Xu Mengyu, Eckard Peter, Burns Peter C
Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, Indiana 46556, United States.
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States.
Inorg Chem. 2020 Jul 20;59(14):9881-9888. doi: 10.1021/acs.inorgchem.0c01080. Epub 2020 Jul 9.
Benzene-1,2-diphosphonic acid (Ppb) was introduced into the uranyl peroxide cluster system, resulting in three Ppb-functionalized uranyl peroxide clusters, (UO)(O)(CHPO) (UPpb), (UO)(O)(CHPO) (UPpb), and (UO)(O)(CHPO) (UPpb). Dissolution experiments were performed for the potassium salts of UPpb and UPpb, which revealed the capacity of UPpb to dissolve in the organic solvent dimethyl sulfoxide (DMSO). Unlike UPpb, the K salt of UPpb did not dissolve in DMSO but was more soluble in water, perhaps due to the lower proportion of Ppb ligands in its structure. In this work, UPpb and UPpb formed as potassium salts and both adopt the fullerene topology of previously reported U. U contains 20 uranyl peroxide units and encapsulates 12 Na cations. It is not possible for unfunctionalized U to incorporate 12 K cations owing to space constraints, as is the case in the new clusters reported here. Transformation of UPpb in water over time to produce U was observed, possibly owing to its ability to incorporate K cations, which have been associated with the formation of U.
将苯 - 1,2 - 二膦酸（Ppb）引入过氧化铀簇体系，得到了三种Ppb功能化的过氧化铀簇，即(UO₂)₂(O₂)(C₆H₄PO₃H)₂（UPpb - 1）、(UO₂)₂(O₂)(C₆H₃(PO₃H)₂)（UPpb - 2）和(UO₂)₂(O₂)(C₆H₂(PO₃H)₃)（UPpb - l）。对UPpb - 1和UPpb - 2的钾盐进行了溶解实验，结果表明UPpb - 1有能力溶解在有机溶剂二甲基亚砜（DMSO）中。与UPpb - 1不同，UPpb - 2的钾盐不溶于DMSO，但在水中的溶解度更高，这可能是由于其结构中Ppb配体的比例较低。在这项工作中，UPpb - 1和UPpb - 2以钾盐形式形成，并且都采用了先前报道的U₆O₅(OH)₃·12H₂O的富勒烯拓扑结构。U₆O₅(OH)₃·12H₂O包含20个过氧化铀单元并封装了12个Na⁺阳离子。由于空间限制，未功能化的U₆O₅(OH)₃·12H₂O不可能容纳12个K⁺阳离子，就像这里报道的新簇的情况一样。观察到UPpb - 1在水中随时间转化为U₆O₅(OH)₃·12H₂O，这可能是由于它有能力结合K⁺阳离子，而K⁺阳离子与U₆O₅(OH)₃·12H₂O的形成有关。
