Self-assembly of three Ag-polyoxovanadates frameworks for their efficient construction of C–N bond and detoxification of simulant sulfur mustard

Three imidazole-modified Ag-polyoxovanadates frameworks(APFs)with a controllable molar ratio of Ag+to polyoxovanadates(POVs)[Ag(IM)_(2)]_(2)V_(4)O_(12)·2Ag(IM)_(2)(APF-1),[Ag_(2)(1-eIM)_(4)]_(2)[Ag(1-eIM)_(2)]_(3)·2Ag(1-eIM)_(2)·3(1-HeIM)[V_(10)O_(28)]_(2)(APF-2)and[Ag(1-pIM)_(2)]_(3)[HV_(10)O_(28)]·2Ag(1-pIM)_(2)·2H_(2)O(APF-3)(IM=imida-zole;1-eIM=1-ethylimidazole and 1-pIM=1-propylimidazole)have been successfully achieved by self-assembly of POVs,Ag+cations,and three different imidazole derivatives.Interestingly,the molar ratios of Ag+to POVs vary from 4:1,4.5:1 to 5:1 by changing the vanadium resources and imidazole deriva-tives.Notably,the coordination environment of Ag+cations and the structure of POVs in the APFs are also different.Specifically,for APF-1,the four Ag atoms adopt three-coordinated and four-coordinated geometries,respectively,and Ag-imidazole complexes and[V_(4)O 1_(2)]_(4)−cluster form the one-dimensional polymeric chains.While Ag atoms in APF-2 and APF-3 exhibit two-,four-and five-coordinated geome-tries for APF-2,four-,five-and six-coordinated geometries for APF-3,respectively.These Ag+cations and decavanadate clusters are assembled into the 2D supramolecular structure through the Ag-O bonds and Ag…Ag argentophilic interaction.Remarkably,thus-obtained APF-2 can serve as powerful efficient hetero-geneous catalyst for construction of C–N bond and detoxification of simulant sulfur mustard(yields up to 99%),which enable successful recycling for three cycles with remained catalytic activities and structure stability.