Bai Xue, Han Xu, Wang Yuxin, Zhang Ange, Yang Yanli, Lu Ying, Liu Shuxia
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, College of Chemistry, Northeast Normal University, Changchun, Jilin 130024, P. R. China.
Inorg Chem. 2023 Aug 21;62(33):13221-13229. doi: 10.1021/acs.inorgchem.3c01393. Epub 2023 Aug 8.
Two new three-dimensional (3D) polyoxometalate-based metal-organic frameworks (POMOFs), [M(btap)(HO)(HPMo MoO)] (M = Co () and Cd (); btap = 3, 5-bis(1', 2', 4'-triazol-1'-yl)pyridine), have been synthesized under mild hydrothermal conditions and characterized in detail. Single-crystal X-ray diffraction (SXRD) analysis indicates that and are isostructural. In complexes and , the metal ion is coordinated with the ligand to form two different left and right helical one-dimensional chains, which are alternately connected in a twisted form to build a two-fold interpenetrated three-dimensional structure, and the polyoxometalate is encapsulated into in the pores generated by the interpenetrating structure. It is noteworthy that and , as recyclable catalysts, possess favorable heterogeneous catalytic activity and excellent sulfoxide selectivity in sulfide oxidation reactions, with HO as an oxidant. By reason of the high dispersion of polyoxometalate with good intrinsic activity in the skeleton structure, the title complex has high activity. In addition, no obvious decrease of sulfoxide yield is observed after at least five cycles. These results indicate the excellent catalytic activity and sustainability of and .
在温和水热条件下合成了两种新型的基于多金属氧酸盐的三维（3D）金属有机框架（POMOFs），即[M(btap)(H₂O)(HPMo₁₂MoO₄₀)]（M = Co（Ⅱ）和Cd（Ⅱ）；btap = 3, 5-双（1', 2', 4'-三唑-1'-基）吡啶），并对其进行了详细表征。单晶X射线衍射（SXRD）分析表明，[Co(btap)(H₂O)(HPMo₁₂MoO₄₀)]和[Cd(btap)(H₂O)(HPMo₁₂MoO₄₀)]是同构的。在配合物[Co(btap)(H₂O)(HPMo₁₂MoO₄₀)]和[Cd(btap)(H₂O)(HPMo₁₂MoO₄₀)]中，金属离子与配体配位形成两条不同的左旋和右旋螺旋一维链，它们以扭曲的形式交替连接以构建一个二重互穿的三维结构，并且多金属氧酸盐被封装在由互穿结构产生的孔中。值得注意的是，[Co(btap)(H₂O)(HPMo₁₂MoO₄₀)]和[Cd(btap)(H₂O)(HPMo₁₂MoO₄₀)]作为可回收催化剂，在以H₂O₂为氧化剂的硫化物氧化反应中具有良好的多相催化活性和优异的亚砜选择性。由于多金属氧酸盐在骨架结构中具有高分散性且具有良好的固有活性，标题配合物具有高活性。此外，至少经过五个循环后，未观察到亚砜产率有明显下降。这些结果表明[Co(btap)(H₂O)(HPMo₁₂MoO₄₀)]和[Cd(btap)(H₂O)(HPMo₁₂MoO₄₀)]具有优异的催化活性和可持续性。
