On‐Surface Fabrication toward Polar 2D Macromolecular Crystals

Abstract

Polar 2D macromolecular structures have attracted significant attention because of their ferroelectricity and ferro‐magnetism. However, it is challenging to synthesize them experimentally because dipoles or spins of these macromolecules tend to cancel each other. So far, there has been no successful strategy for assembling macromolecules in a unidirectional manner, achieving stereoregular polymerization on metal surfaces, and creating polar 2D polymer crystals. Recent progress in molecular assembly, on‐surface polymer synthesis, and direct control of molecules using electric field applications provides an opportunity to develop such strategies. In this regard, we first review past studies on chiral and achiral molecular assembly, on‐surface polymer synthesis, and orientation control of polar molecules. Then, we discuss our newly developed approach called “vectorial on‐surface synthesis”, which is based on “dynamic chirality” of compass precursors, stereoselective polymerization, and favorable interchain interactions originating from CH‐π interactions. Finally, we conclude with a prospective outlook.