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Title: Computational design of intrinsic molecular rectifiers based on asymmetric functionalization of N-phenylbenzamide

Abstract

Here, 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.

Authors:
 [1];  [2];  [2];  [3];  [3];  [1];  [1];  [1];  [1];  [1]
  1. Yale Univ., New Haven, CT (United States); Yale Univ., West Haven, CT (United States)
  2. Yale Univ., West Haven, CT (United States)
  3. Columbia Univ., New York, NY (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1256096
Report Number(s):
LA-UR-15-25235
Journal ID: ISSN 1549-9618
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 11; Journal Issue: 12; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Material Science

Citation Formats

Ding, Wendu, Koepf, Matthieu, Koenigsmann, Christopher, Batra, Arunabh, Venkataraman, Latha, Negre, Christian F. A., Brudvig, Gary W., Crabtree, Robert H., Schmuttenmaer, Charles A., and Batista, Victor S. Computational design of intrinsic molecular rectifiers based on asymmetric functionalization of N-phenylbenzamide. United States: N. p., 2015. Web. doi:10.1021/acs.jctc.5b00823.
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. Computational design of intrinsic molecular rectifiers based on asymmetric functionalization of N-phenylbenzamide. United States. doi:10.1021/acs.jctc.5b00823.
Ding, Wendu, Koepf, Matthieu, Koenigsmann, Christopher, Batra, Arunabh, Venkataraman, Latha, Negre, Christian F. A., Brudvig, Gary W., Crabtree, Robert H., Schmuttenmaer, Charles A., and Batista, Victor S. Tue . "Computational design of intrinsic molecular rectifiers based on asymmetric functionalization of N-phenylbenzamide". United States. doi:10.1021/acs.jctc.5b00823. https://www.osti.gov/servlets/purl/1256096.
@article{osti_1256096,
title = {Computational design of intrinsic molecular rectifiers based on asymmetric functionalization of N-phenylbenzamide},
author = {Ding, Wendu and Koepf, Matthieu and Koenigsmann, Christopher and Batra, Arunabh and Venkataraman, Latha and Negre, Christian F. A. and Brudvig, Gary W. and Crabtree, Robert H. and Schmuttenmaer, Charles A. and Batista, Victor S.},
abstractNote = {Here, 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.},
doi = {10.1021/acs.jctc.5b00823},
journal = {Journal of Chemical Theory and Computation},
number = 12,
volume = 11,
place = {United States},
year = {2015},
month = {11}
}

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