Pyrolysis Free Out‐of‐Plane Co‐Single Atomic Sites in Porous Organic Photopolymer Stimulates Solar‐Powered CO2 Fixation

Abstract Herein, a facile strategy is illustrated to develop pyrolysis‐free out‐of‐plane coordinated single atomic sites‐based M‐POP via a one‐pot Friedel Craft acylation route followed by a post‐synthetic metalation. The optimized geometry of the Co@BiPy‐POP clearly reveals the presence of out‐of‐plane Co‐single atomic sites in the porous backbone. This novel photopolymer Co@BiPy‐POP shows extensive π ‐conjugations followed by impressive light harvesting ability and is utilized for photochemical CO 2 fixation to value‐added chemicals. A remarkable conversion of styrene epoxide (STE) to styrene carbonate (STC) (≈98%) is obtained under optimized photocatalytic conditions in the existence of promoter tert ‐butyl ammonium bromide (TBAB). Synchrotron‐based X‐ray adsorption spectroscopy (XAS) analysis reveals the single atom coordination sites along with the metal (Co) oxidation number of +2.16 in the porous network. Moreover, in situ diffuse reflectance spectroscopy (DRIFTS) and electron paramagnetic resonance (EPR) investigations provide valuable information on the evolution of key reaction intermediates. Comprehensivecomputational analysis also helps to understand the overall mechanistic pathway along with the interaction between the photocatalyst and reactants. Overall, this study presents a new concept of fabricating porous photopolymers based on a pyrolysis‐free out‐of‐plane‐coordination strategy and further explores the role of single atomic sites in carrying out feasible CO 2 fixation reactions.