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:
-
- Yale Univ., New Haven, CT (United States); Yale Univ., West Haven, CT (United States)
- Yale Univ., West Haven, CT (United States)
- Columbia Univ., New York, NY (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- 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. https://doi.org/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. https://doi.org/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 = {Tue Nov 03 00:00:00 EST 2015},
month = {Tue Nov 03 00:00:00 EST 2015}
}
Web of Science
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