3D lanthanide–transition-metal–organic frameworks constructed from tetranuclear {Ln4} SBUs and Cu centres with fsc net
3D lanthanide–transition-metal–organic frameworks constructed from tetranuclear {Ln4} SBUs and Cu centres with fsc net
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DOI：
10.1039/c0ce00800a
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发表时间：
2011-05
期刊：
影响因子：
3.1
通讯作者：
Jing Xu;W. Su;M. Hong
中科院分区：
文献类型：
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作者：
Jing Xu;W. Su;M. Hong
基于六配位铜中心和以硫酸盐作为辅助桥配体的方形平面四核{Ln4} SBU的四种新型镧系元素(III)-铜(II)异金属配位聚合物，即， [Ln2Cu0.5(2,6-pydc)2(2-pyc)(SO4)(H2O)2]·(H2O) (Ln = Nd 1, Sm 2, Eu 3, Gd 4; 2,6-pydc = 吡啶-2,6-二羧酸酯, 2-pyc = 吡啶-2-羧酸酯), 已通过水热合成和结构表征 单晶X射线衍射。化合物 1-4 是同构结构，呈现出罕见报道的双节 (4,6) 连接 fsc 网络，其中 Cu 中心作为四连接节点，四核 {Ln4} SBU 作为六连接节点。据我们所知，异质Ln-TM配位聚合物中的fsc网络从未有过报道。这项工作提供了结合 {Ln4} SBU 和 Cu 中心构建异金属双节网的一个很好的例子。值得注意的是，2-pyc 配体是通过 2,6-pydc 配体在水热条件下脱羧而原位生成的。此外，还对其IR、TGA、PXRD、发光和磁性能进行了研究。
Four novel lanthanide(III)–copper(II) heterometallic coordination polymers based on six-coordinated Cu centres and square-planar tetranuclear {Ln4} SBUs with sulfate as an auxiliary bridging ligand, namely, [Ln2Cu0.5(2,6-pydc)2(2-pyc)(SO4)(H2O)2]·(H2O) (Ln = Nd 1, Sm 2, Eu 3, Gd 4; 2,6-pydc = pyridine-2,6-dicarboxylate, 2-pyc = pyridine-2-carboxylate), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Compounds 1–4 are isostructural and present a rarely reported binodal (4,6)-connected fsc net with the Cu centre as a four-connected node and the tetranuclear {Ln4} SBUs as six-connected nodes. As far as we know, a fsc net in hetero-Ln–TM coordination polymers has never been reported. This work provides a good example of incorporating {Ln4} SBUs and Cu centres to construct a heterometallic binodal net. Notably, the 2-pyc ligand was in situ generated by decarboxylation of the 2,6-pydc ligand under hydrothermal conditions. Furthermore, the IR, TGA, PXRD, luminescent and magnetic properties were also investigated.