Mediation of Electron Transfer by Quadrupolar Interactions: The Constitutional, Electronic, and Energetic Complementarities in Supramolecular Chemistry
Suman Mallick,
Lijiu Cao,
Xiaoli Chen,
Junpeng Zhou,
Yi Qin,
Gang Yi Wang,
Yi Yang Wu,
Miao Meng,
Guang Yuan Zhu,
Ying Ning Tan,
Tao Cheng,
Chun Y. Liu
Affiliations
Suman Mallick
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China
Lijiu Cao
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China
Xiaoli Chen
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China
Junpeng Zhou
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China
Yi Qin
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China
Gang Yi Wang
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China
Yi Yang Wu
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China
Miao Meng
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China
Guang Yuan Zhu
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China
Ying Ning Tan
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China
Tao Cheng
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China
Chun Y. Liu
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, China; Corresponding author
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
