Jiang Long, Feng Xiao-Long, Lu Tong-Bu, Gao Song
State Key Laboratory of Optoelectronic Materials and Technologies and School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Inorg Chem. 2006 Jun 26;45(13):5018-26. doi: 10.1021/ic052168x.
The preparation and crystal structures of five cyano-bridged Fe-Mn complexes, [(bipy)2Fe(II)(CN)2Mn(II)(bipy)2]2(ClO4)4 (1), [(bipy)2Fe(II)(CN)2Mn(II)(DMF)3(H2O)]2(ClO4)4 (2), {[(Tp)Fe(III)(CN)3]2Mn(II)(DMF)2(H2O)}2 (3), {[(Tp)Fe(III)(CN)3]2Mn(II)(DMF)2}n (4), and Na2[Mn(II)Fe(II)(CN)6] (5) (bipy = 2,2'-bipyridine, Tp = tris(pyrazolyl)hydroborate), are reported here. Compounds 1-4 contain the basic Fe2(CN)4Mn2 square building units, of which 1-3 show the motif of discrete molecular squares of Fe2(CN)4Mn2 and 4 possesses a 1D double-zigzag chain-like structure, while compound 5 is a 3D cubic framework analogous to that of Prussian blue. Compounds 1 and 2 show weak ferromagnetic interactions between two Mn(II) ions through the bent -NC-Fe(II)-CN- bridges. Compound 3 shows weak antiferromagnetic coupling between the Fe(III) and Mn(II) ions, while compound 4 displays a metamagnetic-like behavior with TN = 5.2 K and Hc = 10.5 kOe. Compound 5 exhibits a ferromagnetic ordering with Tc= 3.5 K, coercive field, Hc, = 330 G, and a remnant magnetization of 503 cm3 Oe mol(-1).
本文报道了五种氰基桥联的铁 - 锰配合物，即[(bipy)₂Fe(II)(CN)₂Mn(II)(bipy)₂]₂(ClO₄)₄ (1)、[(bipy)₂Fe(II)(CN)₂Mn(II)(DMF)₃(H₂O)]₂(ClO₄)₄ (2)、{[(Tp)Fe(III)(CN)₃]₂Mn(II)(DMF)₂(H₂O)}₂ (3)、{[(Tp)Fe(III)(CN)₃]₂Mn(II)(DMF)₂}ₙ (4)和Na₂[Mn(II)Fe(II)(CN)₆] (5)（bipy = 2,2'-联吡啶，Tp = 三(吡唑基)硼氢化物）的制备方法和晶体结构。化合物1 - 4包含基本的Fe₂(CN)₄Mn₂方形结构单元，其中1 - 3呈现出离散的Fe₂(CN)₄Mn₂分子方形结构，4具有一维双之字形链状结构，而化合物5是类似于普鲁士蓝的三维立方框架。化合物1和2通过弯曲的 -NC-Fe(II)-CN- 桥在两个Mn(II)离子之间表现出弱铁磁相互作用。化合物3在Fe(III)和Mn(II)离子之间表现出弱反铁磁耦合，而化合物4表现出类变磁行为，居里温度TN = 5.2 K，矫顽场Hc = 10.5 kOe。化合物5表现出铁磁有序，居里温度Tc = 3.5 K，矫顽场Hc = 330 G，剩余磁化强度为503 cm³ Oe mol⁻¹。
