V═O Functionalized {Tm₂}–Organic Framework Designed by Postsynthesis Modification for Catalytic Chemical Fixation of CO₂ and Oxidation of Mustard Gas

Abstract

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 [Tm2(CO2)8] SBUs and 3d [VIVO­(H2O)2] units generated the functionalized porous metal–organic framework {(Me2NH2)2[VO­(H2O)]­[Tm2(BDCP)2]·3DMF·3H2O} n (NUC-11), in which [Tm2(CO2)8] SBUs constitute the fundamental 3D host framework of {[Tm2]­(BDCP)2} n along with [VIVO­(H2O)2] units being further docked on the inner wall of channels by covalent bonds. Significantly, NUC-11 represents the first example of VO modified porous MOFs, in which uncoordinated carboxylic groups (−CO2H) further grasp the functional [VIVO­(H2O)2] units on the initial basic skeleton along with the formation of covalent bonds as fixed ropes. Furthermore, activated samples of NUC-11 displayed a good catalytic performance for the chemical synthesis of carbonates from related epoxides and CO2 with high conversion rate. Moreover, by employing NUC-11 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.

Nanocage-Based Tb3+-Organic Framework for Efficiently Catalyzing the Cycloaddition Reaction of CO2 with Epoxides and Knoevenagel Condensation

“…The molecular sizes of various benzaldehyde derivatives are shown in Table S10. It is important to note that the TON value of model reaction is 784, which is obviously superior to most of the previously studied MOFs, such as Tb-DCBA, [Co 2 (bptc) (H 2 O) 2 ]·5DMA, [Zn­(κN-H 3 L) (H 2 O) 3 ]·3H 2 O, etc., shown in Table . − All the 1 H HMR spectra of Knoevenagel condensation products could be found in Figures S21–S26.…”

Reversible Structural Transformation and Catalytic Potential of Lanthanide-Azobenzenetetracarboxylates

“…It is also worth noting that the TON and TOF values yielded from II both with and without the activation process exceed those of the other LnCP-based catalysts previously reported for the same reactions (Table S3). ,,− …”

Synthesis of a novel nitrogen mustard–conjugated bis-terpyridine ruthenium(II) complex as a potent anticancer agent that induces cell cycle arrest and apoptosis

“…First, dichloride 2 was synthesized by the Vilsmeier–Haack reaction 18 of 2,2'-(phenylazanediyl)bis(ethan-1-ol) ( 1 ), excess POCl 3 , and DMF. Dichloride 2 was then converted into compound 3 in EtOH at room temperature by via a Knoevenagel condensation reaction, 19 in which compound 2 , 1-(pyridin-2-yl)ethan-1-one, and NH 4 OH were involved as the reactants and NaOH as the base. It is noteworthy that compound 3 is a small-sized ligand incorporating an aryl nitrogen mustard and terpyridine.…”