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  

Synthesis, Structure and Magnetic Property of One-dimension Thenoyltrifluoroacetate Transition Metal Complexes Bridged by 4, 4'-Bipyridine

作　　者：李明星[1] 徐正[1] 游效曾[1] 陈成刚[2] 

机构地区：[1]南京大学配位化学研究所 [2]杭州大学中心实验室,杭州310028

出　　处：《化学学报》1994年第3期274-279,共6页Acta Chimica Sinica

基　　金：国家自然科学基金;国家科学技术委员会重大项目资助

摘　　要：本文合成了六个4,4’-联吡啶桥联配合物:[M(TTA)_2(μ-4,4’-bipy)],[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、~1HNMR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;a=65.99(3),β=83.96(4),γ=68.89(3)°;V=0.9017(4)nm^3;Z=1;D_c=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谱近似计算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.Six one-dimensional complexes with the 4, 4'-bipyridine as bridging ligand, of formula [M(TTA)2(μ-4, 4'-bipy)]n(M = Mn(Ⅱ), Fe(Ⅱ), CO(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Zn (Ⅱ); TTA = thenoyltrifluoroacetone), have been prepared and characterized by elemental analysis, IR, 1HNMR and X-ray crystal structural analysis. It is confirmed that the M(TTA)2 and 4, 4'-bipy form one-dimensional infinite linear structure. The crystals of Mn(Ⅱ) complex belong to triclinic system, and space group is PI. Its unit cell parameters are: a=0.9549 (2), b = 0.9600 (3), c = 1.1656 (3) nm; α=65.99 (3),β= 83.96(4),γ= 68.89(3)°,V=0.9017(4)nm3,Z = 1;Dc = 1.417g·cm-3;μ= 5.3cm-1; F(000) = 398. Final R=0.067. The local coordination geometry around Mn(Ⅱ) is a distorted octahedron. From ESR spectral parameters, the coefficients of molecular orbitals and bond parameters are calculated approximately. The determination of variable-temperature magnetic susceptibility shows that the magnetic susceptibility of Mn(Ⅱ) and Cu(Ⅱ) complexes obeys the Curie law.

关 键 词：联吡啶 桥联 过渡元素 络合物 磁性 

分 类 号：O614.8[理学—无机化学]