由M（II）-CN-Fe（III）（M = Fe、Ru、Os）组成的四种一维氰基桥联配合物的合成、晶体结构、单分子磁体行为及磁性

Syntheses, crystal structures, MMCT and magnetic properties of four one-dimensional cyanide-bridged complexes comprised of M(II)-CN-Fe(III) (M = Fe, Ru, Os).

作者信息

Wang Yong, Ma Xiao, Hu Shengmin, Wen Yuehong, Xue Zhenzhen, Zhu Xiaoquan, Zhang Xudong, Sheng Tianlu, Wu Xintao

机构信息

State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.

出版信息

Dalton Trans. 2014 Dec 14;43(46):17453-62. doi: 10.1039/c4dt02272f.

DOI:10.1039/c4dt02272f

PMID:25337674

Abstract

Four new one-dimensional (1D) zigzag chain cyanide-bridged complexes cis-MII(L)2(CN)2FeIII(salen) (M = Fe, L = bpy, 3; M = Fe, L = phen, 4; M = Ru, L = bpy, 5; M = Os, L = bpy, 6) (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, salen = N,N′-ethylenebis(salicylideneaminato) dianion) have been synthesized and structurally as well as magnetically characterized, especially 3 and 4 are mixed-valence complexes. Fortunately, the crystals of complexes 3, 4 and 6 suitable for single-crystal X-ray diffraction analysis were obtained. In addition, the electronic absorption spectra indicate the existence of the MMCT (metal-to-metal charge transfer) bands in complexes 3–6. The temperature dependent magnetic susceptibilities reveal that the Fe(III)–Fe(III) exchange coupling separated by a diamagnetic cyanidometal –NC–M(II)–CN– bridge is weakly ferromagnetic for 3–5, but weakly anti-ferromagnetic for 6. Moreover, the specific heat measurements suggest complexes 3–5 exhibit a phase transition at 2.8 K, 2.7 K and 2.6 K, respectively.

摘要

合成了四种新型一维（1D）之字形链状氰基桥联配合物顺式-MII(L)2(CN)2FeIII(salen)（M = Fe，L = 2,2′-联吡啶，3；M = Fe，L = 1,10-菲咯啉，4；M = Ru，L = 2,2′-联吡啶，5；M = Os，L = 2,2′-联吡啶，6）（bpy = 2,2′-联吡啶，phen = 1,10-菲咯啉，salen = N,N′-亚乙基双（水杨醛氨基）二价阴离子），并对其进行了结构和磁性表征，特别是3和4是混合价配合物。幸运的是，获得了适合单晶X射线衍射分析的配合物3、4和6的晶体。此外，电子吸收光谱表明配合物3-6中存在MMCT（金属-金属电荷转移）带。变温磁化率表明，由抗磁性氰基金属–NC–M(II)–CN–桥隔开的Fe(III)–Fe(III)交换耦合对于3-5是弱铁磁性的，但对于6是弱反铁磁性的。此外，比热测量表明配合物3-5分别在2.8 K、2.7 K和2.6 K处表现出相变。