Synthesis, structures and properties of Mn(II) coordination frameworks based on R-isophthalate (R = –CH3 or –C(CH3)3) and various dipyridyl-type co-ligands
Synthesis, structures and properties of Mn(II) coordination frameworks based on R-isophthalate (R = –CH3 or –C(CH3)3) and various dipyridyl-type co-ligands
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DOI：
10.1039/b811725j
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发表时间：
2009-01
期刊：
影响因子：
3.1
通讯作者：
Lufang Ma;Liya Wang;Yaoyao Wang;M. Du;Jian-ge Wang
中科院分区：
文献类型：
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作者：
Lufang Ma;Liya Wang;Yaoyao Wang;M. Du;Jian-ge Wang
[Mn（tbip）（bipy）]n（1），{[Mn（tbip）（dpe）]·1.5H2O}n（2），[Mn（tbip）（bpa）]n（3），[Mn（mip）（bpa）]n（4）和{[Mn 3（mip）2（Hmip）2（bpp）2（H2O）2]·2H2O}n（5），通过醋酸锰与H2 tbip的水热反应制备了（H2 tbip = 5-叔丁基丁二酸）或H2 mip（H2 mip = 5-甲基间苯二甲酸）在不同联吡啶共配体存在下的反应（bipy = 4，4 '-联吡啶，dpe = 1，2-双（4-吡啶基）乙烯，bpa = 1，2-双（4-吡啶基）乙烷，bpp = 1，3-二（4-吡啶基）丙烷）。通过元素分析、红外光谱和X-射线单晶衍射对其结构进行了表征。1和2的结构由[Mn 2（tbip）2]n层构成，其由交替的左手和右手螺旋链组成，并进一步由bipy或dpe配体柱撑成3D多孔框架。有趣的是，在1和2中有两种不同大小的孔。从拓扑学的角度来看，配合物1和2都表现出基于二聚体[Mn（COO）]2亚基作为6-连接节点的稀有rob网络。在3和4中具有8-和16-元环的带状链由通过H2 tbip或H2 mip配体桥接的二聚Mn（II）单元产生，所述配体通过柔性dpa连接成2D开放层。配合物5中含有罕见的桥联三锰簇合物作为结构单元，这些簇合物通过mip阴离子进一步连接形成一维梯形链，并以较少的单齿配位bpp作为侧基进行修饰。热稳定性和X射线粉末衍射研究表明，2的微孔骨架在失去客体水分子后仍能保持稳定。此外，在化合物1-3和5中观察到占主导地位的反铁磁耦合。
Five new Mn(II) metal–organic coordination polymers, [Mn(tbip)(bipy)]n (1), {[Mn(tbip)(dpe)]·1.5H2O}n (2), [Mn(tbip)(bpa)]n (3), [Mn(mip)(bpa)]n (4) and {[Mn3(mip)2(Hmip)2(bpp)2(H2O)2]·2H2O}n (5), were prepared through hydrothermal reactions of Mn(II) acetate with H2tbip (H2tbip = 5-tert-butyl isophthalic acid) or H2mip (H2mip = 5-methylisophthalic acid) in the presence of different dipyridyl co-ligands (bipy = 4,4′-bipyridine, dpe = 1,2-bi(4-pyridyl)ethene, bpa = 1,2-bi(4-pyridyl)ethane and bpp = 1,3-di(4-pyridyl)propane). All these compounds were characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. The structures of 1 and 2 are constructed of [Mn2(tbip)2]n layers, which consist of alternate left- and right-handed helical chains, and further pillared by bipy or dpe ligands into a 3D porous framework. Interestingly, there are two different sizes of pores in 1 and 2. From the topology point of view, both complexes 1 and 2 exhibit the rare rob network based on the dimeric [Mn(COO)]2 subunits as the 6-connected nodes. The ribbon-like chains having 8- and 16-membered rings in 3 and 4 result from dimeric Mn(II) units bridged by H2tbip or H2mip ligands, which are connected by the flexible dpa into 2D open layers. Complex 5 contains rare isophthalato-bridged trimanganese clusters as building units, which are further linked by mip anions to form a one-dimensional ladder-like chain with less common unidentate coordinated bpp decorated as pendants. The thermal stabilities and X-ray powder diffraction studies indicate that the microporous framework of 2 can keep stable even after the loss of guest water molecules. In addition, dominant antiferromagnetic coupling was observed in compounds 1–3 and 5.