title: Supramolecular assembly of diplatinum species through weak Pt(II)⋅⋅⋅Pt(II) intermolecular interactions: a combined experimental and computational study.
abstract: The present study elucidates the factors that govern the spontaneous self-assembly of a family of dimetal [Pt(2)L(4)] (L=dithiocarboxylato ligand) complexes. Experimental data show that variables such as temperature, concentration, solvent and the nature of the ligand L have a critical effect on the reversible self-assembly of supramolecular [Pt(2)L(4)](n) entities. In solution, new UV/Vis spectroscopic features emerge at low temperatures and/or high concentrations, which are attributed to the formation of oligomeric [Pt(2)L(4)](n) species. The description of intermolecular Pt⋅⋅⋅Pt interactions, the main driving force for the association, was addressed from a computational perspective. The contributions from intermolecular Pt⋅⋅⋅S and S⋅⋅⋅S interactions to these supramolecular assemblies were found to be repulsive. Experimental UV/Vis data have been interpreted by means of computational spectroscopy.
authors.affiliation: Nano-Bio Spectroscopy Group, Departamento de Física de Materiales, Universidad del País Vasco, Centro de Física de Materiales, CSIC-UPV/EHU-MPC and DIPC, Donostia, San Sebastián, Spain.
authors.forename: Alejandro
authors.initials: A
authors.lastname: Pérez Paz
authors.forename: Leonardo A
authors.initials: LA
authors.lastname: Espinosa Leal
authors.forename: Mohammad-Reza
authors.initials: MR
authors.lastname: Azani
authors.forename: Alejandro
authors.initials: A
authors.lastname: Guijarro
authors.forename: Pablo J
authors.initials: PJ
authors.lastname: Sanz Miguel
authors.forename: Gonzalo
authors.initials: G
authors.lastname: Givaja
authors.forename: Oscar
authors.initials: O
authors.lastname: Castillo
authors.forename: Rubén
authors.initials: R
authors.lastname: Mas-Ballesté
authors.forename: Félix
authors.initials: F
authors.lastname: Zamora
authors.forename: Angel
authors.initials: A
authors.lastname: Rubio