Observing polymerization in 2D dynamic covalent polymers

The quality of crystalline two-dimensional (2D) polymers 1 – 6 is intimately related to the elusive polymerization and crystallization processes. Understanding the mechanism of such processes at the (sub)molecular level is crucial to improve predictive synthesis and to tailor material properties for applications in catalysis 7 – 10 and (opto)electronics 11 , 12 , among others 13 – 18 . We characterize a model boroxine 2D dynamic covalent polymer, by using in situ scanning tunnelling microscopy, to unveil both qualitative and quantitative details of the nucleation–elongation processes in real time and under ambient conditions. Sequential data analysis enables observation of the amorphous-to-crystalline transition, the time-dependent evolution of nuclei, the existence of ‘non-classical’ crystallization pathways and, importantly, the experimental determination of essential crystallization parameters with excellent accuracy, including critical nucleus size, nucleation rate and growth rate. The experimental data have been further rationalized by atomistic computer models, which, taken together, provide a detailed picture of the dynamic on-surface polymerization process. Furthermore, we show how 2D crystal growth can be affected by abnormal grain growth. This finding provides support for the use of abnormal grain growth (a typical phenomenon in metallic and ceramic systems) to convert a polycrystalline structure into a single crystal in organic and 2D material systems. In situ scanning tunnelling microscopy reveals the dynamic nature of the early stages of two-dimensional (2D) polymer formation and crystallization at the solid–liquid interface.