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Fabrication and Transport Properties of Single-Molecule-Thick Electrochemical Junctions

Wong, Eric W. and Collier, Charles P. and Běhloradský, Martin and Raymo, Françisco M. and Stoddart, J. Fraser and Heath, James R. (2000) Fabrication and Transport Properties of Single-Molecule-Thick Electrochemical Junctions. Journal of the American Chemical Society, 122 (24). pp. 5831-5840. ISSN 0002-7863. doi:10.1021/ja993890v.

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A V-shaped compound incorporating two bipyridinium units, which emanate from a central hydrophilic core and bear hydrophobic tetraarylmethane-based stoppers at each end, was designed and synthesized. In a thermodynamically controlled self-assembly process in solution, either one or two 1,4-dioxybenzene-based macrocyclic polyethers can be slipped over the bulky stoppers of the V-shaped compound, affording either a [2]rotaxane or a [3]rotaxane, respectively. The parent V-shaped compound and the two rotaxanes incorporate two redox-active bipyridinium units that can be reduced reversibly and two redox-active phenoxy groups in the stoppers that can be oxidized irreversibly. Furthermore, these three compounds have amphiphilic character and, as a result, form stable monolayers at the air/water interface. Langmuir−Blodgett monolayers of these compounds were sandwiched between two electrodes to afford molecule-based solid-state switches. In forward bias mode, the I−V characteristics of the junction are reversible, but upon application of a sufficient reverse bias the junction resistance is irreversibly decreased, thereby switching the device. As a result, the current flowing through the device at forward bias voltages is lowered by a factor of 60−80. The behavior of the solid-state devices can be interpreted on the basis of the redox properties determined in solution for the three compounds. Initially, current flow at forward bias is determined by resonant tunneling through the molecular LUMO states associated with the bipyridium units. The irreversible decrease in current that occurs at reverse biases suggests a similarity to the solution-phase oxidation of the phenoxy groups.

Item Type:Article
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Stoddart, J. Fraser0000-0003-3161-3697
Heath, James R.0000-0001-5356-4385
Additional Information:© 2000 American Chemical Society. Received 2 November 1999. Published online 31 May 2000. This research was supported by the North Atlantic Treaty Organization (Collaborative Research Grant No. 960659), the National Science Foundation, and the Defense Advanced Research Projects Agency. We acknowledge helpful discussions with Dr. Stan Williams and Dr. Sang-Ho Kim.
Funding AgencyGrant Number
North Atlantic Treaty Organization (NATO)960659
Defense Advanced Research Projects Agency (DARPA)UNSPECIFIED
Issue or Number:24
Record Number:CaltechAUTHORS:20180302-081722324
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Official Citation:Fabrication and Transport Properties of Single-Molecule-Thick Electrochemical Junctions Eric W. Wong,Charles P. Collier,Martin Běhloradský,Françisco M. Raymo,J. Fraser Stoddart,* and, and James R. Heath* Journal of the American Chemical Society 2000 122 (24), 5831-5840 DOI: 10.1021/ja993890v
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85055
Deposited By: Ruth Sustaita
Deposited On:02 Mar 2018 16:28
Last Modified:15 Nov 2021 20:25

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