恭喜郑滔在Inorg. Chem.上发表锕系有机膦酸盐文章！
Tao Zheng, Qun-Yan Wu, Yang Gao, Daxiang Gui, Shiwen Qiu, Lanhua Chen, Daopeng Sheng, Juan Diwu, Wei-Qun Shi, Zhifang Chai, Thomas E. Albrecht-Schmitt, and Shuao Wang, Probing the Influence of Phosphonate Bonding Modes to Uranium(VI) on Structural Topology and Stability: A Complementary Experimental and Computational Investigation, Inorg. Chem., 2015, 54 (8), pp 3864–3874
Abstract: Systematic control of the reactions between U(VI) and 1,4-phenylenebis(methylene))bis(phosphonic acid) (pmbH4) 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(pmbH3)(pmbH2)H2O]·2H2O (1), [NH4]2[UO2(pmb)] (2), UO2(pmbH2) (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 P212121, P1̅, P21/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 pmbH4 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 ****ysis, 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.