【作者】 王海龙；

【导师】 姜建壮；

【作者基本信息】 山东大学 ， 无机化学， 2010， 硕士

【摘要】 配位化学是无机化学和有机化学交叉的一门学科,其研究的对象是配位化合物(简称配合物)。作为配位化合物的主要体系之一,氰基桥联的金属配合物和基于有机配体构筑的羧基桥联的配位聚合物以其独特荧光、气体吸附、磁性和催化等特性受到各国学者的广泛关注,因而这两类化合物的合成、表征以及性质研究成为配位化学领域中研究的热点之一。分子磁学是人们广泛关注的配位聚合物中的热点领域,它的基本内容就是研究开壳层分子或离子作为自旋载体之间的磁性相互作用。其下属研究范畴包括分子的内部微观磁性行为及分子聚集体的外部宏观磁性行为。外部宏观磁性行为是内部微观磁性行为外化的集中表现形式。微观磁性是分子中自旋载体受到其周围环境影响的外化结果。这些影响包括开壳层离子的配位环境的变化对磁性的影响以及含有多自旋载体分子体系中的载体之间的微观磁行为(即自旋载体间的磁耦合)。这就使得设计合成含有具有新型磁性拓扑结构配合物、发现新的磁学现象以及探讨对金属配合物拓扑结构和磁性的可预测性和可调控性成为科学家们研究内部微观磁性的热门问题。本文正是基于上面描述的分子磁学热点问题,旨在设计具有新型拓扑结构的氰基桥联的三异金属磁性配合物和基于有机羧酸配体的磁性配位聚合物,并初步的探索磁性与结构之间的构效关系。本论文选取修饰的氰基化合物K[M(L)CN2] [M=FeⅢ和CrⅢ并且L=bpb,Clbpb和dmbpb]为前躯体与5-甲基-2羟基-1,3苯二甲醛与相应的系列双胺缩合的双金属配合物反应得到了五个新颖的三异金属磁性配合物,{[CuPb(L1)][Fe(bpb)(CN)2]}2·(ClO4)2·(CH3CN)2·(H2O)2 (1), {[CuPb(L1)][Fe(Clbpb)(CN)2]}·(ClO4)·(CH3CN)·(H2O) (2), {[CuPb(L1)][Fe(bpb)(CN)2]}2·(ClO4)2·(CH3OH)2 (3), {[CuMn(L1)][Fe(bpb)(CN)2]}n·(ClO4)n·(H2O)n (4), {[CuMn(L1)][Cr(bpb)(CN)2]}n·(ClO4)n·(H2O)n (5).对这些化合物进行了系统的合成探索、结构研究和性质表征,丰富了现有的仅有20余例的三异金属配合物的种类,积累了一定的设计和合成新颖的三异金属磁性配合物的经验。初步探讨了磁性拓扑结构和磁性的关系,并根据分子轨道理论对三异金属配合物的金属离子间的作用的成因进行了分析和总结。此外,引入四个从未在晶体工程学中研究过的半刚性V-型的不对称的多羧酸配体,在4,4’-联吡啶配体的帮助下与醋酸钴通过水热合成的反应,成功的合成了四个新颖的Co(Ⅱ)的配位聚合物,[Co(HL1)(u-4,4’-bpy)(H2O)3]n·(4,4’-bpy)n·(H2O)2n (6), [Co1.5(L2)(u-4,4’-bpy)1.5]n·(4,4’-bpy)0.5n (7), [Co3(L3)(HL3)(OH)(H2O)2(u-4,4’-bpy)2]n·(H2O)2.5n (8), [Co1.5(L4)(u-4,4’-bpy)2(H2O)3]n(H2O)3n (9)。讨论了羧酸中的配位构型和四个羧酸配体的羧基不对称位置效应对配位聚合物的分子结构的影响,以及羧酸根的桥联方式与磁性的关系,并通过粗略的拟合模型对这几个化合物进行了拟合,评价了金属离子间的耦合作用性质和强弱。更多还原

【Abstract】 Coordination chemistry is an intercrossed branch between inorganic chemistry and organic chemistry, its investigation subject is coordination compounds (complexes). As a main exploration system, cyanide and carboxyl bridged metal-organic complexes have attracted extensive attentions due to their unique luminescence, gas absorption, magnetism, and catalysis properties, and so on. Therefore, the synthesis, characterization, and investigation on the property of these two kinds of compounds have been the focus in the field of coordination chemistry. Molecule-based magnetism is the hot research field, of which the basic content is to explore the relationship between the neighboring open-shell molecules or ions as spin carriers. There are two branch fields subordinate to the main research field, namely, intramolecular micro-magnetic behavior and macro-magnetic behavior of the molecule aggregates. The macromagnetic behavior is the expression form of the intramolecular magnetic action. The micromagnetism is the result of the spin carriers being influenced by the surrounding. These influences are mainly from the changes of coordination enviroment around the open-shell ions and their micromagnetic action between the spin carriers (magnetic coupling). Accoundingly, the design and synthesis of the new metal-organic complexes with novel magnetic topologies together with discovery of the new magnetic phenomena are the hot research issues, as well as exploration the possibilities of prediction and control for the magnetic topologies and magnetic properties. This thesis mainly concerns about the above mentioned hot issues to design and synthesize cyanide-bridged heterotrimetallic complexes with new magnetic topologies and coordination polymers constructed from semirigid V-shaped asymmetric carboxylic acid as well as to explore the relationship between magnetic propertiy and structure.In this thesis, the modified dicyanometallates K[M(L)CN2] [M= FeⅢand CrⅢ, L=bpb, Clbpb, and dmbpb] as precusors were used to react with the dinuclear metal complexes based on the ligands formed from 2-hydroxy-5-methyl-benzene-1,3-dicarbaldehyde and corresponding diamine. Five novel cyanide bridged heterotrimatallic compounds have been obtained including {[CuPb(L1)][Fe(bpb)(CN)2]}2·(ClO4)2·(CH3CN)2·(H2O)2 (1), {[CuPb(L1)] [Fe(Clbpb)(CN)2]}·(C1O4)·(CH3CN)·(H2O) (2), {[CuPb(L1)][Fe(bpb)(CN)2]}2·(ClO4)2·(CH3OH)2 (3), {[CuMn(L1)] [Fe(bpb)(CN)2]} n·(C104)n·(H20)n (4), {[CuMn(L1)][Cr(bpb)(CN)2]}n·(C104)n·(H20)n (5). The investigation on the synthesis, crystal structure, and magnetic characterization enrich the system of heterotrimetallic species and the experience to construct the heterotrimetallic compounds. The relastionship between the magnetic topology and the magnetic behavior has also been discussed, and the magnetic coupling between the neighboring metal ion s in the herterotrimetallic complexes has been analysized and explained according to the orbit theory.In addition, fourmultidentate O-donor ligands with three coordinating carboxylic groups attached at asymmetrical positions of a semirigid V-shaped central molecular framework has been applied to generate the magnetic materials, which have never been directly employed in the crystal engineering field. Using these four semirigid V-shaped multicarboxylate ligands with the help of a 4,4’-bpy secondary ligand, a series of four novel Co(II) coordination polymers with diverse molecular structures including [Co(HL1)(u,4’-bpy)(H2O)3]n·(4,4’-bpy)n-(H2O)2n (6), [Co1.5(L2)(u-4,4’-bpy)1.5]n·(4,4’-bpy)0.5n (7), [Co3(L3)(HL3)(OH)(H2O)2(u,4’-bpy)2]n·(H2O)2.5n (8), [Co1.5(L4)(u-4,4’-bpy)2(H2O)3]n(H2O)3n (9) has been obtained. The effect between the coordination molecular configurations of the carboxylic acid together with the asymmetric position on the molecular structure of the coordination polymers has been discussed. This is also true for the relationship between the linking mode of the carboxylic substituents and the magnetic properties. According to the easy model, the magnetic coupling between the neighboring metal ions has been evaluated.更多还原