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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)]
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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)]
 
AuthorsYip, HK2
Lin, HM1
Cheung, KK2
Che, CM2
Wang, Y1
 
Issue Date1994
 
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
 
CitationInorganic Chemistry, 1994, v. 33 n. 8, p. 1644-1651 [How to Cite?]
DOI: http://dx.doi.org/10.1021/ic00086a014
 
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.
 
ISSN0020-1669
2012 Impact Factor: 4.593
2012 SCImago Journal Rankings: 1.778
 
DOIhttp://dx.doi.org/10.1021/ic00086a014
 
DC FieldValue
dc.contributor.authorYip, HK
 
dc.contributor.authorLin, HM
 
dc.contributor.authorCheung, KK
 
dc.contributor.authorChe, CM
 
dc.contributor.authorWang, Y
 
dc.date.accessioned2012-10-08T03:05:55Z
 
dc.date.available2012-10-08T03:05:55Z
 
dc.date.issued1994
 
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.
 
dc.description.natureLink_to_subscribed_fulltext
 
dc.identifier.citationInorganic Chemistry, 1994, v. 33 n. 8, p. 1644-1651 [How to Cite?]
DOI: http://dx.doi.org/10.1021/ic00086a014
 
dc.identifier.doihttp://dx.doi.org/10.1021/ic00086a014
 
dc.identifier.epage1651
 
dc.identifier.issn0020-1669
2012 Impact Factor: 4.593
2012 SCImago Journal Rankings: 1.778
 
dc.identifier.issue8
 
dc.identifier.scopuseid_2-s2.0-0001499935
 
dc.identifier.spage1644
 
dc.identifier.urihttp://hdl.handle.net/10722/167350
 
dc.identifier.volume33
 
dc.languageeng
 
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
 
dc.publisher.placeUnited States
 
dc.relation.ispartofInorganic Chemistry
 
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)]
 
dc.typeArticle
 
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<contributor.author>Che, CM</contributor.author>
<contributor.author>Wang, Y</contributor.author>
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<description.abstract>The 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) &#197;, b = 16.372(4) &#197;, c = 14.846(6) &#197;, and &#946; = 92.17(2)&#176;. The intramolecular Pt&#8943;Ag distance is 3.002(1) &#197;. The absorption spectra of [AuPt(dppm)2(CN)2]ClO4 and [AgPt(dppm)2(CN)2(CF3SO3)] exhibit intense 1(d&#963;* &#8594; p&#963;) transitions at 323 nm and 317 nm, respectively. The results of extended H&#252;ckel molecular orbital calculations suggested that the d&#963;* 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 &#956;s) at 570 nm. The emitting state has been suggested to be 3(d&#948;*p&#963;). 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- &#8594; [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. &#169; 1994 American Chemical Society.</description.abstract>
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Author Affiliations
  1. National Taiwan University
  2. The University of Hong Kong