Porous Uranium Diphosphonate Frameworks with Trinuclear Units Templated by Organic Ammonium Hydrolyzed from Amine Solvents

• DOI: 10.1021/acs.inorgchem.7b02019
• Publication Date: 2017-10-17T18:50:27Z
• Authors: Zhi-Hui Zhang; Ganna A. Senchyk; Yi Liu; Tyler Spano-Franco; Jennifer E. S. Sz...; Peter C. Burns
• Keywords: 01 natural sciences; 0104 chemical sciences

By varying solvent systems, the solvothermal treatment of uranyl nitrate and methylenediphosphonic acid (H4PCP) afforded three new porous uranyl-organic frameworks (UOFs). All were structurally characterized by single-crystal X-ray diffraction formulated as (Et2NH2)2[(UO2)3(PCP)2](H2O)2.5 (1), (MeNH3)(H3O)[(UO2)3(PCP)2(H2O)3] (2), [Na(H2O)4](H3O)[(UO2)3(PCP)2(H2O)2](H2O)5 (3). These compounds crystallize with three-dimensional anionic containing U(VI) distinct cationic species due to in situ hydrolysis. The systems diethylformamide (DEF), N-methyl-2-pyrrolindone (NMP), additive sodium vanadate (Na3VO4) significantly impact resultant structures, affording diethyl ammonium, methyl cations captured channels 1-3. In 1, a trinuclear U3O18 unit formed polyhedra that share edges is connected into framework. Compound 2 has framework from uranyl-methylenediphosphonate layer pillared UO7 pentagonal bipyramids. With inclusion cations, 3 bipyramids within layer, UO6 square linking adjacent layers. Compounds 1-3 feature uranyl/ligand ratio 3:2, but present diverse structural building units ranging edge-shared heteronuclear assemblies. have been infrared (IR), Raman, UV-vis spectroscopies, diffraction, thermogravimetric analysis.