Multi-functional metal–organic frameworks based on H4mdip: Crystal structure, photoluminescence, selective ion-exchange and catalysis
Multi-functional metal–organic frameworks based on H4mdip: Crystal structure, photoluminescence, selective ion-exchange and catalysis
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DOI：
10.1039/c1ce05751k
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发表时间：
2011-11
期刊：
影响因子：
3.1
通讯作者：
S. Xiong;Shujuan Li;Sujing Wang;Zhiyong Wang
中科院分区：
文献类型：
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作者：
S. Xiong;Shujuan Li;Sujing Wang;Zhiyong Wang
四种基于柔性V型四羧酸盐配体的新型金属有机骨架[Me 2 NH][In（mdip）]·2.5DMF·4 H2O（1），[Zn 2（mdip）（bpe）2]·3 H2O（2），[Co2（mdip）（4，4 ′-bipy）2]·2.5DMF·7H2O（3），[Co4（mdip）2（μ2-O）2（py）7]·3DMF·7.5H2O（4）用溶剂热法合成了5，5 ′-亚甲基二草酸（H4 mdip），4，4 ′-联吡啶（4，4 ′-bipy），1，2-二（吡啶-4-基）乙烯（bpe），吡啶（py）。化合物1为三维阴离子骨架，Schlafli符号为（42·63·8），具有选择性离子交换（M = Li+，Na+，K+，Mg 2+，Ca 2+，Sr 2+，Ba 2+，Cu 2+，Fe 3+）。此外，化合物1具有合适的刘易斯酸性和良好的化学稳定性，这使其成为吡咯与硝基烯烃的Friedel-Crafts烷基化反应的良好多相催化剂。化合物2具有一个新的（62·84）（64·82）2 Schlafli符号的三维骨架，这是首次在4-连通二结点网络中发现的。化合物3具有三维开放的多孔骨架结构，并具有（4，6）-连接的双结点网络，其Schlafli符号为（44·610·8）（44·62）。化合物4的手性空间群为P32，具有三维4-连接单结点网络，Schlafli符号为（65·8）。它具有规则的三角形（1D）的同手性通道，沿c轴沿着的边缘为14.7。讨论了H4 midp的晶体结构、配位模式以及N-给体共配体在这些化合物中的调节作用。研究了这些晶体材料的固态性质，如热稳定性、粉末X射线衍射。还研究了化合物1和2的发光波长和发光寿命。
Four new metal organic frameworks based on flexible V-type tetracaboxylate ligands [Me2NH][In(mdip)]·2.5DMF·4H2O (1), [Zn2(mdip)(bpe)2]·3H2O (2), [Co2(mdip)(4,4′-bipy)2]·2.5DMF·7H2O (3), [Co4(mdip)2(μ2-O)2(py)7]·3DMF·7.5H2O (4) (H4mdip = 5,5′-methylenediisophthalic acid, 4,4′-bipy = 4,4′-bipyridine, bpe = (E)-1,2-di(pyridin-4-yl)ethene, py = pyridine), have been synthesized by using solvothermal reactions. Compound 1 was a 3D anionic framework with a (42·63·8) Schlafli symbol and exhibits selective ion exchange (M = Li+, Na+, K+, Mg2+, Ca2+, Sr2+, Ba2+, Cu2+, Fe3+). What is more, Compound 1 has a suitable Lewis acidity and good chemical stability, which makes it a good heterogeneous catalyst for the Friedel–Crafts alkylation of pyrrole with nitroolefins. Compound 2 has a 3D framework with a novel (62·84)(64·82)2 Schlafli symbol, which is first found for 4-connected binodal network. Compound 3 exhibits a 3D open porous framework and exhibits a (4,6)-connected binodal network with a (44·610·8)(44·62) Schlafli symbol. Compound 4 crystallizes in a chiral space groupP32 and has a 3D 4-connected uninodal network with a Schlafli symbol of (65·8). It possesses regular triangular (1D) homochiral channels with an edge of 14.7 A along the c axis. The crystal structures and coordination modes of H4midp, as well as regulatory effect of N-donor co-ligands in these compounds are discussed. Solid-state properties for these crystalline materials, such as thermal stability, powder X-ray diffraction have been investigated. Emissive wavelengths and the radiative lifetime of their luminescent emissions for compounds 1 and 2 have also been investigated.