Playing with the weakest supramolecular interactions in a 3D crystalline hexakisfullerene induces control over hydrogenation selectivity†
Weak forces can play an essential role in chemical reactions. Controlling such subtle forces in reorganization processes by applying thermal or chemical stimuli represents a novel synthetic strategy and one of the main targets in supramolecular chemistry. Actually, to separate the different supramolecular contributions to the stability of the 3D assemblies is still a major challenge. Therefore, a clear differentiation of these contributions would help in understanding the intrinsic nature as well as the chemical reactivity of supramolecular ensembles. In the present work, a controlled reorganization of an hexakisfullerene-based molecular compound purely governed by the weakest van der Waals interactions known, i.e. the dihydrogen interaction – usually called sticky fingers – is illustrated. This pre-reorganization of the hexakisfullerene under mild conditions allows a further selective hydrogenation of the crystalline material via hydrazine vapors exposure. This unique two-step transformation process is monitored by single-crystal to single-crystal diffraction (SCSC) which allows the direct observation of the molecular movements in the lattice and the subsequent solid–gas hydrogenation reaction.