Non-covalent interactions including dispersion, hydrogen bonding and metallophilicity play subtle yet decisive roles in determining molecular conformation and crystal structure, as well as functionalities such as catalysis and charge/energy transfer. The intensity and nature of these interactions are sensitive to both the local chemical environment and geometry; however, controlling these factors independently is challenging with conventional synthetic chemistry. High-pressure mechanochemistry presents exciting opportunities to this end. Mechanical pressure generates and stabilizes new ground-state geometries without changing molecular compositions, thereby deconvoluting the chemical and geometric factors. In this talk I will discuss our recent works using high pressure to probe and control non-covalent interaction in the solid state. First, we demonstrate pressure tuning of non-bonding interactions between d<sup>10</sup> metals in a cyclic trinuclear copper(I) (CTC) crystal, which presents clear evidence of competing inter- and intra-molecular metallophilicity. Second, we report pressure-dependent interactions between d<sup>8</sup> metals and C-H bonds in a series of metal tetraamine molecular crystals, and evaluate their potentials for C-H activation. These results demonstrate high pressure as a powerful tool for both mechanistic studies and novel synthesis in the solid state, and offers an alternative route toward the harvesting of mechanical energy.

Controlling non-covalent interactions in the solid state by high-pressure mechanochemistry

ACS Spring 2022

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