V═O Functionalized {Tm}-Organic Framework Designed by Postsynthesis Modification for Catalytic Chemical Fixation of CO and Oxidation of Mustard Gas.

In terms of recently documented references, the introduction of V═O units into porous MOF/COF frameworks can greatly improve their original performance and expand their application prospects due to a change in their electronegativity. In this work, by a cation-exchange strategy, a consummate combination of separate 4f [Tm(CO)] SBUs and 3d [VO(HO)] units generated the functionalized porous metal-organic framework {(MeNH)[VO(HO)][Tm(BDCP)]·3DMF·3HO} (), in which [Tm(CO)] SBUs constitute the fundamental 3D host framework of {Tm} along with [VO(HO)] units being further docked on the inner wall of channels by covalent bonds. Significantly, represents the first example of V═O modified porous MOFs, in which uncoordinated carboxylic groups (-COH) further grasp the functional [VO(HO)] units on the initial basic skeleton along with the formation of covalent bonds as fixed ropes. Furthermore, activated samples of displayed a good catalytic performance for the chemical synthesis of carbonates from related epoxides and CO with high conversion rate. Moreover, by employing as a catalyst, a simulator of mustard gas, 2-chloroethyl ethyl sulfide, could be quickly and efficiently oxidized into low-toxicity products of oxidized sulfoxide (CEESO). Thus, this study offers a brand new view for the design and synthesis of functional-units-modified porous MOFs, which could be potentially applied as an excellent candidate in the growing field of efficient catalysis.