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Article: Luminescent heterobimetallic complexes. Electronic structure, spectroscopy, and photochemistry of [AuPt(dppm)2(CN)2]ClO4 and the X-ray crystal structure of [AgPt(dppm)2(CN)2(CF3SO3)]

TitleLuminescent heterobimetallic complexes. Electronic structure, spectroscopy, and photochemistry of [AuPt(dppm)2(CN)2]ClO4 and the X-ray crystal structure of [AgPt(dppm)2(CN)2(CF3SO3)]
Authors
Issue Date1994
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1994, v. 33 n. 8, p. 1644-1651 How to Cite?
AbstractThe d10-d8 heterobimetallic complexes [AuPt(dppm)2(CN)2]ClO4 and [AgPt(dppm)2(CN)2(CF3SO3)] (dppm = bis(diphenylphosphino)methane) were prepared by literature methods. The X-ray crystal structure of [AgPt-(dppm)2(CN)2(CF3SO3)] has been determined. Crystal data for [AgPt(dppm)2(CN)2(CF3SO3)]: monoclinic, space group P21, a = 10.453(2) Å, b = 16.372(4) Å, c = 14.846(6) Å, and β = 92.17(2)°. The intramolecular Pt⋯Ag distance is 3.002(1) Å. The absorption spectra of [AuPt(dppm)2(CN)2]ClO4 and [AgPt(dppm)2(CN)2(CF3SO3)] exhibit intense 1(dσ* → pσ) transitions at 323 nm and 317 nm, respectively. The results of extended Hückel molecular orbital calculations suggested that the dσ* orbital in each case is mainly composed of the Pt (5dz2) orbital. In acetonitrile and at room temperature, [AuPt(dppm)2(CN)2]ClO4 exhibits a broad emission (lifetime = 18 μs) at 570 nm. The emitting state has been suggested to be 3(dδ*pσ). The effect of solvent on the emission properties has been investigated. The [AgPt(dppm)2(CN)2(CF3SO3)] complex shows metal-perturbed intraligand emission in glass solution at 77 K. The rate constants of quenching of the excited state of [AuPt(dppm)2(CN)2]+ by pyridinium acceptors have been treated by Marcus quadratic, Rehn-Weller, and Agmon-Levine equations and the excited state reduction potential of [AuPt(dppm)2(CN)2]+, [Au-Pt]2+ + e- → [Au-Pt]+*, is estimated to be about -1.73 to -1.80 V vs SCE. The photoreactions of [AuPt(dppm)2(CN)2]+ with halocarbons were investigated by Stern-Volmer quenching, flash photolysis, and steady-state photolysis experiments. An electron transfer mechanism is suggested. © 1994 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167350
ISSN
2014 Impact Factor: 4.762
2014 SCImago Journal Rankings: 1.681
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorYip, HKen_US
dc.contributor.authorLin, HMen_US
dc.contributor.authorCheung, KKen_US
dc.contributor.authorChe, CMen_US
dc.contributor.authorWang, Yen_US
dc.date.accessioned2012-10-08T03:05:55Z-
dc.date.available2012-10-08T03:05:55Z-
dc.date.issued1994en_US
dc.identifier.citationInorganic Chemistry, 1994, v. 33 n. 8, p. 1644-1651en_US
dc.identifier.issn0020-1669en_US
dc.identifier.urihttp://hdl.handle.net/10722/167350-
dc.description.abstractThe d10-d8 heterobimetallic complexes [AuPt(dppm)2(CN)2]ClO4 and [AgPt(dppm)2(CN)2(CF3SO3)] (dppm = bis(diphenylphosphino)methane) were prepared by literature methods. The X-ray crystal structure of [AgPt-(dppm)2(CN)2(CF3SO3)] has been determined. Crystal data for [AgPt(dppm)2(CN)2(CF3SO3)]: monoclinic, space group P21, a = 10.453(2) Å, b = 16.372(4) Å, c = 14.846(6) Å, and β = 92.17(2)°. The intramolecular Pt⋯Ag distance is 3.002(1) Å. The absorption spectra of [AuPt(dppm)2(CN)2]ClO4 and [AgPt(dppm)2(CN)2(CF3SO3)] exhibit intense 1(dσ* → pσ) transitions at 323 nm and 317 nm, respectively. The results of extended Hückel molecular orbital calculations suggested that the dσ* orbital in each case is mainly composed of the Pt (5dz2) orbital. In acetonitrile and at room temperature, [AuPt(dppm)2(CN)2]ClO4 exhibits a broad emission (lifetime = 18 μs) at 570 nm. The emitting state has been suggested to be 3(dδ*pσ). The effect of solvent on the emission properties has been investigated. The [AgPt(dppm)2(CN)2(CF3SO3)] complex shows metal-perturbed intraligand emission in glass solution at 77 K. The rate constants of quenching of the excited state of [AuPt(dppm)2(CN)2]+ by pyridinium acceptors have been treated by Marcus quadratic, Rehn-Weller, and Agmon-Levine equations and the excited state reduction potential of [AuPt(dppm)2(CN)2]+, [Au-Pt]2+ + e- → [Au-Pt]+*, is estimated to be about -1.73 to -1.80 V vs SCE. The photoreactions of [AuPt(dppm)2(CN)2]+ with halocarbons were investigated by Stern-Volmer quenching, flash photolysis, and steady-state photolysis experiments. An electron transfer mechanism is suggested. © 1994 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_US
dc.relation.ispartofInorganic Chemistryen_US
dc.titleLuminescent heterobimetallic complexes. Electronic structure, spectroscopy, and photochemistry of [AuPt(dppm)2(CN)2]ClO4 and the X-ray crystal structure of [AgPt(dppm)2(CN)2(CF3SO3)]en_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ic00086a014-
dc.identifier.scopuseid_2-s2.0-0001499935en_US
dc.identifier.volume33en_US
dc.identifier.issue8en_US
dc.identifier.spage1644en_US
dc.identifier.epage1651en_US
dc.identifier.isiWOS:A1994NF72100014-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridYip, HK=15068942100en_US
dc.identifier.scopusauthoridLin, HM=15068551600en_US
dc.identifier.scopusauthoridCheung, KK=7402406613en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridWang, Y=36072665800en_US

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