Wang Xiufeng, Li Yungai, Hu Peng, Wang Juanjuan, Li Licun
Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry and Tianjin Key Laboratory of Metal and Molecule-based Material Chemistry, Nankai University, Tianjin 300071, China.
Dalton Trans. 2015 Mar 14;44(10):4560-7. doi: 10.1039/c4dt01878h.
The combination of lanthanide ions and nitronyl nitroxide radicals resulted in four new Ln-radical one-dimensional compounds, namely, [Ln(hfac)3{NIT-Ph(OMe)2}]n(Ln(III) = Sm (1), Eu (2), Gd (3), Dy (4); hfac = hexafluoroacetylacetonate; NIT-Ph(OMe)2 = 2-(2',4'-dimethoxyphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxide). The four complexes were found to be isomorphous and exhibit nitronyl nitroxide radicals-bridged lanthanides linear chains. DC magnetic susceptibilities show that the directly bonded nitronyl nitroxide interacts ferromagnetically with Gd and Dy ions. The Dy complex exhibits three-step metamagnetism and frequency-dependent ac magnetic susceptibilities, indicating single-chain magnet behavior. This work shows that the magnetic behaviors of one-dimensional Ln-nitronyl nitroxide chains can be fine tuned by the substituents of the radicals.
镧系离子与硝酰基氮氧化物自由基相结合,生成了四种新型的一维镧系 - 自由基化合物,即[Ln(hfac)3{NIT - Ph(OMe)2}]n(Ln(III) = Sm (1)、Eu (2)、Gd (3)、Dy (4);hfac = 六氟乙酰丙酮;NIT - Ph(OMe)2 = 2 - (2',4' - 二甲氧基苯基) - 4,4,5,5 - 四甲基 - 4,5 - 二氢 - 1H - 咪唑基 - 1 - 氧基 - 3 - 氧化物)。发现这四种配合物为同晶型,且呈现出由硝酰基氮氧化物自由基桥连的镧系线性链。直流磁化率表明,直接键合的硝酰基氮氧化物与Gd和Dy离子发生铁磁相互作用。Dy配合物表现出三步变磁性和频率依赖性交流磁化率,表明其具有单链磁体行为。这项工作表明,一维Ln - 硝酰基氮氧化物链的磁行为可通过自由基的取代基进行微调。