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Article: Novel luminescent polynuclear gold(I) phosphine complexes. Synthesis, spectroscopy, and X-ray crystal structure of [Au3(dmmp) 2]3+ [dmmp = bis(dimethylphosphinomethyl)methylphosphine]
Title | Novel luminescent polynuclear gold(I) phosphine complexes. Synthesis, spectroscopy, and X-ray crystal structure of [Au3(dmmp) 2]3+ [dmmp = bis(dimethylphosphinomethyl)methylphosphine] |
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Authors | |
Issue Date | 1990 |
Publisher | Royal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton |
Citation | Journal Of The Chemical Society, Dalton Transactions, 1990 n. 12, p. 3747-3752 How to Cite? |
Abstract | Reaction of K[AuCl4] with bis(dimethylphosphinomethyl)methylphosphine (dmmp) in the presence of thiodiglycol (2,2′-thiodiethanol) in methanol yielded [Au3(dmmp)2]3+, which was isolated as its perchlorate salt. The X-ray crystal structure of [Au3 (dmmp)2][ClO4]3 has been determined: monoclinic, space group P21/n, a = 1 2.880(3), b = 14.210(1), c = 21.208(2) Å, β = 106.25(1)°, Z = 4, R = 0.047 for 2 927 observed Mo-Kα data. The Au-Au-Au bond angle of 136.26(4)° is greatly distorted from rectilinear geometry, with intramolecular Au⋯Au distances of 2.981(1) and 2.962(1) Å. Excitation of a degassed acetonitrile solution of [Au3(dmmp) 2]3+ at 300-370 nm resulted in dual phosphorescence (λ = 467 nm, τ0 = 1.6 ± 0.2 μs; λ = 580 nm, τ0 = 7.0 ± 0.5 μs). A comparison between the electronic absorption and emission spectra of [Au3(dmmp) 2]3+ and [Au2 (dmpm) 2]2+ [[dmpm = bis(dimethylphosphino)methane] has been made. The assignment of the lowest electronic excited state in the (P2Au)n system has been suggested to be 3 [(dδ*)(pσ)]. The excited-state redox potentials of [Au3(dmmp)2]3+* and [Au2(dmpm)2]2+* have been determined through oxidative quenching experiments with a series of pyridinium acceptors of variable reduction potential. |
Persistent Identifier | http://hdl.handle.net/10722/168197 |
ISSN | |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Yam, VWW | en_US |
dc.contributor.author | Lai, TF | en_US |
dc.contributor.author | Che, CM | en_US |
dc.date.accessioned | 2012-10-08T03:16:10Z | - |
dc.date.available | 2012-10-08T03:16:10Z | - |
dc.date.issued | 1990 | en_US |
dc.identifier.citation | Journal Of The Chemical Society, Dalton Transactions, 1990 n. 12, p. 3747-3752 | en_US |
dc.identifier.issn | 1472-7773 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/168197 | - |
dc.description.abstract | Reaction of K[AuCl4] with bis(dimethylphosphinomethyl)methylphosphine (dmmp) in the presence of thiodiglycol (2,2′-thiodiethanol) in methanol yielded [Au3(dmmp)2]3+, which was isolated as its perchlorate salt. The X-ray crystal structure of [Au3 (dmmp)2][ClO4]3 has been determined: monoclinic, space group P21/n, a = 1 2.880(3), b = 14.210(1), c = 21.208(2) Å, β = 106.25(1)°, Z = 4, R = 0.047 for 2 927 observed Mo-Kα data. The Au-Au-Au bond angle of 136.26(4)° is greatly distorted from rectilinear geometry, with intramolecular Au⋯Au distances of 2.981(1) and 2.962(1) Å. Excitation of a degassed acetonitrile solution of [Au3(dmmp) 2]3+ at 300-370 nm resulted in dual phosphorescence (λ = 467 nm, τ0 = 1.6 ± 0.2 μs; λ = 580 nm, τ0 = 7.0 ± 0.5 μs). A comparison between the electronic absorption and emission spectra of [Au3(dmmp) 2]3+ and [Au2 (dmpm) 2]2+ [[dmpm = bis(dimethylphosphino)methane] has been made. The assignment of the lowest electronic excited state in the (P2Au)n system has been suggested to be 3 [(dδ*)(pσ)]. The excited-state redox potentials of [Au3(dmmp)2]3+* and [Au2(dmpm)2]2+* have been determined through oxidative quenching experiments with a series of pyridinium acceptors of variable reduction potential. | en_US |
dc.language | eng | en_US |
dc.publisher | Royal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton | en_US |
dc.relation.ispartof | Journal of the Chemical Society, Dalton Transactions | en_US |
dc.title | Novel luminescent polynuclear gold(I) phosphine complexes. Synthesis, spectroscopy, and X-ray crystal structure of [Au3(dmmp) 2]3+ [dmmp = bis(dimethylphosphinomethyl)methylphosphine] | en_US |
dc.type | Article | en_US |
dc.identifier.email | Yam, VWW:wwyam@hku.hk | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.authority | Yam, VWW=rp00822 | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1039/DT9900003747 | en_US |
dc.identifier.scopus | eid_2-s2.0-37049073407 | en_US |
dc.identifier.issue | 12 | en_US |
dc.identifier.spage | 3747 | en_US |
dc.identifier.epage | 3752 | en_US |
dc.identifier.isi | WOS:A1990EP09800029 | - |
dc.publisher.place | United Kingdom | en_US |
dc.identifier.scopusauthorid | Yam, VWW=18539304700 | en_US |
dc.identifier.scopusauthorid | Lai, TF=7202203523 | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.issnl | 1364-5447 | - |