Li Xing-Jun, Jiang Fei-Long, Wu Ming-Yan, Chen Lian, Qian Jin-Jie, Zhou Kang, Yuan Da-Qiang, Hong Mao-Chun
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, Fujian 350002, People's Republic of China.
Inorg Chem. 2014 Jan 21;53(2):1032-8. doi: 10.1021/ic402481b. Epub 2013 Dec 30.
By employment of a tripodal phosphoric carboxylate ligand, tris(4-carboxylphenyl)phosphine oxide (H3TPO), two novel porous metal-organic frameworks, namely, [Zn4(μ3-OH)2(TPO)2(H2O)2] (1) and Zn6(μ6-O)(TPO)24·3H2O (2), have been synthesized by solvothermal methods. Complexes 1 and 2 exhibit three-dimensional microporous frameworks with flu and pyr topologies and possess rare butterfly-shaped Zn4(μ3-OH)2(CO2)6 and octahedral Zn6(μ6-O)(CO2)6 secondary building units, respectively. Large cavities and one-dimensional channels are observed in these two frameworks. Gas-sorption measurements indicate that complex 2 has a good H2 uptake capacity of 171.9 cm(3) g(-1) (1.53 wt %) at 77 K and 1.08 bar, and its ideal adsorbed solution theory calculation predicts highly selective adsorption of CO2 over N2 and CH4. Furthermore, complexes 1 and 2 exhibit excellent blue emission at room temperature.
通过使用三脚架状的磷酸羧酸配体三（4-羧基苯基）氧化膦（H3TPO），采用溶剂热法合成了两种新型多孔金属有机骨架化合物，即[Zn4(μ3-OH)2(TPO)2(H2O)2]（1）和Zn6(μ6-O)(TPO)24·3H2O（2）。配合物1和2呈现出具有flu和pyr拓扑结构的三维微孔骨架，分别拥有罕见的蝴蝶形Zn4(μ3-OH)2(CO2)6和八面体Zn6(μ6-O)(CO2)6二级结构单元。在这两种骨架中观察到了大的空腔和一维通道。气体吸附测量表明，配合物2在77 K和1.08 bar下具有171.9 cm(3) g(-1)（1.53 wt%）的良好氢气吸附容量，其理想吸附溶液理论计算预测对CO2相对于N2和CH4具有高度选择性吸附。此外，配合物1和2在室温下表现出优异的蓝色发光。
