On the supramolecular interactions into a pH- and Metal-Actuated Molecular Shuttle: some insights from QTAIM modeling

Supramolecular contacts responsible for chemical interaction of cucurbit[7]uril (CB[7]) macrocycle on a Tolyl-Viologen-Phenylene-Imidazole (T-VPI) molecular thread, at acid pH (T-VPI-H⁺) or after Ag⁺ cation addition (T-VPI-Ag⁺), are analytically addressed in a computational framework combining Quantum Theory of Atoms in Molecules (QTAIM) with Density Functional Theory (DFT). In this respect, the crystallographic structure (CCDC number 2217466) is taken as reference condition for addressing the nature of the chemical interactions driving the shuttling of the CB[7] between T and P stations recently observed in dilute water solutions. Beside the host(CB[7]) vs guest(T-VPI-H⁺ or T-VPI-Ag⁺) complexation, the coordination sphere of the Ag⁺ cation is also investigated by means of local electronic energy density - H(r) - descriptors. The derived non-covalent interaction patterns are found to support diagnostic ¹H NMR signals used for detecting the mutual position of the CB[7] along the axle. This work highlights the potentialities of a QTAIM based approach in the characterization of supramolecular and metal-complexation effects in molecular aggregates such as not-interlocked synthetic molecular shuttles.