Computational Design of Intrinsic Molecular Rectifiers Based on Asymmetric Functionalization of N‑Phenylbenzamide

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 b...

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Bibliographic Details
Published in:Journal of chemical theory and computation 2015-12, Vol.11 (12), p.5888-5896
Main Authors: Ding, Wendu, Koepf, Matthieu, Koenigsmann, Christopher, Batra, Arunabh, Venkataraman, Latha, Negre, Christian F. A., Brudvig, Gary W., Crabtree, Robert H., Schmuttenmaer, Charles A., Batista, Victor S.
Format: Article
Language:English
Subjects:
Asymmetry
Channels
Computation
Design engineering
Electron transport
Material Science
MATERIALS SCIENCE
Rectification
Rectifiers
Screening
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Summary: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.
ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.5b00823