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Article: Aurophilic attraction and luminescence of binuclear gold(I) complexes with bridging phosphine ligands: Ab initio study

TitleAurophilic attraction and luminescence of binuclear gold(I) complexes with bridging phosphine ligands: Ab initio study
Authors
KeywordsAb initio calculations
Aurophilic interaction
Gold
Luminescence
Solvent effects
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. 22, p. 4887-4893 How to Cite?
AbstractElectronic structure and spectroscopic properties of [Au2-(dpm)2]2+ (dpm = bis(diphosphino)methane) were studied by ab initio calculations. The absorption and emission spectra of this binuclear gold(I) complex in acetonitrile and in the solid state were calculated by single excitation configuration interaction (CIS) method. In the calculations, the solvent effect was taken into account by the weakly solvated [Au2(dpm)2]2+ · (MeCN)2 complex. The ground state structures of [Au2(dpm)2]2+ and [Au2(dpm)2]2+ · (MeCN)2 were optimized by the second-order Møller-Plesset perturbation (MP2) method, while the emissive triplet excited state structures were optimized by the CIS calculations. The results reveal that coordination of acetonitrile to the gold atom in the 3[dσ*sσ] excited state causes a significant red shift in emission energy. The weak aurophilic attraction exists in the ground states of [Au2(dpm)2]2+ and [Au2(dpm)2]2+ · (MeCN)2, and is greatly enhanced in their 3[dσ*sσ] excited states. In acetonitrile, the 3Au(sσ) → 1Ag(dσ*) transition (phosphorescence) of [Au2(dpm)2]2+ was calculated at 557 nm, in consistent with the observed emission of [Au2(dppm)2](ClO4)2 (dppm = bis(diphenylphosphino)methane) at 575 nm. A high energy emission at 331 nm is predicted for [Au2(dpm)2]2+ in the absence of the interaction between the gold atom and solvent molecule and/ or neighboring anion in the excited state. The CIS calculations on the excited states also reveal that the two absorption bands at 278 and 218 nm recorded for [Au2(dcpm)2](ClO4)2 in acetonitrile can be attributed to the 1Ag(dσ*) → 1Au(pσ) and 1Ag(dσ*) → 1Au((sp)σ) transitions, respectively. © Wiley-VCH Verlag GmbH, 2001.
Persistent Identifierhttp://hdl.handle.net/10722/69044
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorZhang, HXen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:10:02Z-
dc.date.available2010-09-06T06:10:02Z-
dc.date.issued2001en_HK
dc.identifier.citationChemistry - A European Journal, 2001, v. 7 n. 22, p. 4887-4893en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69044-
dc.description.abstractElectronic structure and spectroscopic properties of [Au2-(dpm)2]2+ (dpm = bis(diphosphino)methane) were studied by ab initio calculations. The absorption and emission spectra of this binuclear gold(I) complex in acetonitrile and in the solid state were calculated by single excitation configuration interaction (CIS) method. In the calculations, the solvent effect was taken into account by the weakly solvated [Au2(dpm)2]2+ · (MeCN)2 complex. The ground state structures of [Au2(dpm)2]2+ and [Au2(dpm)2]2+ · (MeCN)2 were optimized by the second-order Møller-Plesset perturbation (MP2) method, while the emissive triplet excited state structures were optimized by the CIS calculations. The results reveal that coordination of acetonitrile to the gold atom in the 3[dσ*sσ] excited state causes a significant red shift in emission energy. The weak aurophilic attraction exists in the ground states of [Au2(dpm)2]2+ and [Au2(dpm)2]2+ · (MeCN)2, and is greatly enhanced in their 3[dσ*sσ] excited states. In acetonitrile, the 3Au(sσ) → 1Ag(dσ*) transition (phosphorescence) of [Au2(dpm)2]2+ was calculated at 557 nm, in consistent with the observed emission of [Au2(dppm)2](ClO4)2 (dppm = bis(diphenylphosphino)methane) at 575 nm. A high energy emission at 331 nm is predicted for [Au2(dpm)2]2+ in the absence of the interaction between the gold atom and solvent molecule and/ or neighboring anion in the excited state. The CIS calculations on the excited states also reveal that the two absorption bands at 278 and 218 nm recorded for [Au2(dcpm)2](ClO4)2 in acetonitrile can be attributed to the 1Ag(dσ*) → 1Au(pσ) and 1Ag(dσ*) → 1Au((sp)σ) transitions, respectively. © Wiley-VCH Verlag GmbH, 2001.en_HK
dc.languageengen_HK
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistryen_HK
dc.relation.ispartofChemistry - A European Journalen_HK
dc.subjectAb initio calculationsen_HK
dc.subjectAurophilic interactionen_HK
dc.subjectGolden_HK
dc.subjectLuminescenceen_HK
dc.subjectSolvent effectsen_HK
dc.titleAurophilic attraction and luminescence of binuclear gold(I) complexes with bridging phosphine ligands: Ab initio studyen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0947-6539&volume=7&issue=22&spage=4887&epage=4893&date=2001&atitle=Aurophilic+attraction+and+luminescence+of+binuclear+gold(I)+complexes+with+bridging+phosphine+ligands:++ab+initio+studyen_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/1521-3765(20011119)7:22<4887::AID-CHEM4887>3.0.CO;2-C-
dc.identifier.pmid11763457-
dc.identifier.scopuseid_2-s2.0-0035914627en_HK
dc.identifier.hkuros72372en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0035914627&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume7en_HK
dc.identifier.issue22en_HK
dc.identifier.spage4887en_HK
dc.identifier.epage4893en_HK
dc.identifier.isiWOS:000172434500014-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridZhang, HX=36077448000en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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