Mandal Sukhendu, Chandra Manabendra, Natarajan Srinivasan
Framework Solids Laboratory, Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012, India.
Inorg Chem. 2007 Sep 17;46(19):7935-43. doi: 10.1021/ic700866f. Epub 2007 Aug 24.
Three new amine templated uranium phosphites, [C2N2H10][U2IVF6(HPO3)2], 1, [C4N2H12][U2IVF6(HPO3)2], 2, and [C4N2H12][(UVIO2)2F2(HPO3)2], 3, have been synthesized by hydrothermal methods. All of the compounds are built up from a connectivity between U(O/F)x (x = 7, 8) and HPO3 polyhedral units. The observation of a well-established secondary building unit, SBU-4, in 1 and 2 is noteworthy. In 1, the SBU-4 units are connected to form U-F-U chains, which are linked by U-O-P chains, forming the layered structure. In 2, the SBU-4 units are edge-shared and also interconnected forming the 3D structure. In 3, the connectivity between the building units forms a layer, the topology of which is similar to the mineral, johannite. To the best of our knowledge, this is the first observation of a well-known secondary building unit (SBU-4) in actinide framework compounds. Optical studies on 1 and 2, containing U(4+) species, indicate an intense blue emission through an upconversion process, and the magnetic susceptibility studies show antiferromagnetic behavior.
通过水热法合成了三种新型胺模板亚磷酸铀，即[C2N2H10][U2IVF6(HPO3)2]（1）、[C4N2H12][U2IVF6(HPO3)2]（2）和[C4N2H12][(UVIO2)2F2(HPO3)2]（3）。所有化合物均由U(O/F)x（x = 7, 8）和HPO3多面体单元之间的连接构成。值得注意的是，在1和2中观察到了一种成熟的二级结构单元SBU - 4。在1中，SBU - 4单元连接形成U - F - U链，这些链通过U - O - P链相连，形成层状结构。在2中，SBU - 4单元通过边共享且相互连接形成三维结构。在3中，结构单元之间的连接形成了一层，其拓扑结构与矿物磷铜铀矿相似。据我们所知，这是在锕系骨架化合物中首次观察到一种知名的二级结构单元（SBU - 4）。对含有U(4+)物种的1和2进行的光学研究表明，通过上转换过程有强烈的蓝色发射，并且磁化率研究显示出反铁磁行为。
