摘要：SummaryCharacterization of covalency of intermolecular interactions in the van der Waals distance limit remains challenging because the interactions between molecules are weak, dynamic, and not measurable. Herein, we approach this issue in a series of supramolecular mixed-valence (MV) donor(D)-bridge(B)-acceptor(A) systems consisting of two bridged Mo2units with a C6H6molecule encapsulated, as characterized by the X-ray crystal structures. Comparative analysis of the intervalence charge transfer spectra in benzene and dichloromethane substantiates the strong electronic decoupling effect of the solvating C6H6molecule that breaks down the dielectric solvation theory.Ab initioand DFT calculations unravel that the intermolecular orbital overlaps between the complex bridge and the C6H6molecule alter the electronic states of the D-B-A molecule through intermolecular nuclear dynamics. This work exemplifies that site-specific intermolecular interaction can be exploited to control the chemical property of supramolecular systems and to elucidate the functionalities of side-chains in biological systems.Graphical abstractDisplay OmittedHighlights•Decoupling mixed-valence complexes by an encapsulated benzene molecule•Demonstrating intermolecular orbital interactions in the van der Waals distances•Illustrating interplay between intermolecular electronic and nuclear degrees of freedomChemistry; Organic chemistry; Physical organic chemistry
