Palladium-Anchored Calix[4]Arene-Derived Porous Organic Polymer Towards Efficient Hydrolytic Cleavage of Carbon Disulfide

The release of carbon disulfide can have adverse effects on our environment and human health. The stability of carbon disulfide and the slow kinetics of hydrolysis can make it challenging to achieve efficient and practical cleavage of the C=S bonds. Herein, a calix[4]arene-based porous organic polymer (CPOP-1) is innovatively synthesized through an optimized polycondensation reaction using C-Methylcalix[4]resorcinarene and hexafluoro-hexaazatriphenylene as monomers. Subsequently, palladium-induced calix[4]arene-based porous organic polymer was also synthesized via strong Pd−N coordination bonds to construct the metal-induced porous catalyst (CPOP-2). The polymeric catalyst active center [Pd2+(N^N)(NO3-)2] demonstrated outstanding catalytic hydrolysis performance (11.14 μmol g-1 h-1) in 10.5 h which is significantly enhanced by ca.13.2 times as compared to reported mononuclear Bpy-Pd(NO3)2, and 7.2 times than model trinuclear complex catalyst HATN-Pd-1, respectively. The control experiments revealed that POP catalysts showcased robust stability, prolonged effectiveness, and feasible recyclability during the hydrolytic cleavage of carbon disulfide at room temperature in aqueous solutions. Furthermore, the coordination environment of [Pd2+(N^N)] was validated through XPS, EXAFS, and isotope labeling measurements, and the hydrolysis cleavage products were confirmed e. g. CO2, sulfide, and protons. More importantly, a reaction mechanism was formulated coupled with theoretical calculations, and simulations. The proposed mechanism involves sequential OH- nucleophilic attacks on the carbon atoms of insert-coordinated CS2 and COS, leading to the cleavage of double C=S bonds and the formation of C=O bonds. The concurrent dissociation of the C−S bond and liberation of CO2 result in an intermediate structure characterized by [(N^N)Pd2+](SH-)2. This intermediate motif serves as the source of the thermodynamic driving force for the reaction.