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Article: Structures and luminescent properties of polynuclear gold(I) halides containing bridging phosphine ligands

TitleStructures and luminescent properties of polynuclear gold(I) halides containing bridging phosphine ligands
Authors
Issue Date1997
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Journal Of The Chemical Society - Dalton Transactions, 1997 n. 2, p. 221-226 How to Cite?
AbstractThe complexes [AuI(PPh3)] 1, [Au2(μ-dppm)Cl2] 2 [dppm = bis(diphenylphosphine)methane], [Au2(μ-dppm)I2] 3, [Au3(μ-tppm)Cl3] 4 [tppm = tris(diphenylphosphino)methane], [Au3(μ-dpmp)I3] 5, [Au3(μ-dpmp)2Cl2]Cl 6 [dpmp = bis(diphenylphosphinomethyl)phenylphosphine] and [Au3(μ-dpmp)2I2]I 7 were prepared. The crystal structures of 5-7 have been established by X-ray crystal analysis. The measured intramolecular Au-Au distances are 3.136(1) Å in 5, 2.946(3) and 2.963(3) Å in 6 and 2.952(1) and 3.020(1) Å in 7. Extended-Hückel molecular orbital calculations revealed that the 6p orbitals of iodide and 5d orbitals of gold(I) make a significant contribution to the highest occupied molecular orbitals of 5 and of 2 and 4 respectively. The lowest unoccupied molecular orbitals of these complexes mainly comprise π* orbitals of the phosphines. The photophysical properties of 1-6 have been studied. All show dual emissions. The low-energy emissions at around 660-680 nm have a small red shift in energy from chloro to iodo complexes, and a much higher intensity at room temperature than at 77 K. These are attributed to triplet states with mixed 3m.m.l.c.t. (metal-metal to ligand charge transfer, gold→phosphine) and 3l.l.c.t. (ligand to ligand charge transfer, halide to phosphine) characters. The high-energy emissions at around 460-530 nm are more prominent at 77 K and assigned to intraligand and or 3m.l.c.t. (metal to ligand charge transfer) transitions. The temperature effects on the luminescence lifetimes of these complexes have also been studied.
Persistent Identifierhttp://hdl.handle.net/10722/69715
ISSN
1999 Impact Factor: 2.31
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorXiao, Hen_HK
dc.contributor.authorWeng, YXen_HK
dc.contributor.authorWong, WTen_HK
dc.contributor.authorMak, TCWen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:16:11Z-
dc.date.available2010-09-06T06:16:11Z-
dc.date.issued1997en_HK
dc.identifier.citationJournal Of The Chemical Society - Dalton Transactions, 1997 n. 2, p. 221-226en_HK
dc.identifier.issn0300-9246en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69715-
dc.description.abstractThe complexes [AuI(PPh3)] 1, [Au2(μ-dppm)Cl2] 2 [dppm = bis(diphenylphosphine)methane], [Au2(μ-dppm)I2] 3, [Au3(μ-tppm)Cl3] 4 [tppm = tris(diphenylphosphino)methane], [Au3(μ-dpmp)I3] 5, [Au3(μ-dpmp)2Cl2]Cl 6 [dpmp = bis(diphenylphosphinomethyl)phenylphosphine] and [Au3(μ-dpmp)2I2]I 7 were prepared. The crystal structures of 5-7 have been established by X-ray crystal analysis. The measured intramolecular Au-Au distances are 3.136(1) Å in 5, 2.946(3) and 2.963(3) Å in 6 and 2.952(1) and 3.020(1) Å in 7. Extended-Hückel molecular orbital calculations revealed that the 6p orbitals of iodide and 5d orbitals of gold(I) make a significant contribution to the highest occupied molecular orbitals of 5 and of 2 and 4 respectively. The lowest unoccupied molecular orbitals of these complexes mainly comprise π* orbitals of the phosphines. The photophysical properties of 1-6 have been studied. All show dual emissions. The low-energy emissions at around 660-680 nm have a small red shift in energy from chloro to iodo complexes, and a much higher intensity at room temperature than at 77 K. These are attributed to triplet states with mixed 3m.m.l.c.t. (metal-metal to ligand charge transfer, gold→phosphine) and 3l.l.c.t. (ligand to ligand charge transfer, halide to phosphine) characters. The high-energy emissions at around 460-530 nm are more prominent at 77 K and assigned to intraligand and or 3m.l.c.t. (metal to ligand charge transfer) transitions. The temperature effects on the luminescence lifetimes of these complexes have also been studied.en_HK
dc.languageengen_HK
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_HK
dc.relation.ispartofJournal of the Chemical Society - Dalton Transactionsen_HK
dc.titleStructures and luminescent properties of polynuclear gold(I) halides containing bridging phosphine ligandsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1472-7773&volume=&spage=221&epage=226&date=1997&atitle=Structures+and+luminescent+properties+of+polynuclear+gold(I)+halides+containing+bridging+phosphine+ligandsen_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_fulltext-
dc.identifier.doi10.1039/A605911B-
dc.identifier.scopuseid_2-s2.0-33748621207en_HK
dc.identifier.hkuros27139en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33748621207&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.issue2en_HK
dc.identifier.spage221en_HK
dc.identifier.epage226en_HK
dc.identifier.isiWOS:A1997WF57300015-
dc.identifier.scopusauthoridXiao, H=36893832200en_HK
dc.identifier.scopusauthoridWeng, YX=7103321459en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK
dc.identifier.scopusauthoridMak, TCW=7401931058en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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