Temperature-Triggered Chiral Self-Assembly of Achiral Molecules at the Liquid-Solid Interface

ACS Appl Mater Interfaces. 2016 Nov 23;8(46):32004-32010. doi: 10.1021/acsami.6b10883. Epub 2016 Nov 9.

Abstract

Temperature triggered chiral nanostructures have been investigated on two-dimensional (2D) surfaces by means of scanning tunneling microscopy. Achiral molecules 1 and 2 tend to self-assemble into strip structures on graphite before heating. However, R and S flower-like structures are observed when heated to certain temperature. The transition temperatures of 1 and 2 systems are 55 and 60 °C, respectively. The density functional theory calculations demonstrate that R and S flower-like structures are more stable than strip structures. The coexistence of flower-like structures and strip structures demonstrates the thermodynamic equilibrium. Further, when chiral solvent is added to the sample with other conditions remaining the same, the racemic phenomenon disappears and homochirality emerges. This is an efficient method to control the chirality of 2D molecular assemblies.

Keywords: achiral molecules; chiral self-assembly; flower-like structure; scanning tunneling microscopy; temperature-triggered.