Probing the Influence of Phosphonate Bonding Modes to Uranium(VI) on Structural Topology and Stability: A Complementary Experimental and Computational Investigation

	Probing the Influence of Phosphonate Bonding Modes to Uranium(VI) on Structural Topology and Stability: A Complementary Experimental and Computational Investigation
	Zheng, T; Wu QY(吴群燕); Wu, QY; Gao, Y; Gui, DX; Qiu, SW; Chen, LH; Sheng, DP; Diwu, J; Shi, WQ
刊名	INORGANIC CHEMISTRY
	2015
卷号	54 期号:8 页码:3864-3874
通讯作者	石伟群
英文摘要	Systematic control of the reactions between U(VI) and 1,4-phenylenebis(methylene))bis(phosphonic acid) (pmbH(4)) allows for alterations in the bonding between these constituents and affords three uranyl phosphonate compounds with chiral one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) structures, namely, [TPA][UO2(pmbH(3))(pmbH(2))H2O]center dot 2H(2)O (1), [NH4](2)[UO2(pmb)] (2), UO2(pmbH(2)) (3), and the first uranyl mixed phosphite/phosphonate compound [TMA](2)[(UO2)2(pmb)(HPO3)] (4) (TPA = NPr4+, TMA = NMe4+). These compounds crystallize in the space groups P2(1)2(1)2(1), P (1) over bar, P2(1)/c, and Cmcm, respectively. Further investigation of the local uranyl coordination environment reveals that in 1 only oxygen atoms from P-O moieties ligate the uranium centers; whereas in 2 only P-O- oxygen atoms are involved in bonding and yield a layered topology. Compound 3 differs sharply from the first two in that conjugated P-O and P-O- oxygen atoms chelate the uranium centers resulting in a 3D framework. In compound 4, a phosphonate group bridges three uranyl centers further coordinated with a phosphite ligand HPO32-, which is a product of pmbH(4) decomposing, forming a 2D layered structure. Compounds 3 and 4 also contain a different coordination environment for U(VI) than that found in 1 or 2. In this case, tetragonal bipyramidal UO6 units occur instead of the far more common UO7 pentagonal bipyramids found in 1 and 2. Interestingly, 1 converts to 3 at elevated reaction temperatures, indicating that the formation of 1 is likely under kinetic control. This is supported by thermal analysis, which reveals that 3 has higher thermal stability than 1 or 2. UV-vis-near-IR absorption and fluorescence spectroscopy show that the absorption and photoluminescence intensity increases from 1 to 4. Density functional theory electronic structure calculations provide insight into the nature of the interactions between U(VI) and the phosphonate ligands.
学科主题	Chemistry
类目[WOS]	Chemistry, Inorganic & Nuclear
收录类别	SCI
WOS记录号	WOS:000353429500020
公开日期	2016-05-03
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/228523]
专题	高能物理研究所_多学科研究中心
推荐引用方式 GB/T 7714	Zheng, T,Wu QY,Wu, QY,et al. Probing the Influence of Phosphonate Bonding Modes to Uranium(VI) on Structural Topology and Stability: A Complementary Experimental and Computational Investigation[J]. INORGANIC CHEMISTRY,2015,54(8):3864-3874.
APA	Zheng, T.,吴群燕.,Wu, QY.,Gao, Y.,Gui, DX.,...&石伟群.(2015).Probing the Influence of Phosphonate Bonding Modes to Uranium(VI) on Structural Topology and Stability: A Complementary Experimental and Computational Investigation.INORGANIC CHEMISTRY,54(8),3864-3874.
MLA	Zheng, T,et al."Probing the Influence of Phosphonate Bonding Modes to Uranium(VI) on Structural Topology and Stability: A Complementary Experimental and Computational Investigation".INORGANIC CHEMISTRY 54.8(2015):3864-3874.