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Title: Structure–function relationships in single molecule rectification by N-phenylbenzamide derivatives

Abstract

Here, we examine structure–function relationships in a series of N-phenylbenzamide (NPBA) derivatives by using computational modeling to identify molecular structures that exhibit both rectification and good conductance together with experimental studies of bias-dependent single molecule conductance and rectification behavior using the scanning tunneling microscopy break-junction technique. From a large number of computationally screened molecular diode structures, we have identified NPBA as a promising candidate, relative to the other structures that were screened. We demonstrate experimentally that conductance and rectification are both enhanced by functionalization of the NPBA 4-carboxamido-aniline moiety with electron donating methoxy groups, and are strongly correlated with the energy of the conducting frontier orbital relative to the Fermi level of the gold leads used in break-junction experiments.

Authors:
 [1];  [2];  [3];  [4];  [4];  [5];  [2];  [2];  [2];  [2]
+ Show Author Affiliations
  1. Yale Univ., West Haven, CT (United States); Fordham Univ., Bronx, NY (United States)
  2. Yale Univ., West Haven, CT (United States); Yale Univ., New Haven, CT (United States)
  3. Yale Univ., West Haven, CT (United States)
  4. Columbia Univ., New York, NY (United States)
  5. Yale Univ., West Haven, CT (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (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:
1341855
Report Number(s):
LA-UR-15-28629
Journal ID: ISSN 1144-0546; NJCHE5
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
New Journal of Chemistry
Additional Journal Information:
Journal Volume: 40; Journal Issue: 9; Journal ID: ISSN 1144-0546
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; computer science; energy sciences; material science

Citation Formats

Koenigsmann, Christopher, Ding, Wendu, Koepf, Matthieu, Batra, Arunabh, Venkataraman, Latha, Negre, Christian F. A., Brudvig, Gary W., Crabtree, Robert H., Batista, Victor S., and Schmuttenmaer, Charles A. Structure–function relationships in single molecule rectification by N-phenylbenzamide derivatives. United States: N. p., 2016. Web. doi:10.1039/C6NJ00870D.
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Koenigsmann, Christopher, Ding, Wendu, Koepf, Matthieu, Batra, Arunabh, Venkataraman, Latha, Negre, Christian F. A., Brudvig, Gary W., Crabtree, Robert H., Batista, Victor S., & Schmuttenmaer, Charles A. Structure–function relationships in single molecule rectification by N-phenylbenzamide derivatives. United States. https://doi.org/10.1039/C6NJ00870D
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Koenigsmann, Christopher, Ding, Wendu, Koepf, Matthieu, Batra, Arunabh, Venkataraman, Latha, Negre, Christian F. A., Brudvig, Gary W., Crabtree, Robert H., Batista, Victor S., and Schmuttenmaer, Charles A. Thu . "Structure–function relationships in single molecule rectification by N-phenylbenzamide derivatives". United States. https://doi.org/10.1039/C6NJ00870D. https://www.osti.gov/servlets/purl/1341855.
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@article{osti_1341855,
title = {Structure–function relationships in single molecule rectification by N-phenylbenzamide derivatives},
author = {Koenigsmann, Christopher and Ding, Wendu and Koepf, Matthieu and Batra, Arunabh and Venkataraman, Latha and Negre, Christian F. A. and Brudvig, Gary W. and Crabtree, Robert H. and Batista, Victor S. and Schmuttenmaer, Charles A.},
abstractNote = {Here, we examine structure–function relationships in a series of N-phenylbenzamide (NPBA) derivatives by using computational modeling to identify molecular structures that exhibit both rectification and good conductance together with experimental studies of bias-dependent single molecule conductance and rectification behavior using the scanning tunneling microscopy break-junction technique. From a large number of computationally screened molecular diode structures, we have identified NPBA as a promising candidate, relative to the other structures that were screened. We demonstrate experimentally that conductance and rectification are both enhanced by functionalization of the NPBA 4-carboxamido-aniline moiety with electron donating methoxy groups, and are strongly correlated with the energy of the conducting frontier orbital relative to the Fermi level of the gold leads used in break-junction experiments.},
doi = {10.1039/C6NJ00870D},
journal = {New Journal of Chemistry},
number = 9,
volume = 40,
place = {United States},
year = {Thu Jun 30 00:00:00 EDT 2016},
month = {Thu Jun 30 00:00:00 EDT 2016}
}
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https://doi.org/10.1039/C6NJ00870D
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    Works referencing / citing this record:

    Controlling the rectification properties of molecular junctions through molecule–electrode coupling
    journal, January 2016

    • Koepf, Matthieu; Koenigsmann, Christopher; Ding, Wendu
    • Nanoscale, Vol. 8, Issue 36
    • DOI: 10.1039/c6nr04830g

    Molecular modelling and simulation for the design of molecular diodes using density functional theory
    journal, February 2020

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