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Forniés J, Sicilia V, Casas JM, et al. Pt-Ag clusters and their neutral mononuclear Pt(II) starting complexes: structural and luminescence studies. Dalton Trans. 2011;40(12):2898-912doi: 10.1039/c0dt01451f.
Forniés, J., Sicilia, V., Casas, J. M., Martín, A., López, J. A., Larraz, C., Borja, P., & Ovejero, C. (2011). Pt-Ag clusters and their neutral mononuclear Pt(II) starting complexes: structural and luminescence studies. Dalton transactions (Cambridge, England : 2003), 40(12), 2898-912. https://doi.org/10.1039/c0dt01451f
Forniés, Juan, et al. "Pt-Ag clusters and their neutral mononuclear Pt(II) starting complexes: structural and luminescence studies." Dalton transactions (Cambridge, England : 2003) vol. 40,12 (2011): 2898-912. doi: https://doi.org/10.1039/c0dt01451f
Forniés J, Sicilia V, Casas JM, Martín A, López JA, Larraz C, Borja P, Ovejero C. Pt-Ag clusters and their neutral mononuclear Pt(II) starting complexes: structural and luminescence studies. Dalton Trans. 2011 Mar 28;40(12):2898-912. doi: 10.1039/c0dt01451f. Epub 2011 Feb 11. PMID: 21311801.
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Dalton Trans. 2011 Mar 28;40(12):2898-912. doi: 10.1039/c0dt01451f. Epub 2011 Feb 11.

Pt-Ag clusters and their neutral mononuclear Pt(II) starting complexes: structural and luminescence studies.

Dalton transactions (Cambridge, England : 2003)

Juan Forniés, Violeta Sicilia, José M Casas, Antonio Martín, José A López, Carmen Larraz, Pilar Borja, Carmen Ovejero

Affiliations

  1. Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Facultad de Ciencias, Universidad de Zaragoza-CSIC, Plaza. S. Francisco s/n, 50009, Zaragoza, Spain. [email protected]

PMID: 21311801 DOI: 10.1039/c0dt01451f

Abstract

The mononuclear complexes [Pt(bzq)(S^S)] [S^S = pyrrolidinedithiocarbamate (pdtc 1), dimethyldithiocarbamate (dmdtc 2)] were prepared by reaction of [Pt(bzq)(NCMe)(2)]ClO(4) with an equimolecular amount of [NH(4)(pdtc)] and [Na(dmdtc)·2H(2)O] respectively in MeOH. Reactions of 1 and 2 with AgClO(4) in 1 : 1 and 2 : 1 molar ratios rendered the heteropolinuclear compounds [{Pt(bzq)(S^S)Ag}(2)](ClO(4))(2) (S^S = pdtc 3, dmdtc 4) and [{Pt(bzq)(S^S)}(2)Ag](ClO(4)) (S^S = pdtc 5, dmdtc 6) respectively. The X-ray studies on single crystals of 3 and 4 showed that both consist of tetranuclear [Pt(2)Ag(2)] 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 [Pt(2)Ag(2)] 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 [Pt(2)Ag] 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 CH(2)Cl(2) can be described as a mixture of (1)MLCT, (1)IL and (1)L'LCT transitions. Powdered samples of 1 at 298 K and 77 K show a green-yellow emission band coming mainly from a (3)LC 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 (3)ππ and/or (3)MMLCT (dσ* →π*) low-lying excited states, indicating that the presence of silver in the clusters makes the "Pt(bzq)(S^S)" 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.

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