Chen Fei, Wang Cong-zhi, Li Zi-jie, Lan Jian-hui, Ji Yan-qin, Chai Zhi-fang
†China CDC Key Laboratory of Radiological Pretection and Nuclear Emergency, National Institute for Radiological Protection, China CDC, Beijing 100088, People's Republic of China.
‡Key Lab of Nuclear Radiation and Nuclear Energy Technology, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, People's Republic of China.
Inorg Chem. 2015 Apr 20;54(8):3829-34. doi: 10.1021/acs.inorgchem.5b00013. Epub 2015 Apr 2.
A new 3-fold interpenetrated uranyl organic framework, UO2(bdc)(dmpi), was hydrothermally synthesized using 1,4-benzenedicarboxylic acid (H2bdc) and 1-(4-(1H-imidazol-1-yl)-2,5-dimethylphenyl)-1H-imidazole (dmpi). This framework, which was determined by synchrotron radiation X-ray, exhibited a new 3-fold interpenetrated (2,4)-connected topology with the Schläfli symbol of (12(6))(12)2. Additionally, large incurvation happened to the bond angle of O=U=O, which was always arranged in a rigorous line. Computational results based on density functional theory (DFT) indicated that the bent geometry of uranyl in UO2(bdc)(dmpi) was mainly due to the higher charge populations in the valence 6d shells of uranium, rendered by the electronegative imidazoles.
使用对苯二甲酸（H₂bdc）和1-(4-(1H-咪唑-1-基)-2,5-二甲基苯基)-1H-咪唑（dmpi）通过水热法合成了一种新型的三重穿插铀酰有机框架UO₂(bdc)(dmpi)。通过同步辐射X射线确定的该框架呈现出一种新的三重穿插（2,4）连接拓扑结构，其施莱夫利符号为(12(6))(12)₂。此外，[O=U=O]²⁺的键角发生了较大弯曲，[O=U=O]²⁺原本总是呈严格的直线排列。基于密度泛函理论（DFT）的计算结果表明，UO₂(bdc)(dmpi)中铀酰的弯曲几何形状主要是由于电负性咪唑使铀的6d价壳层具有更高的电荷布居。
