Redox-Driven Folding, Unfolding, and Refolding of Bis(tetrathiafulvalene) Molecular Switch

Jiyoung Jung, Wenjun Liu, Seyong Kim, Dongwhan Lee

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

We report redox-driven folding, unfolding, and refolding motions of a synthetic molecular system, in which two tetrathiafulvalene (TTF) units are tethered onto a conformationally rigid yet torsionally flexible π-conjugated backbone. Upon one-electron oxidation, this molecular switch undergoes swiveling motions from a fully relaxed and freely rotating Z-shaped conformation to a compact folded conformation stabilizing π-stacked radical species. Subsequent one-electron oxidation produces dicationic intermediates, which either engage in intimate π-πinteractions or transition to an open structure. Further oxidation, however, brings the molecule back to the initial conformation to minimize the repulsion between doubly-charged TTF units. Intriguingly, the reaction coordinates of this redox-driven structural change have strong dependence on the environment, such as the solvent (THF vs CH2Cl2) and supporting electrolyte (PF6- vs B(C6F5)4-). With a proper design, factors that are typically considered as "secondary effects" could dictate the solution dynamics and reaction pathways of structural folding and unfolding, all driven by controlled delivery of electrons.

Original languageEnglish (US)
Pages (from-to)6258-6269
Number of pages12
JournalJournal of Organic Chemistry
Volume84
Issue number10
DOIs
StatePublished - May 17 2019

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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