A new chiral uranyl phosphonate framework consisting of achiral building units generated from ionothermal reaction: structure and spectroscopy characterizations.
A new chiral uranyl phosphonate framework consisting of achiral building units generated from ionothermal reaction: structure and spectroscopy characterizations.
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DOI：
10.1039/c5dt02667a
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发表时间：
2015-10
影响因子：
4
通讯作者：
T. Zheng;Yang Gao;Lanhua Chen;Zhiyong Liu;Juan Diwu;Z. Chai;T. Albrecht‐Schmitt;Shuao Wang
中科院分区：
文献类型：
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作者：
T. Zheng;Yang Gao;Lanhua Chen;Zhiyong Liu;Juan Diwu;Z. Chai;T. Albrecht‐Schmitt;Shuao Wang
硝酸铀酰与1，3-pbpH_4的离子化反应在[C4 mim][Dbp]、[C4 mpyr][Br]和[Etpy][Br]离子液体中，分别以（1，3-pbpH 4 = 1，3-亚苯基双膦酸）为配体，合成了三种新的铀酰膦酸盐[C4 mim][（UO 2）2（1，3-pbpH）（1，3-pbpH）·Hmim]（1）、[UO 2（1，3-pbpH2）H2O·mpr]（2）和[Etpy][UO 2（1，3-pbpH2）F]（3）。化合物1展示了由四氢双锥铀多面体和1，3-pbp配体的非手性构建单元构建的手性铀酰膦酸酯3D骨架结构的罕见实例。该结构采用具有沿着B轴延伸的通道的网络，其填充有C4 mim（+）和质子化的1-甲基咪唑。与此形成鲜明对比的是，化合物2和3都显示出由铀酰五角双锥多面体和膦酸酯配体组成的柱撑拓扑结构。化合物2层间为中性层，层间为N-甲基吡咯分子;化合物3层间为阴离子层，层间电荷由N-乙基吡啶阳离子补偿。虽然化合物1，2，和3的合成条件相同，唯一的变化的离子液体物种，所得到的结构显示丰富的多样性，在本地的铀酰离子的配位环境，质子化的膦酸酯配体，离子液体离子的构象，和结构的整体排列。所有化合物的特征在于吸收，温度依赖的荧光，以及红外和拉曼光谱。
The ionothermal reactions of uranyl nitrate and 1,3-pbpH4 (1,3-pbpH4 = 1,3-phenylenebis(phosphonic acid) ligand in ionic liquids of [C4mim][Dbp], [C4mpyr][Br], and [Etpy][Br], respectively, afforded three new uranyl phosphonates, namely [C4mim][(UO2)2(1,3-pbpH)(1,3-pbpH)·Hmim] (1), [UO2(1,3-pbpH2)H2O·mpr] (2), and [Etpy][UO2(1,3-pbpH2)F] (3). Compound 1 exhibits a rare example of a chiral uranyl phosphonate 3D framework structure built from achiral building units of tetragonal bipyramidal uranium polyhedra and 1,3-pbp ligands. The structure adopts a network with channels extending along the b axis, which are filled with C4mim(+) and protonated 1-methylimidazole. In sharp contrast, compounds 2 & 3 both show pillared topology composed of uranyl pentagonal bipyramid polyhedra and phosphonate ligands. The layers are neutral in compound 2 with N-methylpyrrole molecules in the interlayer space, while compound 3 adopts anionic layer, and the charge is compensated with N-ethyl-pyridinium cations between the layers. Although compounds 1, 2, and 3 were synthesized under identical conditions with sole variation of the ionic liquid species, the resulting structures show a rich diversity in the local coordination environment of uranyl ions, the protonation of the phosphonate ligand, the conformation of ionic liquid ions, and the overall arrangement of the structure. All compounds were characterized by absorption, temperature dependent fluorescence, as well as infrared and Raman spectroscopies.