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Article: Computational Studies on the Photophysical Properties and NMR Fluxionality of the Tetranuclear Copper(I) Complexes [Cu4(μ-dppm)4(μ4-E)]2+ (E = PPh and S)

TitleComputational Studies on the Photophysical Properties and NMR Fluxionality of the Tetranuclear Copper(I) Complexes [Cu4(μ-dppm)4(μ4-E)]2+ (E = PPh and S)
Authors
Issue Date2006
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2006, v. 45 n. 23, p. 9434-9441 How to Cite?
AbstractDensity functional theory (DFT) calculations at the hybrid Perdew, Burke, and Ernzerhof functional level were performed to study the electronic structures of the ground and excited states of the luminescent tetranuclear copper(I) complexes [Cu4(mu-dppm)4(mu4-E)]2+ [E = PPh (1) and S (2)] by using model complexes [Cu4(mu-H2PCH2PH2)4(mu4-E)]2+ [E = PPh (1a) and S (2a)]. The time-dependent DFT method at the same level associated with the conductor-like polarizable continuum model was used to study the nature of the low-energy transitions in their electronic absorption spectra. The results indicate that the lowest energy absorptions of both 1 and 2 are attributed to ligand-to-metal charge-transfer (LMCT) (E --> Cu4) with mixing of metal-cluster-centered (MCC) (3d --> 4s/3d --> 4p) singlet-singlet transitions. The geometry optimizations on the lowest energy triplet state reveal that the emissive states of both complexes involve a considerable structural distortion in which they are derived predominantly from an admixture of 3LMCT (E --> Cu4) and 3MCC (3d --> 4p) origin. In addition to the photophysical properties, the fluxional behavior of 2 observed from the NMR studies but not that of 1 was investigated. It is found that the fluxionality in 2 involves the shuttling of the sulfido ligand through the rectangular Cu4 core.
Persistent Identifierhttp://hdl.handle.net/10722/70089
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLam, WHen_HK
dc.contributor.authorCheng, ECCen_HK
dc.contributor.authorYam, VWWen_HK
dc.date.accessioned2010-09-06T06:19:36Z-
dc.date.available2010-09-06T06:19:36Z-
dc.date.issued2006en_HK
dc.identifier.citationInorganic Chemistry, 2006, v. 45 n. 23, p. 9434-9441en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70089-
dc.description.abstractDensity functional theory (DFT) calculations at the hybrid Perdew, Burke, and Ernzerhof functional level were performed to study the electronic structures of the ground and excited states of the luminescent tetranuclear copper(I) complexes [Cu4(mu-dppm)4(mu4-E)]2+ [E = PPh (1) and S (2)] by using model complexes [Cu4(mu-H2PCH2PH2)4(mu4-E)]2+ [E = PPh (1a) and S (2a)]. The time-dependent DFT method at the same level associated with the conductor-like polarizable continuum model was used to study the nature of the low-energy transitions in their electronic absorption spectra. The results indicate that the lowest energy absorptions of both 1 and 2 are attributed to ligand-to-metal charge-transfer (LMCT) (E --> Cu4) with mixing of metal-cluster-centered (MCC) (3d --> 4s/3d --> 4p) singlet-singlet transitions. The geometry optimizations on the lowest energy triplet state reveal that the emissive states of both complexes involve a considerable structural distortion in which they are derived predominantly from an admixture of 3LMCT (E --> Cu4) and 3MCC (3d --> 4p) origin. In addition to the photophysical properties, the fluxional behavior of 2 observed from the NMR studies but not that of 1 was investigated. It is found that the fluxionality in 2 involves the shuttling of the sulfido ligand through the rectangular Cu4 core.-
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleComputational Studies on the Photophysical Properties and NMR Fluxionality of the Tetranuclear Copper(I) Complexes [Cu4(μ-dppm)4(μ4-E)]2+ (E = PPh and S)en_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=45&spage=9434&epage=9441&date=2006&atitle=Computational+Studies+on+the+Photophysical+Properties+and+NMR+Fluxionality+of+the+Tetranuclear+Copper(I)+Complexes+[Cu4(m-dppm)4(m4-E)]2++(E+=+PPh+and+S)en_HK
dc.identifier.emailYam, VWW: wwyam@hku.hken_HK
dc.identifier.authorityLam, SWH=rp00719en_HK
dc.identifier.authorityYam, VWW=rp00822en_HK
dc.identifier.doi10.1021/ic0612855-
dc.identifier.pmid17083244-
dc.identifier.scopuseid_2-s2.0-33751269163-
dc.identifier.hkuros125281en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33751269163&selection=ref&src=s&origin=recordpage-
dc.identifier.volume45-
dc.identifier.issue23-
dc.identifier.spage9434-
dc.identifier.epage9441-
dc.identifier.isiWOS:000241778900041-
dc.publisher.placeUnited States-
dc.identifier.scopusauthoridWai, HL=22433970100-
dc.identifier.scopusauthoridCheng, ECC=7201743424-
dc.identifier.scopusauthoridYam, VWW=18539304700-

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