Liu Dan-Dan, Wang Yu-Ling, Luo Feng, Liu Qing-Yan
College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022, P. R. China.
College of Biology, Chemistry and Material Science, East China Institute of Technology, Nanchang, Jiangxi 34400, P. R. China.
Inorg Chem. 2020 Mar 2;59(5):2952-2960. doi: 10.1021/acs.inorgchem.9b03323. Epub 2020 Feb 11.
Due to the intrinsic coordination preference of the linear uranyl unit, uranyl-organic frameworks (UOFs) are generally prone to exhibiting low-dimensional structures. Reactions of uranyl nitrate with biphenyl-3,3'-disulfonyl-4,4'-dicarboxylic acid dipotassium salt (KHBPDSDC) under different conditions led to three UOFs, namely, {(MeNH)[K(UO)(μ-O)(μ-OH)(μ-OH)(BPDSDC)(HO)]·4DMF} (), {[K(UO)(μ-O)(BPDSDC)(HO)]} (), and {(MeNH)[K(UO)(BPDSDC)(HO)]} (). Compounds and contain one-dimensional (1D) ribbon structures formed from UO units bridged by μ-O atoms and carboxylate groups. The 1D ribbons in are linked by K atoms to form a two-dimensional (2D) layer, which is further pillared by the biphenyl units to give a three-dimensional (3D) framework. For , the oxygen atoms of UO units in each 1D ribbon bridge the K atoms to form four -[K-O-K]- infinite chains located above and below the ribbon. The 1D ribbons in are bridged by sulfonate groups to generate a 3D substructure featuring 1D channels occupied by biphenyl moieties. In , each mononuclear [(UO)(COO)] unit is bridged by three K atoms to form a 3D substructure featuring 1D small left-handed and large righted helical channels occluded by biphenyl moieties. Compound exhibits an excellent proton conductivity with the highest conductivity of 1.07 × 10 S cm. The inner walls of 1D channels of are full of the hydrophilic sulfonate groups, which boost enrichment of the guest water molecules, thus resulting in a high proton conductivity. Finally, temperature dependence of fluorescent studies showed that compounds and display the characteristic uranyl emissions. This work presents the elegant examples of the rarely explored 3D UOFs and expands the potentials of UOFs.
由于线性铀酰单元固有的配位偏好，铀酰有机框架（UOFs）通常易于呈现低维结构。硝酸铀酰与联苯 - 3,3'-二磺酰基 - 4,4'-二羧酸钾盐（KHBPDSDC）在不同条件下反应生成了三种UOFs，即{(MeNH)[K(UO₂)(μ - O)(μ - OH)(μ - OH)(BPDSDC)(H₂O)]·4DMF}（），{[K(UO₂)(μ - O)(BPDSDC)(H₂O)]}（）和{(MeNH)[K(UO₂)(BPDSDC)(H₂O)]}（）。化合物和包含由μ - O原子和羧酸根基团桥连的UO₂单元形成的一维（1D）带状结构。中的1D带通过K原子连接形成二维（2D）层，该二维层进一步由联苯单元支撑形成三维（3D）框架。对于，每个1D带中UO₂单元的氧原子桥连K原子形成位于带上方和下方的四个 -[K - O - K]-无限链。中的1D带由磺酸根基团桥连以生成具有由联苯部分占据的1D通道的3D子结构。在中，每个单核[(UO₂)(COO)]单元由三个K原子桥连形成具有由联苯部分封闭的1D小左旋和大右旋螺旋通道的3D子结构。化合物表现出优异的质子传导性，最高电导率为1.07×10⁻⁵ S cm⁻¹。的1D通道内壁充满亲水性磺酸根基团，这促进了客体水分子的富集，从而导致高质子传导性。最后，荧光研究的温度依赖性表明化合物和显示出特征性的铀酰发射。这项工作展示了很少被探索的3D UOFs的精彩实例，并扩展了UOFs的潜力。
