Liu Chao, Yang Weiting, Qu Ning, Li Lei-Jiao, Pan Qing-Jiang, Sun Zhong-Ming
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , 5625 Renmin Street, Changchun, Jilin 130022, P. R. China.
University of Chinese Academy of Sciences , Beijing 100049, China.
Inorg Chem. 2017 Feb 6;56(3):1669-1678. doi: 10.1021/acs.inorgchem.6b02765. Epub 2017 Jan 24.
The hydrothermal reaction of uranyl ions with (5-methyl-1,3-phenylene)diphosphonic acid (HMPDP) in the presence of additives such as nitric acid, N-bearing species, and heterometal ions yielded five new uranyl organic hybrids: (HO)[(UO)(HO)(HDPB)(HDPB)(HDPB)]·2HO (1), (Hphen)(phen)[(UO)(HDPB)(HDPB)] (2), (Hdipy)[(UO)(MPDP)] (3), Zn(bipy)(UO)(MPDP) (4), and Co(bipy)(UO)(MPDP)·HO (5) (HDPB = 3,5-diphosphonobenzoic acid; phen = 1,10-phenanthroline; dipy = 4,4'-bipyridine; bipy = 2,2'-bipyridine). Single-crystal X-ray diffraction (XRD) demonstrates that 1 and 2 are 3D frameworks constructed of uranyl centers and carboxyphosphonate DPB ligands; the latter were formed via the in situ oxidation of HMPDP. In the homometallic uranyl diphosphonate 3, less common UO square bipyramids connected by MPDP ligands were incorporated to form the 2D assembly. A further introduction of heterometal ions produced two heterobimetallic uranyl phosphonates 4 and 5. Both of them show layered structures, formed by UO square bipyramids linked by MPDP ligands with heterometal-centered polyhedra decorated on the sides of the layers. It is found that the pH and heterometal ions have significant effects on the structures of the complexes. In addition to the syntheses and XRD characterization, the spectroscopic properties of these uranyl complexes were also addressed. To complement the experimental results, density functional theory calculations were carried out on several model complexes that feature a homo- or heterobimetallic molecular skeleton. Geometrical/electronic structures, IR spectra, and electronic absorptions were discussed.
在硝酸、含氮物种和异金属离子等添加剂存在的情况下，铀酰离子与（5-甲基-1,3-亚苯基）二膦酸（HMPDP）发生水热反应，生成了五种新型铀酰有机杂化物：(HO)[(UO)(HO)(HDPB)(HDPB)(HDPB)]·2HO（1）、(Hphen)(phen)[(UO)(HDPB)(HDPB)]（2）、(Hdipy)[(UO)(MPDP)]（3）、Zn(bipy)(UO)(MPDP)（4）和Co(bipy)(UO)(MPDP)·HO（5）（HDPB = 3,5-二膦酰基苯甲酸；phen = 1,10-菲咯啉；dipy = 4,4'-联吡啶；bipy = 2,2'-联吡啶）。单晶X射线衍射（XRD）表明，1和2是由铀酰中心和羧基膦酸酯DPB配体构成的三维框架结构；后者是通过HMPDP的原位氧化形成的。在同金属铀酰二膦酸酯3中，由MPDP配体连接的不太常见的UO四方双锥被并入形成二维组装结构。进一步引入异金属离子生成了两种异双金属铀酰膦酸酯4和5。它们都呈现层状结构，由通过MPDP配体连接的UO四方双锥形成，异金属中心多面体装饰在层的侧面。研究发现，pH值和异金属离子对配合物的结构有显著影响。除了合成和XRD表征外，还研究了这些铀酰配合物的光谱性质。为补充实验结果，对几种具有同双金属或异双金属分子骨架的模型配合物进行了密度泛函理论计算。讨论了几何/电子结构、红外光谱和电子吸收情况。
