Linker Independent Regioselective Protonation Triggered Detoxification of Sulfur Mustards with Smart Porous Organic Photopolymer

Abstract The development of efficient metal‐free photocatalysts for the generation of reactive oxygen species (ROS) for sulfur mustard (HD) decontamination can play a vital role against the stockpiling of chemical warfare agents (CWAs). Herein, one novel concept is conceived by smartly choosing a specific ionic monomer and a donor tritopic aldehyde, which can trigger linker‐independent regioselective protonation/deprotonation in the polymeric backbone. In this context, the newly developed vinylene‐linked ionic polymers (TPA/TPD‐Ionic) are further explored for visible‐light‐assisted detoxification of HD simulants. Time‐resolved‐photoluminescence (TRPL) study reveals the protonation effect in the polymeric backbone by significantly enhancing the life span of photoexcited electrons. In terms of catalytic performance, TPA‐Ionic outperformed TPD‐Ionic because of its enhanced excitons formation and charge carrier abilities caused by the donor‐acceptor (D‐A) backbone and protonation effects. Moreover, the formation of singlet oxygen (¹O₂) species is confirmed via in‐situ Electron Spin Resonance (ESR) spectroscopy and density functional theory (DFT) analysis, which explained the crucial role of solvents in the reaction medium to regulate the (¹O₂) formation. This study creates a new avenue for developing novel porous photocatalysts and highlights the crucial roles of sacrificial electron donors and solvents in the reaction medium to establish the structure‐activity relationship.