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

ABSTRACT: 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 (H_ab) and electron transfer rates (k_et) 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 m

SUBMITTER: Mallick S 

PROVIDER: S-EPMC6909048 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature