Control over the Self-Assembly and Dynamics of Metallacarborane Nanorotors by the Nature of the Polymer Matrix: A Solid-State NMR Study

Abstract

Solids that combine long-range order with rapid molecular reorientation offer a promising approach for the development of a novel class of functional materials with potential applications in materials science and nanotechnology. In this contribution, the capability of dicarbollide ions to undergo self-assembly processes with suitable macromolecules is demonstrated, and a strategy leading to the formation of structurally and dynamically well-defined amphidynamic polymeric composites is introduced. For this purpose, three amphidynamic nanocomposites were synthesized via the self-assembly of cobalt bis(dicarbollide) anions (CoD–), with neutral poly(ethylene oxide) (PEO), and two isomers of poly(vinylpyridine), P2VP and P4VP, in protonated form. All of the systems were characterized by a combined study employing WAXS, advanced solid-state NMR, and quantum chemical calculations. It was found out that the interaction of neutral PEO with CoD– ions driven by weak dihydrogen bonding resulted in the formation of a ...