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dc.contributor.authorCalhorda, Maria José-
dc.contributor.authorCeamanos, Carmen-
dc.contributor.authorCrespo, Olga-
dc.contributor.authorGimeno, M. Concepción-
dc.contributor.authorLaguna, Antonio-
dc.contributor.authorLarraz, Carmen-
dc.contributor.authorVaz, Pedro .D.-
dc.contributor.authorVillacampa, M. Dolores-
dc.identifierdoi: 10.1021/ic100413x-
dc.identifierissn: 0020-1669-
dc.identifiere-issn: 1520-510X-
dc.identifier.citationInorganic Chemistry 49(18): 8255-8269 (2010)-
dc.description.abstractMetalloligands of stoichiometry [AuCl(P−N)] have been obtained by the reaction of the heterofunctional phosphines P−N = PPh2py, PPh2CH2CH2py, or PPhpy2 with [AuCl(tht)] (tht = tetrahydrothiophene). Reactions of these metalloligands with several metal compounds have afforded heteropolynuclear species which exhibit luminescent properties. The stoichiometries depend on the molar ratio and the heterometal. Thus, the reaction with [Cu(NCMe)4]+ in a molar ratio 2:1 gives the trinuclear compounds [Au2CuCl2(P−N)2]+, in which the structure and Au···Cu interactions depend on the phosphine ligand. With rhodium and iridium derivatives the reactivity is different leading to complexes of the type [AuMCl2(cod)(P−N)] for P−N = PPh2py, PPhpy2, and [Au2M2Cl(cod)2(P−N)2]Cl with PPh2CH2CH2py. Using [MCl2(NCPh)2] (M = Pd, Pt) in a 2:1 molar ratio yields [Au2MCl4(P−N)2] and in a 1:1 molar ratio [AuPdCl3(μ3-PPhpy2)]. Several compounds have been characterized by X-ray diffraction showing in many cases short Au···M distances. The luminescence of these derivatives has been studied. The metalloligands display bands assigned to intraligand (IL) transitions. For the bimetallic (Au/M) systems the luminescence depends on the heterometal present and on the metallophilic interactions. The most important excitations in the relevant energy range were assigned essentially a MMLCT character (from Rh/Ir and Au to ligands) based on density functional theory (DFT) calculations in selected complexes. The luminescence behavior in Rh/Ir [AuMCl2(cod)(PPh2py)] complexes was interpreted on the basis of the different nature of the half occupied orbitals in the triplet state.-
dc.description.sponsorshipWe thank the Dirección General de Investigación Científica y Técnica (CTQ2007-67273-C02-01) for financial support. M.J.C. and P.D.V. acknowledge FCT, POCI, and FEDER (project PTDC/QUI/58925/2004) for financial support.-
dc.publisherAmerican Chemical Society-
dc.titleHeteropolynuclear gold complexes with metallophilic interactions: Modulation of the luminescent properties-
dc.description.versionPeer Reviewed-
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