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.
| Original language | English |
|---|---|
| Pages (from-to) | 5888-5896 |
| Number of pages | 9 |
| Journal | Journal of Chemical Theory and Computation |
| Volume | 11 |
| Issue number | 12 |
| DOIs | |
| Publication status | Published - Nov 3 2015 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Computer Science Applications
Cite this
Computational Design of Intrinsic Molecular Rectifiers Based on Asymmetric Functionalization of N-Phenylbenzamide. / 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.
In: Journal of Chemical Theory and Computation, Vol. 11, No. 12, 03.11.2015, p. 5888-5896.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Computational Design of Intrinsic Molecular Rectifiers Based on Asymmetric Functionalization of N-Phenylbenzamide
AU - Ding, Wendu
AU - Koepf, Matthieu
AU - Koenigsmann, Christopher
AU - Batra, Arunabh
AU - Venkataraman, Latha
AU - Negre, Christian F A
AU - Brudvig, Gary W
AU - Crabtree, Robert H.
AU - Schmuttenmaer, Charles A.
AU - Batista, Victor S.
PY - 2015/11/3
Y1 - 2015/11/3
N2 - 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.
AB - 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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UR - http://www.scopus.com/inward/citedby.url?scp=84949681642&partnerID=8YFLogxK
U2 - 10.1021/acs.jctc.5b00823
DO - 10.1021/acs.jctc.5b00823
M3 - Article
VL - 11
SP - 5888
EP - 5896
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
SN - 1549-9618
IS - 12
ER -