Mediation of Electron Transfer by Quadrupolar Interactions: The Constitutional, Electronic, and Energetic Complementarities in Supramolecular Chemistry

Abstract

Summary: Studies of intermolecular interactions enhance our knowledge of chemistry across molecular and supramolecular levels. Here, we show that host-guest quadrupolar interaction has a profound influence on the molecular system. With covalently bonded dimolybdenum complex units as the electron donor (D) and acceptor (A) and a thienylene group (C4H2S) as the bridge (B), the mixed-valence D-B-A complexes are shaped with clefts in the middle of the molecule. Interestingly, in aromatic solvents, the D-A electronic coupling constants (Hab) and electron transfer rates (ket) are dramatically reduced. Theoretical computations indicate that an aromatic molecule is encapsulated in the cleft of the D-B-A array; quadrupole-quadrupole interaction between the guest molecule and the C4H2S bridge evokes a charge redistribution, which increases the HOMO-LUMO energy gap, intervening in the through-bond electron transfer. These results demonstrate that a supramolecular system is unified underlying the characteristics of the assembled molecules through constitutional, electronic, and energetic complementarities. : Supramolecular Chemistry; Computational Molecular Modelling; Molecular Physics Subject Areas: Supramolecular Chemistry, Computational Molecular Modelling, Molecular Physics