2. Academic Validation
  3. Computational Design of Intrinsic Molecular Rectifiers Based on Asymmetric Functionalization of N-Phenylbenzamide

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

  • J Chem Theory Comput. 2015 Dec 8;11(12):5888-96. doi: 10.1021/acs.jctc.5b00823.
Wendu Ding 1 2,  Matthieu Koepf 2,  Christopher Koenigsmann 2,  Arunabh Batra 3,  Latha Venkataraman 3,  Christian F A Negre 1 2,  Gary W Brudvig 1 2,  Robert H Crabtree 1 2,  Charles A Schmuttenmaer 1 2,  Victor S Batista 1 2
Affiliations

Affiliations

  • 1 Department of Chemistry, Yale University , P.O. Box 208107, New Haven, Connecticut 06520-8107, United States.
  • 2 Yale Energy Sciences Institute, Yale University , P.O. Box 27394, West Haven, Connecticut 06516-7394, United States.
  • 3 Department of Applied Physics and Applied Mathematics, Columbia University , New York, New York 10027, United States.
PMID: 26642992 DOI: 10.1021/acs.jctc.5b00823
Abstract

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.

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