Department of Chemistry and International Institute of Nanotechnology , Northwestern University , 2145 Sheridan Road , Evanston , Illinois 60208 , United States.
School of Chemistry and Chemical Engineering , South China University of Technology , Guangzhou 510640 , P. R. China.
Inorg Chem. 2019 Mar 18;58(6):3586-3590. doi: 10.1021/acs.inorgchem.8b03511. Epub 2019 Feb 25.
The crystal structures of thorium clusters are important for understanding the formation and transformation mechanisms of actinide species in solution, which can in turns benefit nuclear waste processing and management. However, stabilizing thorium clusters in aqueous solution is quite challenging because of their fast olation and oxolation reactions. Here, we report a thorium-based metal-organic framework, NU-905, with the formula [Th(μ-O)(HCOO)(HO)(TCPP)] [TCPP = tetrakis(4-carboxyphenyl)porphyrin], synthesized by a solvothermal reaction in N, N-dimethylformamide and water at 120 °C. NU-905 contains a hexanuclear secondary building unit (SBU), [Th(μ-O)(HCOO)(HO)], which has never been reported previously. The SBUs are capped and bridged by the tetratopic linker TCPP to form a three-dimensional network with scu topology. The activated NU-905 exhibits permanent porosity and shows high catalytic activity for the selective photooxidation of a mustard gas simulant.
钍团簇的晶体结构对于理解溶液中锕系元素物种的形成和转化机制非常重要，这反过来又有利于核废料的处理和管理。然而，由于其快速的氧化和配位反应，在水溶液中稳定钍团簇是相当具有挑战性的。在这里，我们报告了一种基于钍的金属-有机骨架 NU-905，其化学式为[Th(μ-O)(HCOO)(HO)(TCPP)] [TCPP = 四(4-羧基苯基)卟啉]，通过在 120°C 的 N，N-二甲基甲酰胺和水中的溶剂热反应合成。NU-905 包含一个六核二级结构单元（SBU），[Th(μ-O)(HCOO)(HO)]，这是以前从未报道过的。SBU 被四面体形的链接剂 TCPP 封闭和桥接，形成具有 scu 拓扑的三维网络。活化后的 NU-905 表现出永久的孔隙率，并对模拟芥子气的选择性光氧化表现出高催化活性。
