Structures and properties of gallium-MOFs with MIL-53-topology based on aliphatic linker molecules
Structures and properties of gallium-MOFs with MIL-53-topology based on aliphatic linker molecules
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DOI：
10.1016/j.micromeso.2014.07.058
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发表时间：
2014-12-01
影响因子：
5.2
通讯作者：
De Vos, Dirk
中科院分区：
文献类型：
--
作者：
Reinsch, Helge;De Vos, Dirk
分别以硝酸镓和反式-1，4-环己烷二甲酸（H_2C_8H_10O_4）或（+）-辛酸（H_2C_10H_14O_4）为原料，在N，N-二甲基甲酰胺中合成了两种具有MIL-53拓扑结构的新型金属有机骨架。所有结构表征均基于粉末XRD数据使用结构关系、力场计算和Rietveld精修的组合进行。基于草酸[GaOH（C10 H14 O 4）]或Ga-MIL-53-Cam（1）的化合物以极性正交空间群P2（1）2（1）2（1）（a = 14.0453（3），B = 12.0124（3），c = 6.7658（2）埃）结晶。Ga-MIL-53-Cam具有无孔的致密框架，在空气中可稳定至280 ℃。第二化合物[GaOH（C8 H10 O 4）]中心点0.5DMF（2）或Ga-CAU-13-lp（lp代表大孔）在三斜晶系空间群P-1中结晶（a = 6.7114（2），B = 10.3019（3），c = 9.6265（2）埃，α = 110.743（2），β = 106.883（3），γ = 94.679（3）度）。虽然该化合物在77 K下对氮气没有显示出孔隙率，但在热去除DMF分子后暴露于空气时，水分子可以被吸附到孔中。由此获得的[GaOH（C8 H10 O 4）]中心点H2O（3）或Ga-CAU-13-np（np代表窄孔）具有与Ga-CAU-13-lp相同的空间群对称性，但改变了晶胞参数（P-1，a = 6.7200（2），B = 9.2179（3），c = 9.5082（3）埃，α = 107.359（2），β =102.691（3），γ = 97.913（2）度），因此观察到框架的呼吸，其显示为可逆的。此外，像对二甲苯这样的大分子可以被吸附到孔隙中，突出了化合物的多孔性。与已知的基于芳族对苯二甲酸的Ga-MIL-53相比，呼吸效应的特定性质基本上不同。(C)2014 Elsevier Inc. All rights reserved.
Employing gallium nitrate and one of the aliphatic dicarboxylic acids trans-1,4-cyclohexanedicarboxylic acid (H2C8H10O4) or (+)-camphoric acid (H2C10H14O4), respectively, two new metal-organic frameworks exhibiting the MIL-53-topology were synthesised in N,N-dimethylformamide. All structural characterisations were carried out based on Powder-XRD data using a combination of structural relationship, force-field calculations and Rietveld refinement. The compound based on camphoric acid [GaOH(C10H14O4)] or Ga-MIL-53-Cam (1) crystallises in the polar orthorhombic space group P2(1)2(1)2(1) (a = 14.0453(3), b = 12.0124(3), c = 6.7658(2) angstrom). Ga-MIL-53-Cam exhibits an unporous dense framework which is stable up to 280 degrees C in air. The second compound [GaOH(C8H10O4)]center dot 0.5DMF (2) or Ga-CAU-13-lp (lp stands for large pore) crystallises in the triclinic space group P-1 (a = 6.7114(2), b = 10.3019(3), c = 9.6265(2) angstrom, alpha = 110.743(2), beta = 106.883(3), gamma = 94.679(3)degrees). While this compound shows no porosity towards nitrogen at 77K, water molecules can be adsorbed into the pores upon exposure to air after thermal removal of the DMF molecules. The thus obtained [GaOH(C8H10O4)]center dot H2O (3) or Ga-CAU-13-np (np stand for narrow pore) exhibits the same space group symmetry as Ga-CAU-13-lp but with changed cell parameters (P-1, a = 6.7200(2), b = 9.2179(3), c = 9.5082(3) angstrom, alpha = 107.359(2), beta=102.691(3), gamma = 97.913(2)degrees) and thus a breathing of the framework is observed, which is shown to be reversible. Moreover, large molecules like p-xylene can be adsorbed into the pores, underlining the compound's porosity. The particular nature of the breathing effect is substantially different compared with that known for Ga-MIL-53 based on the aromatic terephthalic acid. (C) 2014 Elsevier Inc. All rights reserved.