Intermolecular interactions play a key role in the charge transport properties of molecular electronic devices. In this work, we characterize charge transport in redox-active pyridinium-based molecular junctions mediated by host-guest interactions and intermolecular electrostatic effects. Charge transport through single pyridinium molecules generally shows that intramolecular conductance occurs over displacements consistent with the molecular contour length. However, pyridinium-based junctions exhibit charge transport over reduced molecular displacements upon increasing the solution concentration of the charged pyridinium complex, which is attributed to intermolecular electrostatic effects. Interestingly, formation of host-guest complexes via addition of a crown ether resulted in recovery of charge transport over molecular displacements corresponding to single pyridinium junctions at low concentrations, thereby suggesting that host-guest complexes efficiently screen electrostatic repulsions between cationic molecules. Bulk electrochemical characterization shows that pyridinium molecules exhibit stable redox-active properties over a wide array of conditions. Overall, this work opens new avenues for utilizing host-guest interactions that may be useful in informing the design of new redox-active flow batteries or programmable electronic devices.

Original languageEnglish (US)
Article number114070
JournalJournal of Electroanalytical Chemistry
StatePublished - Oct 15 2020


  • Intermolecular interactions
  • Molecular electronics
  • Redox-active molecules
  • Scanning tunneling microscope break-junction (STM-BJ)
  • Single molecule conductance

ASJC Scopus subject areas

  • Analytical Chemistry
  • General Chemical Engineering
  • Electrochemistry


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