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Title: A reversible single-molecule switch based on activated antiaromaticity

Abstract

Single-molecule electronic devices provide researchers with an unprecedented ability to relate novel physical phenomena to molecular chemical structures. Typically, conjugated aromatic molecular backbones are relied upon to create electronic devices, where the aromaticity of the building blocks is used to enhance conductivity. We capitalize on the classical physical organic chemistry concept of Hückel antiaromaticity by demonstrating a single-molecule switch that exhibits low conductance in the neutral state and, upon electrochemical oxidation, reversibly switches to an antiaromatic high-conducting structure. We form single-molecule devices using the scanning tunneling microscope–based break-junction technique and observe an on/off ratio of ~70 for a thiophenylidene derivative that switches to an antiaromatic state with 6-4-6-p electrons. Through supporting nuclear magnetic resonance measurements, we show that the doubly oxidized core has antiaromatic character and we use density functional theory calculations to rationalize the origin of the high-conductance state for the oxidized single-molecule junction. Together, our work demonstrates how the concept of antiaromaticity can be exploited to create single-molecule devices that are highly conducting.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [1]
  1. Columbia Univ., New York, NY (United States). Dept. of Chemistry
  2. Columbia Univ., New York, NY (United States). Dept. of Applied Physics
  3. Fudan Univ., Shanghai (China)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  5. Columbia Univ., New York, NY (United States). Dept. of Chemistry; Columbia Univ., New York, NY (United States). Dept. of Applied Physics
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1432216
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 3; Journal Issue: 10; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yin, Xiaodong, Zang, Yaping, Zhu, Liangliang, Low, Jonathan Z., Liu, Zhen-Fei, Cui, Jing, Neaton, Jeffrey B., Venkataraman, Latha, and Campos, Luis M. A reversible single-molecule switch based on activated antiaromaticity. United States: N. p., 2017. Web. doi:10.1126/sciadv.aao2615.
Yin, Xiaodong, Zang, Yaping, Zhu, Liangliang, Low, Jonathan Z., Liu, Zhen-Fei, Cui, Jing, Neaton, Jeffrey B., Venkataraman, Latha, & Campos, Luis M. A reversible single-molecule switch based on activated antiaromaticity. United States. doi:10.1126/sciadv.aao2615.
Yin, Xiaodong, Zang, Yaping, Zhu, Liangliang, Low, Jonathan Z., Liu, Zhen-Fei, Cui, Jing, Neaton, Jeffrey B., Venkataraman, Latha, and Campos, Luis M. Fri . "A reversible single-molecule switch based on activated antiaromaticity". United States. doi:10.1126/sciadv.aao2615. https://www.osti.gov/servlets/purl/1432216.
@article{osti_1432216,
title = {A reversible single-molecule switch based on activated antiaromaticity},
author = {Yin, Xiaodong and Zang, Yaping and Zhu, Liangliang and Low, Jonathan Z. and Liu, Zhen-Fei and Cui, Jing and Neaton, Jeffrey B. and Venkataraman, Latha and Campos, Luis M.},
abstractNote = {Single-molecule electronic devices provide researchers with an unprecedented ability to relate novel physical phenomena to molecular chemical structures. Typically, conjugated aromatic molecular backbones are relied upon to create electronic devices, where the aromaticity of the building blocks is used to enhance conductivity. We capitalize on the classical physical organic chemistry concept of Hückel antiaromaticity by demonstrating a single-molecule switch that exhibits low conductance in the neutral state and, upon electrochemical oxidation, reversibly switches to an antiaromatic high-conducting structure. We form single-molecule devices using the scanning tunneling microscope–based break-junction technique and observe an on/off ratio of ~70 for a thiophenylidene derivative that switches to an antiaromatic state with 6-4-6-p electrons. Through supporting nuclear magnetic resonance measurements, we show that the doubly oxidized core has antiaromatic character and we use density functional theory calculations to rationalize the origin of the high-conductance state for the oxidized single-molecule junction. Together, our work demonstrates how the concept of antiaromaticity can be exploited to create single-molecule devices that are highly conducting.},
doi = {10.1126/sciadv.aao2615},
journal = {Science Advances},
number = 10,
volume = 3,
place = {United States},
year = {2017},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: Model of the electrochemically activated BTP switch. BTP shows the neutral, low-conductance state. Upon oxidation, BTP gains antiaromatic character to the 6-4-6-π electron state that exhibits high conductance.

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    Works referencing / citing this record:

    A reversible single-molecule switch based on activated antiaromaticity
    text, January 2017

    • Yin, Xiaodong; Zang, Yaping; Zhu, Liangliang
    • Columbia University
    • DOI: 10.7916/d8h431tc

    Multicenter-Bond-Based Quantum Interference in Charge Transport Through Single-Molecule Carborane Junctions
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    • Tang, Chun; Chen, Lijue; Zhang, Longyi
    • Angewandte Chemie International Edition, Vol. 58, Issue 31
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    Dinaphthobenzo[1,2:4,5]dicyclobutadiene: Antiaromatic and Orthogonally Tunable Electronics and Packing
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    Non-aromatic annulene-based aggregation-induced emission system via aromaticity reversal process
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    Dinaphthobenzo[1,2:4,5]dicyclobutadiene: Antiaromatic and Orthogonally Tunable Electronics and Packing
    journal, January 2019

    • Jin, Zexin; Yao, Ze-Fan; Barker, Kayla P.
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    Multicenter-Bond-Based Quantum Interference in Charge Transport Through Single-Molecule Carborane Junctions
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    • Tang, Chun; Chen, Lijue; Zhang, Longyi
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    Non-aromatic annulene-based aggregation-induced emission system via aromaticity reversal process
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