Benmansour Samia, Gómez-García Carlos J
Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán 2, 46980 Paterna, Valencia, Spain.
Polymers (Basel). 2016 Mar 16;8(3):89. doi: 10.3390/polym8030089.
In order to synthesize new coordination polymers with original architectures and interesting magnetic properties, we used the nitranilate ligand (C₆O₄(NO₂)₂ = C₆N₂O₈), derived from the dianionic ligand dhbq (2,5-dihydroxy-1,4-benzoquinone = H₂C₆O₄). The use of this bis-bidentate bridging ligand led to [(DAMS)₂{FeNa(C₆N₂O₈)₃}·CH₃CN] (1) (DAMS⁺ = CHN₂⁺ = 4-[4-(dimethylamino)-α-styryl]-1-methylpyridinium), a 2D heterometallic coordination polymer presenting an unprecedented structure for any anilato-based compound. This structural type is a 3,6-connected 2D coordination polymer derived from the well-known honeycomb hexagonal structure, where Fe(III) ions alternate with Na⁺ dimers (as Na₂O units) in the vertices of the hexagons and with an additional [Fe(C₆N₂O₈)₃] anion located in the center of the hexagons connecting the three Na⁺ dimers. The magnetic properties of compound 1 show the presence of paramagnetic isolated high spin Fe(III) complexes with a zero field splitting, |D| = 8.5 cm.
为了合成具有新颖结构和有趣磁性能的新型配位聚合物,我们使用了源自双阴离子配体dhbq(2,5 - 二羟基 - 1,4 - 苯醌 = H₂C₆O₄)的硝酰苯胺配体(C₆O₄(NO₂)₂ = C₆N₂O₈)。使用这种双齿桥联配体得到了[(DAMS)₂{FeNa(C₆N₂O₈)₃}·CH₃CN](1)(DAMS⁺ = CHN₂⁺ = 4 - [4 - (二甲基氨基) - α - 苯乙烯基] - 1 - 甲基吡啶鎓),这是一种二维异金属配位聚合物,对于任何基于苯胺酸酯的化合物而言都呈现出前所未有的结构。这种结构类型是一种由著名的蜂窝状六边形结构衍生而来的3,6 - 连接二维配位聚合物,其中Fe(III)离子在六边形的顶点处与Na⁺二聚体(作为Na₂O单元)交替排列,并且在六边形的中心有一个额外的[Fe(C₆N₂O₈)₃]阴离子连接着三个Na⁺二聚体。化合物1的磁性能表明存在具有零场分裂的顺磁性孤立高自旋Fe(III)配合物,|D| = 8.5 cm⁻¹ 。