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Pt-Ag clusters and their neutral mononuclear Pt(ii) starting complexes: Structural and luminescence studies

AuthorsForniés, Juan CSIC; Sicilia, Violeta CSIC ORCID; Casas, José M. CSIC ORCID; Martín, Antonio CSIC ORCID; López, José A. CSIC ORCID; Larraz, Carmen CSIC; Borja, Pilar CSIC; Ovejero, Carmen
Issue Date2011
PublisherRoyal Society of Chemistry (UK)
CitationDalton Transactions 40(12): 2898-2912 (2011)
AbstractThe mononuclear complexes [Pt(bzq)(SS)] [SS = pyrrolidinedithiocarbamate (pdtc 1), dimethyldithiocarbamate (dmdtc 2)] were prepared by reaction of [Pt(bzq)(NCMe)2]ClO4 with an equimolecular amount of [NH4(pdtc)] and [Na(dmdtc)·2H2O] respectively in MeOH. Reactions of 1 and 2 with AgClO4 in 1:1 and 2:1 molar ratios rendered the heteropolinuclear compounds [{Pt(bzq)(SS)Ag}2](ClO 4)2 (SS = pdtc 3, dmdtc 4) and [{Pt(bzq)(SS)} 2Ag](ClO4) (SS = pdtc 5, dmdtc 6) respectively. The X-ray studies on single crystals of 3 and 4 showed that both consist of tetranuclear [Pt2Ag2] clusters with the Pt-Ag and the Ag-Ag distances in the range of those corresponding to Pt-Ag dative bonds and argentophilic interactions. In 3 the tetranuclear [Pt2Ag2] clusters are connected into infinite polymeric chains by Pt⋯Pt metallophilic interactions (Pt⋯Pt = 3.1890(7) Å). The X-ray study on a single crystal of 5 showed that it is a polymer based on trinuclear [Pt2Ag] clusters containing two unsupported Pt-Ag dative bonds and connected by Ag-S bonds in such a way that the >Pt-Ag-S-Pt-Ag-S> atoms draw a zigzag polymeric chain. TD-DFT calculations carried out for 1 indicate that the lowest energy absorption band in CH2Cl2 can be described as a mixture of 1MLCT, 1IL and 1L′LCT transitions. Powdered samples of 1 at 298 K and 77 K show a green-yellow emission band coming mainly from a 3LC excited state. However complex 2 shows >luminescence thermochromism>: the colour of its luminescence changes from green-yellow at 77 K to orange-red at 298 K. The emission of the Pt-Ag clusters, 3-6, in the solid state, are due to excimeric 3ππ and/or 3MMLCT (dσ* → π*) low-lying excited states, indicating that the presence of silver in the clusters makes the >Pt(bzq)(SS)> fragments interact to a large extent through Pt⋯Pt and/or π-π interactions. Solid 3 is a highly selective vapochromic compound towards acetonitrile although this behaviour is not fully reversible. © The Royal Society of Chemistry 2011.
Identifiersdoi: 10.1039/C0DT01451F
issn: 1477-9226
e-issn: 1477-9234
Appears in Collections:(ICMA) Artículos
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