Influence of the central diamagnetic cyanidometal on the distant magnetic interaction in cyanide-bridged Fe(III)-M(II)-Fe(III) complexes

被引:21
作者
Wang, Yong [1 ]
Lin, Chensheng [1 ]
Ma, Xiao [1 ]
Xue, Zhenzhen [1 ]
Zhu, Xiaoquan [1 ]
Cao, Wenhai [1 ]
Hu, Shengmin [1 ]
Sheng, Tianlu [1 ]
Wu, Xintao [1 ]
机构
[1] Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Fujian, Peoples R China
基金
美国国家科学基金会;
关键词
SINGLE-MOLECULE MAGNETS; MIXED-LIGAND COMPLEXES; CRYSTAL-STRUCTURES; SPIN-CROSSOVER; M-II; COORDINATION POLYMERS; TRINUCLEAR COMPLEXES; ELECTRONIC-SPECTRA; BUILDING-BLOCKS; RATIONAL DESIGN;
D O I
10.1039/c5dt00383k
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
To investigate how the central diamagnetic cyanidometal influences the distant magnetic interaction of cyanide-bridged Fe(III)-M(II)-Fe(III) complexes, cis-[Cp(dppe)Fe-II(NC)M-II(L)(2)(CN)Fe-II(dppe) Cp][PF6](2) (M = Os, L = bpy 1; M = Os, L = phen 2; M = Fe, L = bpy 3; M = Fe, L = phen 4), and their one-electron oxidation products 5-7 and two-electron oxidation products 8-11 were synthesized and fully characterized. The cyclic voltammetry of complexes 1-4 suggests that both NC-Os-II(L)(2)-CN and NC-Fe-II(L)(2)-CN have electronic communication ability. The electronic absorption spectroscopy suggests the presence of the central M-II to the terminal Fe-III and the terminal Fe-II to the terminal Fe-III metal to metal charge transfers (MMCTs) in 5-7 and the central M-II to the terminal Fe-III MMCTs in 8-11. Moreover, for the two-electron oxidation products the MMCT energy increases with the central metal in the order Fe < Os < Ru. The two-electron oxidation complexes 8 and 9 exhibit a strong antiferromagnetic coupling (J approximate to -26 cm(-1)) between the two distant Fe-III ions although separated by the diamagnetic cyanidometal NC-Os-II(L)(2)-CN bridge. To the best of our knowledge, this is the strongest magnetic coupling between the distant paramagnetic metal ions across a diamagnetic cyanidometal bridge reported by far. For the two-electron oxidation complexes 10 and 11 with the diamagnetic NC-Fe-II(L)(2)-CN bridge, however, the distant two Fe-III ions possess only very weak antiferromagnetic coupling (J = -0.15 and -0.19 cm(-1)). Combined with our previous reported results, it could be found that the magnetic coupling strength between the distant Fe-III ions increases with the diamagnetic cyanidometal bridge in the order of Fe < Ru < Os.
引用
收藏
页码:7437 / 7448
页数:12
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