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

Zhi Hui Zhang; Ganna A. Senchyk; Yi Liu; Tyler Spano-Franco; Jennifer E.S. Szymanowski; Peter C. Burns

doi:10.1021/acs.inorgchem.7b02019

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

Zhi Hui Zhang, Ganna A. Senchyk, Yi Liu, Tyler Spano-Franco, Jennifer E.S. Szymanowski, Peter C. Burns

Research output: Contribution to journal › Article › peer-review

21 Scopus citations

Abstract

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 and formulated as (Et₂NH₂)₂[(UO₂)₃(PCP)₂](H₂O)_2.5 (1), (MeNH₃)(H₃O)[(UO₂)₃(PCP)₂(H₂O)₃] (2), and [Na(H₂O)₄](H₃O)[(UO₂)₃(PCP)₂(H₂O)₂](H₂O)₅ (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 (Na₃VO₄) 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 U₃O₁₈ 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 UO₇ pentagonal bipyramids. With the inclusion of sodium cations, 3 is a porous framework containing UO₇ pentagonal bipyramids within a layer, with sodium cations and UO₆ 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.

Original language	English
Pages (from-to)	13249-13256
Number of pages	8
Journal	Inorganic Chemistry
Volume	56
Issue number	21
DOIs	https://doi.org/10.1021/acs.inorgchem.7b02019
State	Published - Nov 6 2017
Externally published	Yes

Funding

This research was supported by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy, Grant No. DE-FG02-07ER15880. Z.-H.Z. acknowledges the Qing Lan Project of Jiangsu Province that provided an opportunity to conduct research at the University of Notre Dame. Sample characterization was done in the Materials Characterization Facility of the Center for Sustainable Energy at Notre Dame.

Funders	Funder number
U.S. Department of Energy	DE-FG02-07ER15880
Office of Science
Basic Energy Sciences
Chemical Sciences, Geosciences, and Biosciences Division
Qinglan Project of Jiangsu Province of China

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10.1021/acs.inorgchem.7b02019

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title = "Porous Uranium Diphosphonate Frameworks with Trinuclear Units Templated by Organic Ammonium Hydrolyzed from Amine Solvents",

abstract = "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 and formulated as (Et2NH2)2[(UO2)3(PCP)2](H2O)2.5 (1), (MeNH3)(H3O)[(UO2)3(PCP)2(H2O)3] (2), and [Na(H2O)4](H3O)[(UO2)3(PCP)2(H2O)2](H2O)5 (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 (Na3VO4) 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 U3O18 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 UO7 pentagonal bipyramids. With the inclusion of sodium cations, 3 is a porous framework containing UO7 pentagonal bipyramids within a layer, with sodium cations and UO6 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.",

author = "Zhang, {Zhi Hui} and Senchyk, {Ganna A.} and Yi Liu and Tyler Spano-Franco and Szymanowski, {Jennifer E.S.} and Burns, {Peter C.}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acs.inorgchem.7b02019",

language = "English",

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T1 - Porous Uranium Diphosphonate Frameworks with Trinuclear Units Templated by Organic Ammonium Hydrolyzed from Amine Solvents

AU - Zhang, Zhi Hui

AU - Senchyk, Ganna A.

AU - Liu, Yi

AU - Spano-Franco, Tyler

AU - Szymanowski, Jennifer E.S.

AU - Burns, Peter C.

PY - 2017/11/6

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N2 - 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 and formulated as (Et2NH2)2[(UO2)3(PCP)2](H2O)2.5 (1), (MeNH3)(H3O)[(UO2)3(PCP)2(H2O)3] (2), and [Na(H2O)4](H3O)[(UO2)3(PCP)2(H2O)2](H2O)5 (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 (Na3VO4) 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 U3O18 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 UO7 pentagonal bipyramids. With the inclusion of sodium cations, 3 is a porous framework containing UO7 pentagonal bipyramids within a layer, with sodium cations and UO6 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.

AB - 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 and formulated as (Et2NH2)2[(UO2)3(PCP)2](H2O)2.5 (1), (MeNH3)(H3O)[(UO2)3(PCP)2(H2O)3] (2), and [Na(H2O)4](H3O)[(UO2)3(PCP)2(H2O)2](H2O)5 (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 (Na3VO4) 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 U3O18 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 UO7 pentagonal bipyramids. With the inclusion of sodium cations, 3 is a porous framework containing UO7 pentagonal bipyramids within a layer, with sodium cations and UO6 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.

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

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