一维4, 4'-联吡啶桥联噻吩甲酰三氟丙酮过渡金属配合物的合成、结构和磁性

本文合成了六个4, 4'-联吡啶桥联配合物: M(TTA)~2(μ-4, 4'-bipy)]~n,M=Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II); TTA=噻吩甲酰三氟丙酮], 经元素分析、IR、 1^H NMR和晶体结构分析, 确定配合物具有一维无限链状结构。Mn(II)配合物的晶体属三斜晶系, 空间群PI, 晶胞参数: a=0.9549(2),b=0.9600(3), c=1.1556(3)nm, α=65.99(3), β=83.96(4), γ=68.89(3)°;V=0.9017(4)nm^3; Z=1; Dc=1.417g.cm^-3; μ=5.3cm^-1; F(000)=393; 最终R=0.067。Mn(II)处于畸变八面体配位环境中。由Cu(II)配合物的ESR谱近似了分子轨道系数和键合参数。Mn(II), Cu(II)配合物的变温磁化率表明, 金属离子间磁行为服从Curie定律。

Synthesis, structure and magnetic property of one-dimension thenoyltrifluoroacetate transition metal complexes bridged by 4, 4'-bipyridine

Six 1-dimensional complexes with the 4,4'-bipyridine as bridging ligand, M(TTA)2(m-4,4'-bipy)]n (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II); TTAH = thenoyltrifluoroacetone), were prepared and characterized by elemental anal., IR, 1H NMR and x-ray crystal structural anal. The M(TTA)2 and 4,4'-bipy form 1-dimensional infinite linear structure. The crystals of Mn(II) complex belong to triclinic system, and space group is P1. Its unit cell parameters are: a 0.9549(2), b 0.9600(3), c 1.1556(3) nm; a 65.99(3), b 83.96(4), g 68.89(3)? Z = 1; dc = 1.417 g cm-3, m = 5.3 cm-1; F(000) = 393. Final R = 0.067. The local coordination geometry around Mn(II) is a distorted octahedron. From ESR spectral parameters, the coefficients of MOs and bond parameters are calculated approx. The determination of variable-temp. magnetic susceptibility shows that the magnetic susceptibility of Mn(II) and Cu(II) complexes obeys the Curie law.