Computational Design of Intrinsic Molecular Rectifiers Based on Asymmetric Functionalization of N-Phenylbenzamide
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- 作者：Wendu Ding ; Matthieu Koepf ; Christopher Koenigsmann ; Arunabh Batra ; Latha Venkataraman ; Christian F. A. Negre ; Gary W. Brudvig ; Robert H. Crabtree ; Charles A. Schmuttenmaer ; Victor S. Batista
- 刊名：Journal of Chemical Theory and Computation
- 出版年：2015
- 出版时间：December 8, 2015
- 年：2015
- 卷：11
- 期：12
- 页码：5888-5896
- 全文大小：635K
- ISSN：1549-9626
文摘
We report a systematic computational search of molecular frameworks for intrinsic rectification of electron transport. The screening of molecular rectifiers includes 52 molecules and conformers spanning over 9 series of structural motifs. N-Phenylbenzamide is found to be a promising framework with both suitable conductance and rectification properties. A targeted screening performed on 30 additional derivatives and conformers of N-phenylbenzamide yielded enhanced rectification based on asymmetric functionalization. We demonstrate that electron-donating substituent groups that maintain an asymmetric distribution of charge in the dominant transport channel (e.g., HOMO) enhance rectification by raising the channel closer to the Fermi level. These findings are particularly valuable for the design of molecular assemblies that could ensure directionality of electron transport in a wide range of applications, from molecular electronics to catalytic reactions.