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一维铜(Ⅱ)配位聚合物的设计、组装及其磁性研究

Self-Assembly and Magnetic Studies of One-Dimensional Copper (Ⅱ) Coordination Polymer

【作者】 韩纬华

【导师】 刘志亮;

【作者基本信息】 内蒙古大学 , 无机化学, 2009, 硕士

【摘要】 随着超分子配位化学和材料科学的发展,分子基磁体的设计与研究成为近年来最引人注目的课题之一。本论文设计合成了结构新颖的4,4’-联吡啶桥联的Schiff碱配位聚合物和叠氮与氧原子混桥的Schiff碱配位聚合物,并解析了配合物的单晶结构。应用元素分析、红外光谱、X—射线衍射、变温磁化率等手段对配合物进行了表征和性质研究。结果表明:(1)4,4’-联吡啶桥联的Schiff碱配位的聚合物以4,4’-联吡啶作为桥联配体,连接相邻单元中的Cu(Ⅱ)离子,形成一维Zig-Zag链状结构,并且一维链横纵交错编织在一起。利用变温磁化率测定及S=1/2一维链磁耦合模型评估了该配合物中的磁相互作用,结果表明:在配合物中,通过4,4’-联吡啶连接的Cu(Ⅱ)离子之间存在弱铁磁耦合作用,链间的自旋相互作用是弱的反铁磁性相互作用。(2)叠氮与氧原子混桥的Schiff碱配位聚合物是用原位自组装的方法合成,以叠氮桥和酚羟基氧桥一起做为桥联配体,连接相邻单元中的Cu(Ⅱ)离子,形成一维链状化合物,通过氢键作用,得到三维网络结构。利用变温磁化率测定及S=1/2一维链磁耦合模型评估了该配合物中的磁相互作用,结果表明:在配合物中,链内的自旋相互作用是铁磁性相互作用,链间的自旋相互作用是反铁磁性相互作用。

【Abstract】 As the development of supramolecular coordination chemistry and material science, the design and research of molecule-based magnets has become one of the most conspicuous topics in recent years. In present paper, two 1D coordination polymers had been synthesized, and the crystal structures of them had been studied. The characterization and magnetic property study of the complexes had been carried out by means of elemental analysis, infrared spectroscopy, X—ray diffraction, temperature dependence magnetic susceptibilities measurements, andso on.(1) The 4,4’—bipyridine bridged Schiff-base coordination polymer: one-demensional complex {[Cu(L)(4,4’-bpy)]·ClO4}n [L= 2-((2-hydroxyethylimino) methyl)phenol, bpy = 4,4’-bipyridine]. The result of single crystal X-ray diffraction shown that the crystal system of the complex belong to orthorahombic, Pbcn(60) space-group, and the cell parameter a = 1.31648(19) nm b = 1.21952(17) nm c = 2.5037(4) nm . N-(2-hydroxyethyl) salicylaldimine is coordinated in tridentate coordination mode. The coordinated atom of the ligand includes oxygen of hydroxybenzene, oxygen atom of hydroxyethyl, and nitrogen atom of imine. In the complex, Cu(Ⅱ) ions are connected by 4,4’-bipyridine bridging ligands and 1D zig-zag structure is formed. The result of temperature dependence magnetic susceptibilities measurements indicates that weak ferromagnetic coupling interaction exists between Cu(Ⅱ) ions, which are connected by 4,4’-bipyridine.(2) The azido-bridged Schiff-base coordination polymer: A novel one-demensional Cu(Ⅱ) ions coordination polymer with formula [Cu(L1)(μ1,1-N3)]n (L1 = 2-(iminomethyl)phenol), had been prepared via in situ self-assembly. The result of single crystal X-ray diffraction shown that the crystal system of the complex belong to orthorahombic, Pccn(56) space-group, and the cell parameter a = 1.4319(3) nm b = 1.9465(4) nm c = 0.5761(1) nm . Compound consists of 1D uniform chains in which the Cu(Ⅱ) ions are bridged by EO-azide and oxygen of salicylidenimine(L1). Magnetic susceptibility measurement reveals the existence of relatively strong ferromagnetic interactions in the 1D chain.

  • 【网络出版投稿人】 内蒙古大学
  • 【网络出版年期】2010年 04期
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