | en_HK |
dc.identifier.email | Wong, WT: wtwong@hku.hk | en_HK |
dc.identifier.email | Che, CM: cmche@hku.hk | en_HK |
dc.identifier.authority | Wong, WT=rp00811 | en_HK |
dc.identifier.authority | Che, CM=rp00670 | en_HK |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/ic00085a010 | - |
dc.identifier.scopus | eid_2-s2.0-0000196374 | en_HK |
dc.identifier.volume | 33 | en_HK |
dc.identifier.issue | 7 | en_HK |
dc.identifier.spage | 1266 | en_HK |
dc.identifier.epage | 1272 | en_HK |
dc.identifier.isi | WOS:A1994NE10200010 | - |
dc.publisher.place | United States | en_HK |
dc.identifier.scopusauthorid | Chan, CW=7404814723 | en_HK |
dc.identifier.scopusauthorid | Wong, WT=7403973084 | en_HK |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_HK |
dc.identifier.issnl | 0020-1669 | - |