▎ 摘　　要

Hybrid heterostructures formed from ordered molecular layers on two-dimensional materials can have unique properties differing from those of their bulk phases. By employing principles of dynamic covalent chemistry, we have synthesized a series of novel conjugated polyimines that form epitaxial ordered monolayers on graphene. The interplay between molecular physisorption and dynamic polymerization at the solid-liquid interface drives the formation of longer chains at the surface with dramatically higher rates than in solution. The physico-chemical properties of such assemblies at different length scales on graphene were investigated by a combination of experimental techniques. 'Covalent dynamic epitaxy' was also found to modulate the properties of both substrate and dynamers such as doping and photoluminescence, respectively.