Folding of oligoviologens induced by radical-radical interactions

Yuping Wang, Marco Frasconi, Wei Guang Liu, Zhichang Liu, Amy A. Sarjeant, Majed S. Nassar, Youssry Y. Botros, William A. Goddard, J. Fraser Stoddart*

*Corresponding author for this work

Research output: Contribution to journalArticle

42 Scopus citations

Abstract

We report the synthesis of a series of homologous oligoviologens in which different numbers of 4,4′-bipyridinium (BIPY2+) subunits are linked by p-xylylene bridges, as a prelude to investigating how their radical cationic forms self-assemble both in solution and in the solid state. The strong radical-radical interactions between the radical cationic forms of the BIPY2+ units-namely, BIPY•+-in these oligoviologens induce intra- or intermolecular folding of these homologues. UV/Vis/NIR spectroscopic studies and DFT quantum mechanics indicate that the folding of the shorter oligoviologens is dominated by intermolecular radical-radical interactions. In addition to intermolecular interactions, strong intramolecular radical-radical interactions, which give rise to an NIR absorption band at 900 nm, tend to play a crucial role in governing the folding of the longer oligoviologens. The solid-state superstructure of the oligoviologen with three BIPY2+ units reveals that two intertwining chains fold together to form a dimer, stabilized by intermolecular radical-radical interactions. These dimers continue to stack in an infinite column through intermolecular radical-radical interactions between them. This research features an artificial biomimetic system which sustains delicate secondary and tertiary structures, reminiscent of those present in nucleic acids and proteins.

Original languageEnglish (US)
Pages (from-to)876-885
Number of pages10
JournalJournal of the American Chemical Society
Volume137
Issue number2
DOIs
StatePublished - Jan 21 2015

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Wang, Y., Frasconi, M., Liu, W. G., Liu, Z., Sarjeant, A. A., Nassar, M. S., Botros, Y. Y., Goddard, W. A., & Stoddart, J. F. (2015). Folding of oligoviologens induced by radical-radical interactions. Journal of the American Chemical Society, 137(2), 876-885. https://doi.org/10.1021/ja5111305