Transoid-to-Cisoid Conformation Changes of Single Molecules on Surfaces Triggered by Metal Coordination

Abstract

Conformational isomers are stereoisomers that can interconvert over low potential barriers by rotation around a single bond. However, such bond rotation is hampered by geometrical constraints when molecules are adsorbed on surfaces. Here we show that the adsorption of 4,4'-bis(4-carboxyphenyl)-6,6'-dimethyl-2,2'-bipyridine molecules on surfaces leads to the appearance of pro-chiral single-molecules on NiO(001) and to enantiopure supramolecular domains on Au(111) surfaces containing the $transoid$ molecule conformation. Upon additional Fe adatom deposition, molecules undergo a controlled interconversion from a $transoid$ to $cisoid$ conformation as a result of coordination of the Fe atoms to the 2,2'-bipyridine moieties. As confirmed by atomic force microscopy images and X-ray photoelectron spectroscopy measurements, the resulting molecular structures become irreversibly achiral.