Mediation of Electron Transfer by Quadrupolar Interactions: The Constitutional, Electronic, and Energetic Complementarities in Supramolecular Chemistry
| Autor: | Suman Mallick, Xiaoli Chen, Yi Yang Wu, Gang Yi Wang, Junpeng Zhou, Yi Qin, Tao Cheng, Chun Y. Liu, Lijiu Cao, Miao Meng, Ying Ning Tan, Guang Yuan Zhu |
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| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
0301 basic medicine
Multidisciplinary Chemistry Band gap Molecular Physics Intermolecular force Supramolecular chemistry Electron donor 02 engineering and technology macromolecular substances 021001 nanoscience & nanotechnology Acceptor Article Supramolecular Chemistry 03 medical and health sciences Crystallography Electron transfer chemistry.chemical_compound 030104 developmental biology Computational Molecular Modelling Covalent bond Molecule lcsh:Q 0210 nano-technology lcsh:Science |
| Zdroj: | iScience, Vol 22, Iss, Pp 269-287 (2019) iScience |
| ISSN: | 2589-0042 |
| Popis: | 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. Graphical Abstract Highlights • Electron transfer in {[Mo2]-C4H2S-[Mo2]}+ is studied optically in aromatic solvents • Inclusion of a quadrupolar guest molecule gates the donor-acceptor electron transfer • Constitutional, electronic, and energetic complementarities in supramolecular system Supramolecular Chemistry; Computational Molecular Modelling; Molecular Physics |
| Databáze: | OpenAIRE |
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