Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers

摘要: On‐surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N‐containing pentacene‐based precursor (tetraazapentacene) is ex‐professo synthesized endowed with terminal dibromomethylene (:CBr2) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N‐containing conjugated coordination polymer (P1). Subsequently, P1 undergoes ladderization at 200 °C, affording a pyrrolopyrrole‐bridged conjugated …