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Article: The 3[ndσ*(n+1)pσ] emissions of linear silver(I) and gold(I) chains with bridging phosphine ligands

TitleThe 3[ndσ*(n+1)pσ] emissions of linear silver(I) and gold(I) chains with bridging phosphine ligands
Authors
KeywordsDensity functional calculations
Gold
Metal-metal interactions
P ligands
Polymers
Silver
Issue Date2009
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, 2009, v. 15 n. 41, p. 10777-10789 How to Cite?
AbstractThe complexes [Au3(dcmp)2] [X]3 (dcmp = bis(dicyclohexylphosphinomethyl)cyclohexylphosphine; X = Cl- (1), ClO4 - (2), OTf- (3), PF6 - (4), SCN-(5)}, [Ag3(dcmp)2] [ClO 4]3 (6), and [Ag3(dcmp)2Cl 2][ClO4] (7) were prepared and their structures were determined by X-ray crystallography. Complexes 2-4 display a high-energy emission band with λmax at 442-452 nm, whereas 1 and 5 display a low-energy emission with λmax at 558-634 nm in both solid state and in dichloromethane at 298 K. The former is assigned to the 3[5dσ*6pσ] excited state of [Au3-(dcmp) 2]3+, whereas the latter is attributed to an exciplex formed between the 3[5dσ*6pσ] excited state of [Au3-(dcmp)2]3+ and the counterions. In solid state, complex [Ag3(dcmp)2]-[ClO4]3 (6) displays an intense emission band at 375 nm with a Stokes shift of ≈7200 cm-1 from the 1[4dσ*-→5pσ] absorption band at 295 nm. The 375 nm emission band is assigned to the emission directly from the 3[4dσ*5pσ] excited state of 6. Density functional theory (DFT) calculations revealed that the absorption and emission energies are inversely proportional to the number of metal ions (n) in polynuclear AuI and AgI linear chain complexes without close metal⋯anion contacts. The emission energies are extrapolated to be 715 and 446 nm for the infinite linear AuI and AgI chains, respectively, at metal⋯metal distances of about 2.93-3.02 Å. A QM/MM calculation on the model [Au3(dcmp)2Cl 2]+ system, with Au⋯Cl contacts of 2.90-3.10 Å, gave optimized Au⋯Au distances of 2.99-3.11 Å in its lowest triplet excited state and the emission energies were calculated to be at approximately 600-690 nm, which are assigned to a three-coordinate Au I site with its spectroscopic properties affected by Au I⋯AuI interactions. © 2009 Wiley-VCH Verlag GmbH & Cu. KGaA.
Persistent Identifierhttp://hdl.handle.net/10722/68842
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
Funding AgencyGrant Number
Grants Council of the Hong Kong SAR, ChinaHKU 7008/09
National Natural Science Foundation of China/Research Grants Council Joint Research SchemeN HKU 752/08
Chinese Academy of Sciences-Croucher Foundation Funding Scheme for Joint Laboratories
University Development Fund for Synthetic Chemistry of the University of Hong Kong
Funding Information:

We thank the Research Grants Council of the Hong Kong SAR, China [HKU 7008/09]; National Natural Science Foundation of China/Research Grants Council Joint Research Scheme [N HKU 752/08]; The Chinese Academy of Sciences-Croucher Foundation Funding Scheme for Joint Laboratories and The University Development Fund for Synthetic Chemistry of the University of Hong Kong.

References

 

DC FieldValueLanguage
dc.contributor.authorTong, GSMen_HK
dc.contributor.authorKui, SCFen_HK
dc.contributor.authorChao, HYen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:08:13Z-
dc.date.available2010-09-06T06:08:13Z-
dc.date.issued2009en_HK
dc.identifier.citationChemistry - A European Journal, 2009, v. 15 n. 41, p. 10777-10789en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/68842-
dc.description.abstractThe complexes [Au3(dcmp)2] [X]3 (dcmp = bis(dicyclohexylphosphinomethyl)cyclohexylphosphine; X = Cl- (1), ClO4 - (2), OTf- (3), PF6 - (4), SCN-(5)}, [Ag3(dcmp)2] [ClO 4]3 (6), and [Ag3(dcmp)2Cl 2][ClO4] (7) were prepared and their structures were determined by X-ray crystallography. Complexes 2-4 display a high-energy emission band with λmax at 442-452 nm, whereas 1 and 5 display a low-energy emission with λmax at 558-634 nm in both solid state and in dichloromethane at 298 K. The former is assigned to the 3[5dσ*6pσ] excited state of [Au3-(dcmp) 2]3+, whereas the latter is attributed to an exciplex formed between the 3[5dσ*6pσ] excited state of [Au3-(dcmp)2]3+ and the counterions. In solid state, complex [Ag3(dcmp)2]-[ClO4]3 (6) displays an intense emission band at 375 nm with a Stokes shift of ≈7200 cm-1 from the 1[4dσ*-→5pσ] absorption band at 295 nm. The 375 nm emission band is assigned to the emission directly from the 3[4dσ*5pσ] excited state of 6. Density functional theory (DFT) calculations revealed that the absorption and emission energies are inversely proportional to the number of metal ions (n) in polynuclear AuI and AgI linear chain complexes without close metal⋯anion contacts. The emission energies are extrapolated to be 715 and 446 nm for the infinite linear AuI and AgI chains, respectively, at metal⋯metal distances of about 2.93-3.02 Å. A QM/MM calculation on the model [Au3(dcmp)2Cl 2]+ system, with Au⋯Cl contacts of 2.90-3.10 Å, gave optimized Au⋯Au distances of 2.99-3.11 Å in its lowest triplet excited state and the emission energies were calculated to be at approximately 600-690 nm, which are assigned to a three-coordinate Au I site with its spectroscopic properties affected by Au I⋯AuI interactions. © 2009 Wiley-VCH Verlag GmbH & Cu. KGaA.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.subjectDensity functional calculationsen_HK
dc.subjectGolden_HK
dc.subjectMetal-metal interactionsen_HK
dc.subjectP ligandsen_HK
dc.subjectPolymersen_HK
dc.subjectSilveren_HK
dc.titleThe 3[ndσ*(n+1)pσ] emissions of linear silver(I) and gold(I) chains with bridging phosphine ligandsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0947-6539&volume=15&issue=41&spage=10777&epage=10789&date=2009&atitle=The+3[ndσ*(n+1)pσ]+Emissions+of+Linear+Silver(I)+and+Gold(I)+Chains+with+Bridging+Phosphine+Ligandsen_HK
dc.identifier.emailTong, GSM: tongsm@hku.hken_HK
dc.identifier.emailKui, SCF: stevenku@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityTong, GSM=rp00790en_HK
dc.identifier.authorityKui, SCF=rp00715en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/chem.200901757en_HK
dc.identifier.pmid19777520-
dc.identifier.scopuseid_2-s2.0-70350225490en_HK
dc.identifier.hkuros168960en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-70350225490&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume15en_HK
dc.identifier.issue41en_HK
dc.identifier.spage10777en_HK
dc.identifier.epage10789en_HK
dc.identifier.isiWOS:000271605900014-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridTong, GSM=7102328656en_HK
dc.identifier.scopusauthoridKui, SCF=6506763660en_HK
dc.identifier.scopusauthoridChao, HY=7202973715en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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