The formation of atomically precise covalent networks directly on a surface is a promising approach to produce single layers of two-dimensional organic materials (2D polymers). In the emerging field of on-surface synthesis, there is an urgent need for finding a rationale to new reaction pathways taking place directly on the surface. In this feature article we review and put into perspective recent results on the surface polymerisation of boronic acid based systems under ultrahigh vacuum conditions studied by scanning tunnelling microscopy. By presenting several approaches to control the growth of covalent networks, we aim at providing a comprehensive overview of the complex mechanisms involved.
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