Yao Shuo, Xu Tong, Zhao Nian, Zhang Lirong, Huo Qisheng, Liu Yunling
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, P. R. China.
Dalton Trans. 2017 Mar 7;46(10):3332-3337. doi: 10.1039/c7dt00192d.
A novel metal-organic framework, [(CH)NH][CuO(SO)CuL(DMF)(HO)]·9DMF (JLU-Liu39) HL = pyridine-3,5-bis(phenyl-4-carboxylic acid), has been successfully synthesized under solvothermal conditions. Structure analysis indicates that the framework of JLU-Liu39 is constructed by ternary building units which include a rare hexa-nuclear [CuO(SO)] cluster, a classical [Cu(CO)] paddlewheel, and a 3-connected hetero-N, O donor ligand. The whole 3D framework possesses a (3,4,4)-connected fjh topology and a large window size of 25.3 Å with high solvent-accessible volume accounting for approximately 75.8% of the cell volume. On the basis of the anionic framework and large pore volume, JLU-Liu39 can efficiently adsorb cationic dyes such as MLB, MV, RhB and neutral dye NR but exclude anionic dyes such as MO and Orange II. Moreover, JLU-Liu39 also exhibits size-exclusion performance for dyes of different sizes, and the dye adsorption amounts decrease with the increase of dye size. With respect to the proportional mixture dyes with different charges for MO & MLB and Orange II & MLB, JLU-Liu39 can be able to selectively adsorb the cationic dye MLB efficiently. Based on the aforementioned considerations, JLU-Liu39 is a good anionic-skeleton MOF material for the adsorption and separation of organic dyes.
一种新型金属有机框架化合物[(CH)NH][CuO(SO)CuL(DMF)(HO)]·9DMF（JLU-Liu39）（HL = 吡啶-3,5-双（苯基-4-羧酸））已在溶剂热条件下成功合成。结构分析表明，JLU-Liu39的框架由三元构筑单元构建而成，其中包括一个罕见的六核[CuO(SO)]簇、一个经典的[Cu(CO)]桨轮以及一个三连接的杂N、O供体配体。整个三维框架具有(3,4,4)-连接的fjh拓扑结构和25.3 Å的大窗口尺寸，溶剂可及体积大，约占晶胞体积的75.8%。基于阴离子框架和大孔体积，JLU-Liu39能够有效吸附阳离子染料如MLB、MV、RhB和中性染料NR，但排斥阴离子染料如MO和橙黄II。此外，JLU-Liu39对不同尺寸的染料还表现出尺寸排阻性能，染料吸附量随染料尺寸的增加而降低。对于MO与MLB以及橙黄II与MLB的不同电荷比例混合染料，JLU-Liu39能够高效地选择性吸附阳离子染料MLB。基于上述考虑，JLU-Liu39是一种用于有机染料吸附和分离的优良阴离子骨架MOF材料。
