A flexible coordination polymer crystal providing reversible structural and magnetic conversions
A flexible coordination polymer crystal providing reversible structural and magnetic conversions
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DOI：
10.1021/ja074915q
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发表时间：
2007-11-07
影响因子：
15
通讯作者：
Kitagawa, Susumu
中科院分区：
文献类型：
--
作者：
Kaneko, Wakako;Ohba, Masaaki;Kitagawa, Susumu
结构柔韧性是配位聚合物的显著特征，对实现环境响应性具有重要意义。我们制备了一种二维氰化物桥接(MnCrIII)-Cr-II配位聚合物[Mn(NNdmenH)(H2O)][Cr(CN)(6)]中心点H2O （1; NNdmen = N，N-二甲基乙二胺），具有复杂排列的可移动水配体。该化合物在脱水[Mn(NNdmenH)I[Cr(CN)61 （1a）的二维片状和三维柱状片状框架之间明显表现出单晶到单晶的可逆转变。结构变化是可逆的，并伴随着二维薄片间CN-Mn键的脱水/水化生成/裂解。化合物1和la在35.2 K和60.4 K下也表现出铁磁有序，其磁性特征通过客体吸附/解吸可逆转变。此外，脱水la表现出了一种连接化学和物理吸附过程以及其框架收缩/膨胀的尺寸选择性溶剂吸附。结合可移动的配体的柔性磁性框架具有多种化学反应功能。
Structural flexibility is a remarkable characteristic of coordination polymers and significant for the attainment of environmental responsivity. We have prepared a 2D cyanide-bridged (MnCrIII)-Cr-II coordination polymer, [Mn(NNdmenH)(H2O)][Cr(CN)(6)]center dot H2O (1; NNdmen = N,N-dirnethylethylenediamine), with sophisticatedly arranged removable water coligands. The compound clearly showed a reversible single-crystalto-single-crystal transformation between the 2D sheet and a 3D pillared-sheet framework of dehydrated [Mn(NNdmenH)I[Cr(CN)61 (1a). The structural change was reversible and accompanied with generation/cleavage of CN-Mn bonds between 2D sheets by dehydration/hydration. Compounds 1 and la also exhibited a ferrimagnetic ordering at 35.2 and 60.4 K, respectively, and the magnetic characteristics were reversibly converted by guest adsorption/desorption. In addition, the dehydrated la demonstrated a size-selective solvent adsorption linking Chemi- and physisorption processes and shrinkage/expansion of its framework. The flexible magnetic framework incorporating removable coligands delivered multifunctions with chemical response.