Nanoscale tailoring of supramolecular crystals via an oriented external electric field.

The oriented external electric field of a scanning tunneling microscope (STM) has recently been adapted for controlling the chemical reaction and supramolecular phase transition at surfaces with molecular precision. However, to date, advance controls using such electric-fields for crystal engineering have not been achieved yet. Here, we present how the directional electric-field of an STM can be utilized to harness supramolecular crystallization on a solid surface. We show that a glass-like random-tiling assembly composed of p-terphenyl-3,5,3',5'-tetracarboxylic acid can transform into close-packed periodic assemblies under positive substrate bias conditions at the liquid/solid interface. Importantly, the nucleation and subsequent crystal growth for such field-induced products can be artificially tailored at the early stage in a real-time fashion. Through this method, we were able to produce a two-dimensional supramolecular single crystal. The as-prepared crystals with apparent brightness are ascribed to a spectroscopic feature linked to the electron density of states, which is thus strongly STM bias dependent.