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

By Zhi-Hui Zhang (293520), Ganna A. Senchyk (1446733), Yi Liu (36759), Tyler Spano-Franco (4518715), Jennifer E. S. Szymanowski (762967) and Peter C. Burns (1438396)


By varying solvent systems, the solvothermal treatment of uranyl nitrate and methylenediphosphonic acid (H<sub>4</sub>PCP) afforded three new porous uranyl-organic frameworks (UOFs). All were structurally characterized by single-crystal X-ray diffraction and formulated as (Et<sub>2</sub>NH<sub>2</sub>)<sub>2</sub>[(UO<sub>2</sub>)<sub>3</sub>(PCP)<sub>2</sub>]­(H<sub>2</sub>O)<sub>2.5</sub> (<b>1</b>), (MeNH<sub>3</sub>)­(H<sub>3</sub>O)­[(UO<sub>2</sub>)<sub>3</sub>­(PCP)<sub>2</sub>­(H<sub>2</sub>O)<sub>3</sub>] (<b>2</b>), and [Na­(H<sub>2</sub>O)<sub>4</sub>]­(H<sub>3</sub>O)­[(UO<sub>2</sub>)<sub>3</sub>­(PCP)<sub>2</sub>­(H<sub>2</sub>O)<sub>2</sub>]­(H<sub>2</sub>O)<sub>5</sub> (<b>3</b>). These compounds crystallize with three-dimensional anionic frameworks containing U­(VI) and distinct cationic species due to <i>in</i> <i>situ</i> solvent hydrolysis. The solvent systems diethylformamide (DEF), <i>N</i>-methyl-2-pyrrolindone (NMP), and the additive sodium vanadate (Na<sub>3</sub>VO<sub>4</sub>) significantly impact the resultant structures, affording diethyl ammonium, methyl ammonium, and sodium cations captured in channels of the anionic frameworks of <b>1</b>–<b>3</b>. In <b>1</b>, a trinuclear U<sub>3</sub>O<sub>18</sub> unit formed by three uranyl polyhedra that share edges is connected into a three-dimensional framework. Compound <b>2</b> has a three-dimensional framework formed from a uranyl-methylenediphosphonate layer that is pillared by UO<sub>7</sub> pentagonal bipyramids. With the inclusion of sodium cations, <b>3</b> is a porous framework containing UO<sub>7</sub> pentagonal bipyramids within a layer, with sodium cations and UO<sub>6</sub> square bipyramids linking the adjacent layers. Compounds <b>1</b>–<b>3</b> 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

Topics: Biophysics, Medicine, Pharmacology, Biotechnology, Sociology, Space Science, Environmental Sciences not elsewhere classified, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, Physical Sciences not elsewhere classified, single-crystal X-ray diffraction, Trinuclear Units Templated, framework, additive sodium vanadate, Porous Uranium Diphosphonate Frameworks, UOF, trinuclear U 3 O 18 unit, UO 6 square bipyramids, H 4 PCP, UV, Organic Ammonium Hydrolyzed, UO 7 pentagonal bipyramids, Na 3 VO 4, NMP, Et 2 NH 2, DEF, IR, sodium cations, uranyl
Year: 2017
DOI identifier: 10.1021/acs.inorgchem.7b02019.s001
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Provided by: FigShare
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