Heating/Cooling Stimulus Induces Three-State Molecular Switching of Pseudoenantiomeric Aminomethylenehelicene Oligomers: Reversible Nonequilibrium Thermodynamic Processes
- 16 May 2014
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 136 (22), 7972-7980
- https://doi.org/10.1021/ja502009f
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.Keywords
Funding Information
- Japan Society for the Promotion of Science (21229001)
- Japan Society for the Promotion of Science (23790003)
This publication has 70 references indexed in Scilit:
- Isoindolinone-based molecular switchesOrganic & Biomolecular Chemistry, 2012
- High hopes: can molecular electronics realise its potential?Chemical Society Reviews, 2012
- Catenanes and threaded systems: from solution to surfacesChemical Society Reviews, 2009
- Motor Proteins at Work for NanotechnologyScience, 2007
- Synthetic Molecular Motors and Mechanical MachinesAngewandte Chemie-International Edition, 2006
- Toward Intelligent Molecular Machines: Directed Motions of Biological and Artificial Molecules and AssembliesChemical Reviews, 2005
- Molecular SwitchesPublished by Wiley ,2001
- Artificial Molecular MachinesAngewandte Chemie-International Edition, 2000
- The Way Things Move: Looking Under the Hood of Molecular Motor ProteinsScience, 2000
- Motility Powered by Supramolecular Springs and RatchetsScience, 2000