Dissipative and Autonomous Square-Wave Self-Oscillation of a Macroscopic Hybrid Self-Assembly under Continuous Light Irradiation

Abstract

Building a bottom-up supramolecular system to perform continuously autonomous motions will pave the way for the next generation of biomimetic mechanical systems. In biological systems, hierarchical molecular synchronization underlies the generation of spatio-temporal patterns with dissipative structures. However, it remains difficult to build such self-organized working objects via artificial techniques. Herein, we show the first example of a square-wave limit-cycle self-oscillatory motion of a noncovalent assembly of oleic acid and an azobenzene derivative. The assembly steadily flips under continuous blue-light irradiation. Mechanical self-oscillation is established by successively alternating photoisomerization processes and multi-stable phase transitions. These results offer a fundamental strategy for creating a supramolecular motor that works progressively under the operation of molecule-based machines.

Keywords: cooperative effects; molecular devices; non-equilibrium processes; phase transitions; photochromism.