Zhang Zhi-Hui, Senchyk Ganna A, Liu Yi, Spano-Franco Tyler, Szymanowski Jennifer E S, Burns Peter C
Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame , Notre Dame, Indiana 46556, United States.
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou University , Changzhou 213164, P. R. China.
Inorg Chem. 2017 Nov 6;56(21):13249-13256. doi: 10.1021/acs.inorgchem.7b02019.
By varying solvent systems, the solvothermal treatment of uranyl nitrate and methylenediphosphonic acid (HPCP) afforded three new porous uranyl-organic frameworks (UOFs). All were structurally characterized by single-crystal X-ray diffraction and formulated as (EtNH)(UO)(PCP) (1), (MeNH)(HO)[(UO)(PCP)(HO)] (2), and Na(HO)(UO)(PCP)(HO) (3). These compounds crystallize with three-dimensional anionic frameworks containing U(VI) and distinct cationic species due to in situ solvent hydrolysis. The solvent systems diethylformamide (DEF), N-methyl-2-pyrrolindone (NMP), and the additive sodium vanadate (NaVO) significantly impact the resultant structures, affording diethyl ammonium, methyl ammonium, and sodium cations captured in channels of the anionic frameworks of 1-3. In 1, a trinuclear UO unit formed by three uranyl polyhedra that share edges is connected into a three-dimensional framework. Compound 2 has a three-dimensional framework formed from a uranyl-methylenediphosphonate layer that is pillared by UO pentagonal bipyramids. With the inclusion of sodium cations, 3 is a porous framework containing UO pentagonal bipyramids within a layer, with sodium cations and UO square bipyramids linking the adjacent layers. Compounds 1-3 feature the uranyl/ligand ratio of 3:2, but present diverse structural building units ranging from edge-shared trinuclear to heteronuclear assemblies. The compounds have been characterized by infrared (IR), Raman, and UV-vis spectroscopies, X-ray diffraction, and thermogravimetric analysis.
通过改变溶剂体系，对硝酸铀酰和亚甲基二膦酸（HPCP）进行溶剂热处理，得到了三种新型多孔铀酰有机框架材料（UOFs）。所有材料均通过单晶X射线衍射进行结构表征，并分别被确定为（EtNH）(UO)(PCP)（1）、（MeNH）(HO)[(UO)(PCP)(HO)]（2）和Na(HO)(UO)(PCP)(HO)（3）。由于原位溶剂水解，这些化合物结晶形成包含U(VI)和不同阳离子物种的三维阴离子框架。二乙基甲酰胺（DEF）溶剂体系、N-甲基-2-吡咯烷酮（NMP）和添加剂钒酸钠（NaVO）对所得结构有显著影响，使得二乙铵、甲铵和钠离子被捕获在1 - 3的阴离子框架通道中。在1中，由三个共享边的铀酰多面体形成的三核UO单元连接成三维框架。化合物2具有由铀酰-亚甲基二膦酸酯层形成的三维框架，该层由UO五角双锥体支撑。包含钠离子后，3是一种多孔框架，在一层内含有UO五角双锥体，钠离子和UO四方双锥体连接相邻层。化合物1 - 3的铀酰/配体比例为3:2，但呈现出从边共享三核到异核组装的多样结构构建单元。这些化合物已通过红外（IR）、拉曼和紫外可见光谱、X射线衍射以及热重分析进行了表征。
