Self-Assembly of [Pt<sub>3<i>n</i></sub>(CO)<sub>6<i>n</i></sub>]<sup>2−</sup> (<i>n</i> = 4−8) Carbonyl Clusters: from Molecules to Conducting Molecular Metal Wires
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A comprehensive study discussing the different parameters that influence the self-assembly of [Pt3n(CO)6n]2− (n = 4−8) clusters with miscellaneous mono- and dications into 0-D, 1-D, 2-D, and 3-D materials is herein reported. As an unexpected bonus, the use of RuII dications allowed the first structural characterization of the previously unknown [Pt21(CO)42]2− dianion. 0-D structures, which contain isolated ions, are electrical insulators in solid form. Conversely, as soon as infinite chains of clusters are formed, the electrical resistivity, measured in pressed pellets, decreases to 105−106, 104, and 102 Ω cm for discontinuous, semicontinuous, and continuous chains, respectively. Therefore, the resemblance of these materials to molecular metal wires is not only morphological but also functional. Preliminary results of possible self-assembly phenomena in a solution of [Pt15(CO)30]2− and [Pt18(CO)36]2− according to dynamic light scattering experiments are also reported.
