Speaker
Description
Abstract:
Characterization 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. We approach this issue in a series of supramolecular mixed-valence (MV) donor(D)–bridge(B)‒acceptor(A) systems consisting of two bridged Mo2 units with a C6H6 molecule encapsulated, as characterized by the X-ray crystal structures. Herein, the host-guest quadrupolar interaction between the Mo2 integrated D–B–A system and C6H6 molecule shows profound effect on the intramolecular electron transfer. Comparative analysis of the intervalence charge transfer spectra in aromatic and non-aromatic solvents substantiates the strong electronic decoupling effect of the solvating benzene molecule that breaks down the dielectric solvation theory. Ab initio and density functional theory (DFT) calculations indicate that the intermolecular orbital overlaps between the complex bridge and the C6H6 molecule alter the electronic states of the D–B–A molecule through intermolecular nuclear dynamics. This work exemplifies that site-specific intermolecular interaction can be utilized to control the chemical property of supramolecular systems and to elucidate the functionalities of side-chains in biological systems.
