Synthesis on inert surfaces

Extraordinarily robust extended covalent organic nanostructures with unprecedented structures and intriguing chemical and electronic properties are currently synthesized on metal surfaces. Envisaged electronic applications, for instance in field effect transistors or sensors, however, demand insulating supports. To obviate the need for a cumbersome post-synthetic transfer from the metal growth surface to the target substrate, synthesis directly on inert surfaces is highly desirable. Albeit reversible polycondensations are broadly established on inert graphite surfaces, carbon–carbon (C–C) coupling remains mostly elusive. Thermally activated coupling on weakly interacting supports suffers from the “desorption problem”, that is the premature desorption of reactants due to increased reaction barriers, which becomes even worse on inert surfaces due to diminished desorption barriers. Consequently, C–C coupling on inert surfaces requires new paradigms. We propose either photochemical coupling or activation of monomers prior to deposition as possible alternatives, discuss the current state-of-the-art and identify future challenges.