Synthesis of Pyridine-Containing 1D and 2D Conjugated Polymers via Ru-Catalyzed Direct Arylation Polymerization for Applications as Large-Band-Gap Photoelectrocatalysts

This report investigates the untapped potential of ruthenium catalysis to prepare nanoscale, extended Covalent Organic Polymer (COP) networks. We designed and synthesized three distinct nitrogen-doped COP nanostructures via Ru-catalyzed direct arylation polymerization. These nanoscale COPs, termed M1-COP, M2-COP, and M3-COP, were fully characterized using optical microscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and powder X-ray diffraction (PXRD). The resulting nanomaterials consist of large, nanometer-thin, crystalline flakes with low defect densities, confirming the high structural order achieved through the Ru-catalyzed polymerization route. These developed two-dimensional COPs represent a promising class of high-band-gap supports for photoelectrocatalytic applications.