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氰基桥联配合物的合成、晶体结构和磁性质研究

The Studies for the Synthesis, Crystal Structure and Magnetic Properties of Cyano-bridged Complexes

【作者】 袁爱华

【导师】 陆路德; 杨绪杰; 汪信;

【作者基本信息】 南京理工大学 , 应用化学, 2005, 博士

【摘要】 本论文以过渡金属离子为自旋载体,以氰根为桥联配体设计并合成了十个氰基桥联配合物,解析了其单晶结构,其中两个为一维链状结构[Ni(en)2]2[Ni(CN)4]2·5H2O、[NiL][Ni(CN)4]·2H2O,三个具有类似的二维网格结构[Fe(salen)]2[Fe(CN)5NO]、[Mn(salen)]2[Ni(CN)4]·0.5H2O、[Fe(salen)]2[Ni(CN)4],一个具有二维蜂窝状层结构[Ni(L)]3[Cr(CN)6]2·9H2O,两个具有三维网状结构[Ni(tn)][Ni(CN)4]·2H2O、[Cu(L)][Fe(CN)6]ClO4·H2O,还有两个是依靠氢键而形成的超分子化合物(H2teta)2{[Ni(teta])][Fe(CN)6]2}·17H2O、(H2teta)[Fe(CN)5NO]·2H2O。用元素分析、红外光谱、等离子发射光谱、热重-差热分析等手段对配合物进行了表征。对五个配合物[Ni(en)2]2[Ni(CN)4]2·5H2O、[Fe(salen)]2[Fe(CN)5NO]、[Mn(salen)]2[Ni(CN)4]·0.5H2O、[Fe(salen)]2[Ni(CN)4]、[Ni(tn)][Ni(CN)4]·2H2O进行了变温磁化率的测定,研究探讨了其磁性与结构的关系,初步提出了可能的机理,为设计合成新的分子基磁性材料提供了科学依据。

【Abstract】 A total of ten new complexes have been synthesized by using transition metal ions as spin carriers and cyanide as bridging ligands and characterized by element analyses, IR, ICP and TG-DTA. The structures of them have been determined by X-ray crystallographic methods, two of which [Ni(en)2]2[Ni(CN)4]2 5H2O [NiL][Ni(CN)4] 2H2O are one-dimensional chains, three of which [Fe(salen)]2[Fe(CN)5NO] , [Mn(salen)]2[Ni(CN)4] 0.5H2O, [Fe(salen)]2[Ni(CN)4] are analogous two-dimensional network structures consisting of pillow-like octanuclear units, one of which [Ni(L)]3[Cr(CN)6]2 9H2O is an two-dimensional stair-like layer, two of which [Ni(tn)][Ni(CN)4] 2H2O, [Cu(L)][Fe(CN)6]C104-H2 O are three-dimensional net-work, the last two of which (H2teta)2 { [Ni(teta)] [Fe(CN)6]2}17H2O, (H2teta) [Fe(CN)5NO]-2H2O are supramoleculars constructed by hydrogen bonds. Five selected complexes, such as [Ni(en)2]2[Ni(CN)4]2 5H2O, [Fe(salen)]2[Fe(CN)5NO] , [Mn(salen)]2[Ni(CN)4] 0.5H2O [Fe(salen)]2[Ni(CN)4] and[Ni(tn)][Ni(CN)4] 2H2O, have been characterized by means of variable-temperature magnetic susceptibility . The magneto-structural correlations have been explored and the possible magnetic exchange mechanisms are explained.

【关键词】 氰基桥联配合物晶体结构磁性质
【Key words】 cyano-bridgedcomplexescrystal structuremagnetism
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