Assembly of Lanthanide-Containing 3D [MnMo 9 O 32 ] 6- -Based Metal-Organic Frameworks and Oxidative Desulfurization Performance.

Lanthanide-containing polyoxometalate-based metal-organic frameworks (POMOFs) not only enjoy intriguing architectures but also have good application prospects as catalysts. Herein, three novel three-dimensional (3D) POMOFs with the formulas of {H[Ln 3 (2,6-pydc) 2 (H 2 O) 10 (MnMo 9 O 32 )]·2H 2 O} n (Ln = La( 1 ), Pr( 2 ), Nd( 3 )) have been synthesized based on Waugh-type [MnMo 9 O 32 ] 6- anions and pyridine-2,6-dicarboxylate (2,6-H 2 pydc). Compounds 1 - 3 are isomorphic, and there are two kinds of one-dimensional (1D) helical chains with opposite handedness staggered into two-dimensional (2D) layers. Interestingly, the coordinated L - and R -[MnMo 9 O 32 ] 6- anions are encapsulated in 1D chains with the same chirality and are further expanded into 3D structures. The catalytic tests indicate that compounds 1 - 3 exhibit high-efficiency heterogeneous catalytic activity in the oxidative desulfurization reaction for catalyzing the oxidation of sulfides to sulfoxides using tert -butyl hydrogen peroxide (TBHP) as the oxidant. Moreover, a series of control experiments have been conducted to investigate the influence of various parameters such as temperature, time, solvent, catalyst, and substrate on the reaction. Significantly, compound 2 , as an example, exhibits good reusability and structural stability in the oxidative desulfurization reaction. It is worth noting that investigations on the oxidative desulfurization of [MnMo 9 O 32 ] 6- anions are scarce. Moreover, their electrochemical properties are also explored.