Deciphering the factors influencing electric field mediated polymerization and depolymerization at the solution-solid interface.

Strong and oriented electric fields are known to influence structure as well as reactivity. The strong electric field (EF) between the tip of a scanning tunneling microscope (STM) and graphite has been used to modulate two-dimensional (2D) polymerization of aryl boronic acids where switching the polarity of the substrate bias enabled reversible transition between self-assembled molecular networks of monomers and crystalline 2D polymer (2DP) domains. Here, we untangle the different factors influencing the EF-mediated (de)polymerization of a boroxine-based 2DP on graphite. The influence of the solvent was systematically studied by varying the nature from polar protic to polar aprotic to non-polar. The effect of monomer concentration was also investigated in detail with a special focus on the time-dependence of the transition. Our experimental observations indicate that while the nucleation of 2DP domains is not initiated by the applied electric field, their depolymerization and subsequent desorption, are a consequence of the change in the polarity of the substrate bias within the area scanned by the STM tip. We conclude that the reversible transition is intimately linked to the bias-induced adsorption and desorption of the monomers, which, in turn, could drive changes in the local concentration of the monomers.