Radically promoted formation of a molecular lasso

Yuping Wang, Junling Sun, Zhichang Liu, Majed S. Nassar, Youssry Y. Botros, J. Fraser Stoddart*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

Abstract

Two potential viologen-based molecular lasso precursors—both composed of a 4,4′-bipyridinium (BIPY2+) unit as part of a rope appended to a cyclobis(paraquat-p-phenylene) (CBPQT4+) loop—that have been designed to mimic the threading/unthreading motion of lasso peptides, have been synthesised and characterised. Solution and solid-state experiments reveal that, when the BIPY2+ unit in the rope and the CBPQT4+ loop are connected by a bulky linker, no lasso-like conformational transformation is observed between the different redox states on account of steric effects. In sharp contrast, when the linker size is small, the molecule can be switched between (i) a free rope-like conformation in its fully oxidised state and (ii) a self-entangled lasso-like conformation under reducing conditions employing either chemical or electrochemical stimuli: the BIPYandz.rad;+ unit in the rope resides inside the cavity of the CBPQT2(andz.rad;+) loop, forming a pseudo[1]rotaxane. The switching process is reversible and stereochemically unambiguous. This research shows how tiny structural differences can induce significantly different self-complexing properties and sheds light on designing functional artificial actuators.

Original languageEnglish (US)
Pages (from-to)2562-2568
Number of pages7
JournalChemical Science
Volume8
Issue number4
DOIs
StatePublished - 2017

ASJC Scopus subject areas

  • Chemistry(all)

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