Isomeric sp2-C-conjugated porous organic polymer-mediated photo- and sono-catalytic detoxification of sulfur mustard simulant under ambient conditions

•Fully sp2-C-conjugated TPE-based isomeric POPs are reported for CEES detoxification•Porous photosensitizers offer ROS generation even under visible light and ultrasound•Catalytic oxidation of is achieved ambient atmosphere without toxic products•The composition the generated types engineered by POP structures Selective sulfide to sulfoxide, controlling overoxidized products, a highly demanding strategy detoxification sulfur mustard simulants (CEES). Singlet oxygen widely studied mild oxidant, but it utilized mainly in an oxygen-abundant environment rather than atmospheric conditions. Herein, we present porous organic polymers (POPs) photo-oxidize conditions byproducts. Furthermore, also discovered that superoxide hydroxyl radicals participate oxidative mechanism greater extent O2 atmosphere. In addition, demonstrate sono-catalytic selective ultrasound irradiation first time. Our findings will give inspiration further prospective applications as photo- sono-catalysts. The development efficient strategies sustainable gas has longstanding demand human safety. Here, time sono-catalyzed using conveniently prepared polymer (POP) catalysts. We developed microwave-assisted synthesis three tetraphenylethylene-based (TPo, TPm, TPp) bearing fully sp2-hybridized carbon frameworks. Among isomers, TPm efficiently 1O2, whereas TPp both O2.– HO. irradiation, selectively convert 2-chloroethyl ethyl (CEES) into nontoxic sulfoxide (CEESO) conditions, through known conversion mechanism. can generate 1O2 irradiation. This work provides insight designing new sono-catalysts widespread applications. IntroductionThe dangerous chemical warfare agents (CWAs), such phosgene, lewisite, other hazardous substances, have been severe threat humans since their initial use World War I. These chemicals include notorious mustard, 1,2-bis(2-chloroethyl)sulfide (military designation: HD), which resulted millions casualties due its low cost convenient production.1Ganesan K. Raza S.K. 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Following condensation, intensity C=O stretching peak infrared (IR) spectra centered 1,693 cm?1 aldehyde TPE-4CHO decreased, implying extended sp2-C conjugation forming network (Figures S2–S4). Interestingly, distinct C?N peaks 2,250 all red-shifted 2,216 (TPm or 2,197 (TPo) 2A). red-shift attributed weakening C–N bond strength resulting reaction. photoelectron spectroscopy analysis suggested elements C, N, O POPs, shown Figures S5 S6. As group each isomer different, binding energies N1s electrons seen different other. Solid-state 13C nuclear magnetic resonance (13C ssNMR) recorded obtain detailed information 2B). NMR spectra, (region 1) approximately 170 ppm, assigned unreacted aldehyde. more suggesting lower degree polymerization POPs. 2, phenyl ring) sp 3, group) 150–130 110 respectively. Peak positioned region 4 (below 50 ppm) indicates residual n-hexane sp3 carbons benzyl cyanide backbone.Figure 2Characterization TPpShow full caption(A) IR TPp.(B) spectra.(C D) UV-vis solid-state dispersed hexane, respectively.(E) Band diagram, top bottom bars conduction valence bands respectively.(F) N2 isotherms 77 Filled open symbols adsorption desorption, respectively.View Large Image Figure ViewerDownload Hi-res image Download (PPT)Furthermore, investigated optical electronic properties verify photosensitizers. absorption 2C), TPo shows region, display maximum 418 nm 200–600 range. photoluminescence quantum yield (PLQY) determined 0% (0%) 11% (13%) 13% (15%) 400 (450) excitation S7). However, when measure showed disparity among 2D). shifted 488 (TPp) 457 (TPm), no specific observed. To understand difference response, measured particle size scanning microscopy S8). diverse sizes (TPo: ?900 nm, TPm: ?50 TPp: ?500 nm), despite same synthetic method. 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