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Tuning the Rectification Ratio by Changing the Electronic Nature (Open-Shell and Closed-Shell) in Donor–Acceptor Self-Assembled Monolayers

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Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus de la UAB, 08193 Bellaterra, Spain
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
Centre for Advanced 2D Materials and Graphene Research Centre, National University of Singapore, 6 Science Drive 2, Singapore 117546, Singapore
Cite this: J. Am. Chem. Soc. 2017, 139, 12, 4262–4265
Publication Date (Web):March 10, 2017
Copyright © 2017 American Chemical Society

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    This Communication describes the mechanism of charge transport across self-assembled monolayers (SAMs) of two donor–acceptor systems consisting of a polychlorotriphenylmethyl (PTM) electron-acceptor moiety linked to an electron-donor ferrocene (Fc) unit supported by ultraflat template-stripped Au and contacted by a eutectic alloy of gallium and indium top contacts. The electronic and supramolecular structures of these SAMs were well characterized. The PTM unit can be switched between the nonradical and radical forms, which influences the rectification behavior of the junction. Junctions with nonradical units rectify currents via the highest occupied molecular orbital (HOMO) with a rectification ratio R = 99, but junctions with radical units have a new accessible state, a single-unoccupied molecular orbital (SUMO), which turns rectification off and drops R to 6.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.6b12601.

    • General methods for synthesis and characterization; synthesis and characterization of 1, 2, and 3; general procedures for the SAMs preparation and characterization, and transport measurements, including Figures S1–S21 and Tables S1–S4 (PDF)

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