【作者】 王莉；

【导师】 刘欣；

【作者基本信息】 南开大学 ， 无机化学， 2012， 博士

【摘要】 近年来，配位聚合物在催化、吸附、电学、光学和磁学等研究领域展现出优良的特性，并具有潜在的应用价值。本论文选用四、五和六元环多酸为配体通过溶剂热自组装得到了32个稀土金属配位聚合物，对其进行了晶体结构、元素分析、波谱等性质表征，并重点探讨了部分配合物的磁学性质和固体荧光性质。以刚性方酸为配体，通过溶剂热自组装得到了14个稀土配位聚合物，发现了方酸三种文献未见报道的桥联模式，Eu(Ⅲ)配合物拥有新颖的拓扑构型，Schl fli符号为{411.610}2{44.62}{45.65}2。磁性测量表明，Gd(Ⅲ)配合物具有铁磁特性，并采用近似模型对其磁性进行了初步拟合。分别测定了部分稀土配合物固体的近红外区荧光光谱和可见光区固体荧光光谱，并测定了Sm(Ⅲ)，Eu(Ⅲ)和Tb(Ⅲ)配合物的荧光寿命，发现其中Eu(Ⅲ)配合物具有良好的发光特性和较长的荧光寿命，可能具有潜在应用价值。以手性D樟脑酸为配体，通过溶剂热自组装合成了6个稀土配位聚合物，研究了其结构、磁性和荧光特性，CD谱研究发现配合物均具有三维手性。采用近似模型，在2-300K温度区间对Eu(Ⅲ)配合物进行了磁性拟合，增加了文献鲜见报道的低温Eu(Ⅲ)配合物变温磁化率拟合范例，同时，得到了一例铁磁性的Tb(Ⅲ)配合物。荧光测试表明，Sm(Ⅲ)、Eu(Ⅲ)和Tb(Ⅲ)配合物具有良好的发光性质和较长的荧光寿命，可能具备潜在应用价值。以柔性1,2,4,5-环己烷四羧酸为配体，通过溶剂热自组装得到了10个三维稀土配位聚合物和两个Gd(Ⅲ)-Co(Ⅱ)和Eu(Ⅲ)-Co(Ⅱ)的混金属配合物，发现了未见文献报道的1,2,4,5-环己烷四羧酸的三种桥联模式。其中Gd(Ⅲ)配合物具有铁磁行为，采用近似模型评估出其磁相互作用参数。对部分稀土配合物进行了近红外光区或可见光区固体荧光性质测试，表明Sm(Ⅲ)和Eu(Ⅲ)配合物具有良好的发光特性，可能具备潜在的应用价值。更多还原

【Abstract】 Recently, the synthesis of coordination polymers has attracted a great deal ofinterest for its potential heterogeneous catalysis, physical absorption, applications inoptoelectronics and emission spectra et, al. In this contribution, thirty-two complexesbased on four, five and six-member ring multidentate acid have been self-assemblysynthesized by solvothermal method. The complexes were characterized by singlecrystal X-ray diffraction, elemental analysis, IR and UV vis spectra, the magneticproperties and the solid-state luminescent properties were also studied.By using squarate acid as ligand, fourteen lanthanide complexes have beensynthesized, in which three new coordination modes were found. The Eu(Ⅲ)complex displays a new topology with the novel short Schl fli symbol of{411.610}2{44.62}{45.65}2. The Gd(Ⅲ) complex shows ferromagnetic interactions andits magnetic properties was estimated by using the approximate model. Thesolid-state near-infrared and the visible region luminescence properties of thecomplexes were investigated. The luminescence life of Sm(Ⅲ)、Eu(Ⅲ) and Tb(Ⅲ)complexes were also explored and the Eu(Ⅲ) complex has attracted a great deal ofinterest for its long luminescence life.By using camphor acid as ligand, six chiral lanthanide complexes have beensynthesized. The chiral properties of the complexes were confirmed by CD spectra.The Tb(Ⅲ) complex shows ferromagnetic interactions and its magnetic propertieswas also assessed. The solid-state near-infrared and the visible region luminescenceproperties of the complexes were also solved. The luminescence life of Sm(Ⅲ),Eu(Ⅲ) and Tb(Ⅲ) complexes were investigated and the Eu(Ⅲ) complex has attracteda great deal of interest for its long luminescence life.By using1,2,4,5-cyclohexanetetracarboxylic acid as ligand, ten lanthanidecomplexes and two lanthanide-transition complexes have been synthesized.1,2,4,5-cyclohexanetetracarboxylic acid displays three new coordination modes. TheGd(Ⅲ) complex shows ferromagnetic interactions. The solid-state near-infrared and visible region luminescence properties of the complexes were explored and theluminescence life of Sm(Ⅲ) and Eu(Ⅲ) complexes were studied.更多还原