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How the constitutional dynamics of a dynamic covalent library (DCL) adapts to the presence of a surface is of fundamental importance for the design of adaptive materials. In this work, we show that amine exchange can be achieved at the liquid/solid interface within one-dimensional and two-dimensional imine polymers, which were characterized on the submolecular scale by scanning tunneling microscopy (STM). The potential of a surface to influence the thermodynamic equilibrium in a mixture of constitutionally interrelated building blocks with different molar ratio was explored. Our investigation demonstrates that the substrate and molar ratio of precursors markedly rearrange the composition of the DCC libraries.

Dynamic covalent chemistry of imine polymers at the liquid/solid interface investigated by scanning tunneling microscopy