Synthesis, structures and magnetic properties of two chiral mixed-valence iron(ii,iii) coordination networks.
Synthesis, structures and magnetic properties of two chiral mixed-valence iron(ii,iii) coordination networks.
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DOI：
10.1039/c7dt03411c
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发表时间：
2017-12
影响因子：
4
通讯作者：
Yun-Shan Xue;X. Tan;Mengjie Zhou;Hua Mei;Yan Xu
中科院分区：
文献类型：
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作者：
Yun-Shan Xue;X. Tan;Mengjie Zhou;Hua Mei;Yan Xu
在溶剂热条件下合成了两个罕见的手性混合价铁（ii，iii）配位网络d-和l-{[FeIIFeO（BTC）3（DEF）3]·0.5H2O}n（d-1和l-1）（H3 BTC = 1，3，5-苯三甲酸; DEF = N，N-二乙基甲酰胺），并通过单晶X射线衍射对其结构进行了表征.结构分析表明这两种聚合物d-1和l-1是对映体。d-1和l-1的唯一区别是化合物l-1的骨架由左手双螺旋链组成，而d-1由右手双螺旋链组成。在两种结构中同时观察到两个不同的亚基（SBU）{（μ3-O）Fe（COO）6（DEF）3}和{Fe II（COO）6}。两个不同的SBU的集成导致了一个三结点（3，3，6）-连接的网络与一个不寻常的结构拓扑。有趣的是，尽管H3 BTC具有非手性性质，但所得框架显示出罕见的手性螺旋通道。实验表明，十二钨硅酸作为催化剂，可以提高初始反应物的转化率。磁性研究表明Fe ~（3+）离子之间存在反铁磁相互作用。此外，发光研究表明，该化合物在室温下表现出较强的光致发光发射，峰值在457 nm处，这是由于有机连接体和金属簇之间的强相互作用。
Two rare chiral mixed-valence iron(ii,iii) coordination networks d-and l-{[FeIIFeO(BTC)3(DEF)3]·0.5H2O}n (d-1 and l-1) (H3BTC = 1,3,5-benzenetricarboxylic acid; DEF = N,N-diethylformamide) have been synthesized without any chiral auxiliary under the solvothermal conditions and structurally characterized by single crystal X-ray crystallography. Structural analysis indicates that these two polymers d-1 and l-1 are enantiomers. The only difference between d-1 and l-1 is that the framework of compound l-1 consists of left-handed double helical chains, while d-1 consists of right-handed double helical chains. Two distinct subunits (SBUs), {(μ3-O)Fe(COO)6(DEF)3} and {FeII(COO)6}, are observed in both structures simultaneously. The integration of two distinct SBUs leads to a trinodal (3,3,6)-connected net with an unusual structural topology. Interestingly, despite the achiral nature of H3BTC, the resulting framework exhibits rare chiral helical channels. The experiments show that dodecatungstosilic acid acts as a catalyst which could increase the conversion of the initial reactant. The magnetic studies indicate antiferromagnetic interactions between Fe3+ ions. Additionally, the luminescence studies revealed that the compound exhibited strong photoluminescence emissions at room temperature with a peak at 457 nm, owing to the strong interactions between organic linkers and metal clusters.