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Article: Electronic excited states of [Au2(dmpm)3](CIO4)2 (dmpm = bis(dimethylphosphine)methane)

TitleElectronic excited states of [Au2(dmpm)3](CIO4)2 (dmpm = bis(dimethylphosphine)methane)
Authors
Issue Date2002
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2002, v. 41 n. 8, p. 2054-2059 How to Cite?
AbstractWe present studies of the resonance Raman and electronic luminescence spectra of the [Au 2(dmpm) 3](CIO 4) 2 (dmpm=bis(dimethylphosphine) methane) complex, including excitation into an intense band at 256 nm and into a weaker absorption system centered about ∼300 nm. The resonance Raman spectra confirm the assignment of the 256 nm absorption band to a 1(dσ* → pσ) transition, a metal-metal-localized transition, in that v(Au-Au) and overtones of it are strongly enhanced. A resonance Raman intensity analysis of the spectra associated with the 256 nm absorption band gives the ground-state and excited-state v(Au-Au) stretching frequencies to be 79 and 165 cm -1, respectively, and the excited-state Au-Au distance is calculated to decrease by about 0.1 Å from the ground-state value of 3.05 Å. The ∼300 nm absorption displays a different enhancement pattern, in that resonance-enhanced Raman bands are observed at 103 and 183 cm -1 in addition to v(Au-Au) at 79 cm -1 The compound exhibits intense, long-lived luminescence (in room-temperature CH 3CN, for example, τ= 0.70, μs, Φemission = 0.037) with a maximum at 550-600 nm that is not very medium-sensitive. We conclude, in agreement with an earlier proposal of Mason (Inorg. Chem. 1989, 28, 4366-4369), that the lowest-energy, luminescent excited state is not 3(dσ* → pσ) but instead derives from 3(d x 2- y 2,xy → pσ) pGr) excitations. We compare the Au(I)-Au(I) interaction shown in the various transitions of the [Au 2(dmpm) 3](CIO 4) 2 tribridged compound with previous results for solvent or counterion exciplexes of [Au 2(dcpm) 2] 2+ salts (J. Am. Chem. Soc. 1999, 121, 4799-4803; Angew. Chem. 1999, 38, 2783-2785; Chem. Eur. J. 2001, 7, 4656-4664) and for planar, mononuclear Au(I) triphosphine complexes. It is proposed that the luminescent state in all of these cases is very similar in electronic nature.
Persistent Identifierhttp://hdl.handle.net/10722/167765
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLeung, KHen_US
dc.contributor.authorPhillips, DLen_US
dc.contributor.authorMao, Zen_US
dc.contributor.authorChe, CMen_US
dc.contributor.authorMiskowski, VMen_US
dc.contributor.authorChan, CKen_US
dc.date.accessioned2012-10-08T03:11:17Z-
dc.date.available2012-10-08T03:11:17Z-
dc.date.issued2002en_US
dc.identifier.citationInorganic Chemistry, 2002, v. 41 n. 8, p. 2054-2059en_US
dc.identifier.issn0020-1669en_US
dc.identifier.urihttp://hdl.handle.net/10722/167765-
dc.description.abstractWe present studies of the resonance Raman and electronic luminescence spectra of the [Au 2(dmpm) 3](CIO 4) 2 (dmpm=bis(dimethylphosphine) methane) complex, including excitation into an intense band at 256 nm and into a weaker absorption system centered about ∼300 nm. The resonance Raman spectra confirm the assignment of the 256 nm absorption band to a 1(dσ* → pσ) transition, a metal-metal-localized transition, in that v(Au-Au) and overtones of it are strongly enhanced. A resonance Raman intensity analysis of the spectra associated with the 256 nm absorption band gives the ground-state and excited-state v(Au-Au) stretching frequencies to be 79 and 165 cm -1, respectively, and the excited-state Au-Au distance is calculated to decrease by about 0.1 Å from the ground-state value of 3.05 Å. The ∼300 nm absorption displays a different enhancement pattern, in that resonance-enhanced Raman bands are observed at 103 and 183 cm -1 in addition to v(Au-Au) at 79 cm -1 The compound exhibits intense, long-lived luminescence (in room-temperature CH 3CN, for example, τ= 0.70, μs, Φemission = 0.037) with a maximum at 550-600 nm that is not very medium-sensitive. We conclude, in agreement with an earlier proposal of Mason (Inorg. Chem. 1989, 28, 4366-4369), that the lowest-energy, luminescent excited state is not 3(dσ* → pσ) but instead derives from 3(d x 2- y 2,xy → pσ) pGr) excitations. We compare the Au(I)-Au(I) interaction shown in the various transitions of the [Au 2(dmpm) 3](CIO 4) 2 tribridged compound with previous results for solvent or counterion exciplexes of [Au 2(dcpm) 2] 2+ salts (J. Am. Chem. Soc. 1999, 121, 4799-4803; Angew. Chem. 1999, 38, 2783-2785; Chem. Eur. J. 2001, 7, 4656-4664) and for planar, mononuclear Au(I) triphosphine complexes. It is proposed that the luminescent state in all of these cases is very similar in electronic nature.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_US
dc.relation.ispartofInorganic Chemistryen_US
dc.titleElectronic excited states of [Au2(dmpm)3](CIO4)2 (dmpm = bis(dimethylphosphine)methane)en_US
dc.typeArticleen_US
dc.identifier.emailPhillips, DL:phillips@hku.hken_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.authorityPhillips, DL=rp00770en_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ic011084ven_US
dc.identifier.pmid11952358-
dc.identifier.scopuseid_2-s2.0-0037156204en_US
dc.identifier.hkuros72426-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0037156204&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume41en_US
dc.identifier.issue8en_US
dc.identifier.spage2054en_US
dc.identifier.epage2059en_US
dc.identifier.isiWOS:000175110500011-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridLeung, KH=7401860609en_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US
dc.identifier.scopusauthoridMao, Z=7202633924en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridMiskowski, VM=6603008214en_US
dc.identifier.scopusauthoridChan, CK=27170510400en_US

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