Heating/cooling stimulus induces three-state molecular switching of pseudoenantiomeric aminomethylenehelicene oligomers: Reversible nonequilibrium thermodynamic processes

Masanori Shigeno, Yo Kushida, Masahiko Yamaguchi

Research output: Contribution to journalArticlepeer-review

36 Citations (Scopus)

Abstract

A 1:1 mixture of pseudoenantiomeric aminomethylenehelicene (P)-tetramer and (M)-pentamer formed three states, namely, the heterodouble helices B and C and the random coil A. At high temperatures, A is the most stable. At low temperatures, C is the most stable, and the structural changes from A to the metastable state B to the product C occur, where B and C have pseudoenantiomeric helical structures. Heating then converts C to A. Essentially, all the molecules change their structure from A to B to C to A. Various nonequilibrium reversible thermodynamic responses appeared depending on thermal conditions: The metastable states A and B can be interconverted with thermal hysteresis without forming C in a far-from-equilibrium manner; three-state hysteresis occurs; states A and B can be frozen at low temperatures and defrosted by warming. An energy and population model for the three-state switching is given, involving inversion of thermodynamic stability and thermal hysteresis.

Original languageEnglish
Pages (from-to)7972-7980
Number of pages9
JournalJournal of the American Chemical Society
Volume136
Issue number22
DOIs
Publication statusPublished - 2014 Jun 4

ASJC Scopus subject areas

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

Fingerprint Dive into the research topics of 'Heating/cooling stimulus induces three-state molecular switching of pseudoenantiomeric aminomethylenehelicene oligomers: Reversible nonequilibrium thermodynamic processes'. Together they form a unique fingerprint.

Cite this