Playing with the weakest supramolecular interactions in a 3D crystalline hexakis[60]fullerene induces control over hydrogenation selectivity

Weak forces can play an essential role in chemical reactions. Controlling such subtle forces inreorganization processes by applying thermal or chemical stimuli represents a novel synthetic strategyand one of the main targets in supramolecular chemistry. Actually, to separate the differentsupramolecular 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 asthe chemical reactivity of supramolecular ensembles. In the present work, a controlled reorganization ofan hexakis[60]fullerene-based molecular compound purely governed by the weakest van der Waalsinteractions known,i.e.the dihydrogen interaction-usually called stickyfingers-is illustrated. This pre-reorganization of the hexakis[60]fullerene under mild conditions allows a further selective hydrogenationof the crystalline materialviahydrazine vapors exposure. This unique two-step transformation process ismonitored by single-crystal to single-crystal diffraction (SCSC) which allows the direct observation of themolecular movements in the lattice and the subsequent solid-gas hydrogenation reaction