Electrochemically Generated Nanoparticles of Halogen-Bridged Mixed-Valence Binuclear Metal Complex Chains

Spherical nanoparticles composed of MMX chains can be made by a polymerization strategy driven by electrochemical processes. In particular, the [Pt2(MeCS2)4I2] (MMI2) dimetal subunit is employed as a monomer for the formation of [Pt2(MeCS2)4I]n spherical nanostructures on surfaces. We have paid particular attention to elucidating the general mechanism of the deposition process on the basis of in situ electrochemical measurements. The reduction of MMI2 to give the electrodeposition of nanostructures agrees well with formation of the reduced [MMI2]− species followed by a disproportionation mechanism mediated by iodide anions. The chemical composition of the particles was determined by energy‐dispersive X‐ray spectroscopy (EDX) and X‐ray photoelectron spectroscopy (XPS) to reveal the MMI2 polymer. Chain reaction: Halogen‐bridged mixed‐valence binuclear metal complex (MMX) chain nanospheres have been electrochemically generated on a gold surface by assembly of the corresponding monomers (see figure).