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Article: Structural and spectroscopic evidence for weak metal-metal interactions and metal-substrate exciplex formations in d10 metal complexes

TitleStructural and spectroscopic evidence for weak metal-metal interactions and metal-substrate exciplex formations in d10 metal complexes
Authors
KeywordsClosed shell
Exciplex
Luminescence
Metallophilicity
Spectroscopy
Issue Date2005
PublisherElsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/ccr
Citation
Coordination Chemistry Reviews, 2005, v. 249 n. 13-14, p. 1296-1309 How to Cite?
AbstractStructural investigations of homometallic di- and tri-nuclear coinage metal complexes with bridging phosphine ligands, [M2(P∩P) 2]X2 and [M3(P∩P ∩P)2]X3 (M = Cu(I), Au(I), and Ag(I); X = anion), have revealed close intramolecular metal-metal and metal-anion contacts in their crystal lattices, thus providing solid-state evidence for metallophilicity and metal-substrate interactions in two-coordinate d 10 metal ions. To verify the existence of weak closed-shell metal-metal interactions, UV-vis absorption and resonance Raman spectroscopic techniques have been employed. Comparisons of the absorption spectra of [M 2(P∩P)2]2+ and [M 3(P∩P∩P)2]3+ show that the spin- and dipole-allowed [ndσ* → (n + 1)pσ] transition red-shifts in energy from [M2(P∩P) 2]2+ to [M3(P∩P ∩P)2]3+. This spectral assignment was confirmed by resonance Raman spectroscopy, which reveals stronger metal-metal interaction in the 1[(n + 1)pσ, ndσ*] state compared to the ground state. Photoluminescence from the 3[(n + 1)pσ, ndσ*] excited state was also recorded for the [M 2(P∩P)2]X2 and [M 3(P∩P∩P)2]X3 solids, where X is a non-coordinating anion. The spectroscopic data for these metal-centered transitions are supported by theoretical calculations. Perturbations of the MM bonded excited states through interaction with neighboring solvent molecules or anions lead to exciplex formations with emission in the visible region. The sensitivity of photoluminescence of two-coordinate d10 metal complexes to metal-ligand coordination provides an entry to new classes of luminescent sensory materials for substrate-binding processes. The 3[(n + 1)pσ, ndσ*] excited states of [M2(P∩P)2]2+ (M = Cu and Au) systems are powerful reductants and light-induced multi-electron photocatalysis by these systems have been observed. © 2005 Elsevier B.V. All rights reserved.
Persistent Identifierhttp://hdl.handle.net/10722/70090
ISSN
2015 Impact Factor: 12.994
2015 SCImago Journal Rankings: 4.100
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorChe, CMen_HK
dc.contributor.authorLai, SWen_HK
dc.date.accessioned2010-09-06T06:19:37Z-
dc.date.available2010-09-06T06:19:37Z-
dc.date.issued2005en_HK
dc.identifier.citationCoordination Chemistry Reviews, 2005, v. 249 n. 13-14, p. 1296-1309en_HK
dc.identifier.issn0010-8545en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70090-
dc.description.abstractStructural investigations of homometallic di- and tri-nuclear coinage metal complexes with bridging phosphine ligands, [M2(P∩P) 2]X2 and [M3(P∩P ∩P)2]X3 (M = Cu(I), Au(I), and Ag(I); X = anion), have revealed close intramolecular metal-metal and metal-anion contacts in their crystal lattices, thus providing solid-state evidence for metallophilicity and metal-substrate interactions in two-coordinate d 10 metal ions. To verify the existence of weak closed-shell metal-metal interactions, UV-vis absorption and resonance Raman spectroscopic techniques have been employed. Comparisons of the absorption spectra of [M 2(P∩P)2]2+ and [M 3(P∩P∩P)2]3+ show that the spin- and dipole-allowed [ndσ* → (n + 1)pσ] transition red-shifts in energy from [M2(P∩P) 2]2+ to [M3(P∩P ∩P)2]3+. This spectral assignment was confirmed by resonance Raman spectroscopy, which reveals stronger metal-metal interaction in the 1[(n + 1)pσ, ndσ*] state compared to the ground state. Photoluminescence from the 3[(n + 1)pσ, ndσ*] excited state was also recorded for the [M 2(P∩P)2]X2 and [M 3(P∩P∩P)2]X3 solids, where X is a non-coordinating anion. The spectroscopic data for these metal-centered transitions are supported by theoretical calculations. Perturbations of the MM bonded excited states through interaction with neighboring solvent molecules or anions lead to exciplex formations with emission in the visible region. The sensitivity of photoluminescence of two-coordinate d10 metal complexes to metal-ligand coordination provides an entry to new classes of luminescent sensory materials for substrate-binding processes. The 3[(n + 1)pσ, ndσ*] excited states of [M2(P∩P)2]2+ (M = Cu and Au) systems are powerful reductants and light-induced multi-electron photocatalysis by these systems have been observed. © 2005 Elsevier B.V. All rights reserved.en_HK
dc.languageengen_HK
dc.publisherElsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/ccren_HK
dc.relation.ispartofCoordination Chemistry Reviewsen_HK
dc.rightsCoordination Chemistry Reviews. Copyright © Elsevier BV.en_HK
dc.subjectClosed shellen_HK
dc.subjectExciplexen_HK
dc.subjectLuminescenceen_HK
dc.subjectMetallophilicityen_HK
dc.subjectSpectroscopyen_HK
dc.titleStructural and spectroscopic evidence for weak metal-metal interactions and metal-substrate exciplex formations in d10 metal complexesen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0010-8545&volume=249&spage=1296&epage=1309&date=2005&atitle=Structural+and+Spectroscopic+Evidence+For+Weak+Metal-Metal+Interactions+and+Metal-Substrate+Exciplex+Formations+in+d10+Metal+Complexesen_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.emailLai, SW: swlai@hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.identifier.authorityLai, SW=rp00717en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1016/j.ccr.2004.11.026en_HK
dc.identifier.scopuseid_2-s2.0-23044507131en_HK
dc.identifier.hkuros107310en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-23044507131&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume249en_HK
dc.identifier.issue13-14en_HK
dc.identifier.spage1296en_HK
dc.identifier.epage1309en_HK
dc.identifier.isiWOS:000231398600002-
dc.publisher.placeNetherlandsen_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridLai, SW=7402937200en_HK

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