【作者】 林维红；

【导师】 孙维林；

【作者基本信息】 浙江大学 ， 高分子化学与物理， 2009， 博士

【摘要】 本论文利用超分子自组装方法设计合成了有序性的超分子粉末型和层层组装薄膜型金属配合物。对它们的磁性能进行了研究，并进一步探索了配合物结构及其内部金属离子有序性与磁性能的关系，为制备具有较强铁磁性的有机材料提供一种新的方法。论文的主要工作是制备了联噻唑环、吡啶环、邻菲咯啉环三种不同类型的超分子粉末型和多层薄膜型金属配合物。超分子粉末在溶液中制得，多层膜则是以高密度聚乙烯HDPE为基底以配位相互作用为主要推动力经层层自组装得到。通过FT-IR、¹H NMR、UV-vis、AFM、元素分析等测试方法对单体、聚合物、超分子粉末以及多层膜进行了表征，采用EDTA络合滴定和等离子体发射光谱仪测定了超分子粉末及多层膜中的金属含量。磁性能测试结果表明，对于联噻唑类的配合物，经两种不同的方法制得的超分子粉末及多层膜虽然具有类似的组分及内部结构，其磁性能却完全不同。在超分子粉末型配合物中，除DABT／PAA-Cu²⁺和DABT-Fe²⁺／PAA是亚铁磁体外，其余均为较好的铁磁体。联噻唑类薄膜型配合物均显示很好的铁磁性，其磁滞回线表现为典型的S形。对于含Cu²⁺的薄膜，(DABT／Cu²⁺／PAA)_15×2和（PAA／DABT）_20×2-Cu²⁺不仅具有比相应超分子粉末型配合物高2-4倍的相对磁饱和强度（M_s），其顺磁居里-外斯温度（θ）的增大幅度也超过5倍。更突出的是，膜（PAA／DABT）_20×2-Ni²⁺的相对磁饱和强度可以达到37.3emu.g^-1，膜(DABT／Ni²⁺／PAA)_15×2的顺磁居里-外斯温度可以达到242K。对于含吡啶环的超分子粉末型配合物，除含对位吡啶环类的（PSSCu／P4MAAP）_powder为亚铁磁体外，其余均显示铁磁性，并且间位吡啶环类表现出较好的铁磁性，能够在较高的温度就进入磁有序状态。四种含吡啶环组装膜都显示出较强的铁磁性，它们的特征温度（包括进入磁有序状态的温度、磁相达到饱和的温度以及从顺磁性向铁磁性转换的温度）都高于超分子粉末型配合物。其中，膜（PSSCu／P3MAAP）_20×2具有最高的顺磁居里-外斯温度212K，而膜（PSSNi／P4MAAP）_20×2具有最高的相对磁饱和强度8.79emu.g^-1。着重研究了含有邻菲咯啉环的多层膜体系的磁性能。随着组装层数的增加，膜的顺磁居里-外斯温度显示出不断增大的趋势；磁滞回线的S形越来越明显，相对磁饱和强度的值也越来越大。随着耦合作用的不断增强，膜的表观磁性能经历了抗磁性、温控磁转换到铁磁性的变化。不论是含Cu²⁺或Ni²⁺，多层膜（PSSCu／PMPMA）_20×2和（PSSNi／PMPMA）_20×2都具有比相应超分子粉末型配合物较高的顺磁居里-外斯温度和较高的相对磁饱和强度。本文研究还发现，含有P3MAAP、P4MAAP及PMAMP的超分子粉末型或薄膜型配合物的相对磁饱和强度要小于含有DABT的相应超分子粉末型或薄膜。主要是因为与含有小分子组分DABT的体系相比，前面两类体系所用到的组分PSS、P3MAAP、P4MAAP及PMAMP都是分子量相对较高的聚合物，这便使得物质的质量有很大增加，从而引起相对磁饱和强度的值下降。更多还原

【Abstract】 The main content of this paper is the preparation of novel ordered organic supramolecularpowdered and layer-by-layer multilayer thin-filmed metal complexes based on the self-assemblyapproach, and the study of their magnetic behaviors. The aim is quest for the relationship of thestructure of polymer, the kind of metal ions and the magnetic property of the correspondingcomplex. The studies of the magnetic properties of these multilayer films and supramolecularpowders will not only contribute to the research concerning the relationship of structure andmagnetism, but also provide some useful information for the novel functional materials withelectric and magnetic properties.Three kinds of polymers, which containing bithiazole ring, pyridine ring or phenanthrolinering, have been synthesized in this paper. The coordinated supramolecules and correspondingmultilayer films, such as DABT/PAA-M²⁺, DABT-Ni²⁺/PAA, （PAA/DABT）_20×2-M²⁺,(DABT/M²⁺/PAA)_15×2, （PSSM/P3MAAP）_powde, （PSSM/P4MAAP）_powder, （PSSM/P3MAAP）_20×2,（PSSM/P4MAAP）_20×2, （PSSM/PMPMA）_powder and （PSSM/PMPMA）_20×2 have been prepared bythe self-assembly method. The multilayer films were obtained on the HDPE substrate, while thesupramolecules were prepared in solutions. The structures of the molecule, polymers,supramolecules and multilayer films were determined by FT-IR、¹H NMR、UV-vis、AFM andelemental analysis. The metal contents were measured by complexometric titration andinductively coupled plasma emission spectrometer （ICP）.The magnetic properties of these materials were measured by a PPMS-9T magnetometer（QUANTUM DESIGN）, which include magnetization versus temperature, magnetization versusapplied field, magnetic susceptibility versus temperature and magnetic hysteresis. Themeasurement results reveal that the system containing bithiazole rings displayed differentmagnetic behaviours not only for the supramolecules but also for the multilayer films, althoughthe component and structure are similar. Most of the supramolecular powders are softferromagnet, except that DABT/PAA-Cu²⁺ and DABT-Fe²⁺/PAA exhibit special ferrimagneticproperties. All multilayer films display strong ferromagnetic properties with typical "S" shape of the hysteresis loop. For the system containing copper ions, the relative saturation magnetization（M_s） of the multilayer films (DABT/Cu²⁺/PAA)_15×2 and （PAA/DABT）_20×2-Cu²⁺ is about 2-4times as high as that of the corresponding supramolecular powders, and the value ofCurie-Weiss temperature also increases more than 5 times. The film (DABT/Ni²⁺/PAA)_15×2 showhigh specific magnetization, up to Curie-Weiss temperature （θ=242 K）. It is noteworthy that afairly high value of relative saturation magnetization (M_s=37.3 emu.g^-1) is observed for the film（PAA/DABT）_20×2-Ni²⁺.In the pyridine system, for the bulk supramolecular powders, （PSSNi/P3MAAP）_powder and（PSSCu/P3 MAAP）_powder display better ferromagnetic behaviours, while the（PSSCu/P4MAAP）_powder is a ferrimagnet. And the temperature of the magnetic order phase forthe powders containing P3MAAP is higher than others, which coule be attributed to the differentcoordinated structure. All films display strong soft ferromagnetic properties, and thecharacteristic temperature, including the temperature of the magnetic order phase, thetemperature of the magnetic saturation phase and the temperature of the magnetic trasition phase,is higher than those of the corresponding supramolecules. It is found that the multilayer film（PSSNi/P4MAAP）_20×2 exhibits a fairly high value of relative saturation magnetization (M_s=8.79emu.g^-1), while the film （PSSCu/P3MAAP）_20×2 shows a high Curie-Weiss temperature （θ=212K）.The PSSM/PMPMA multilayer films exhibit a self-improvement behavior with the increasingnumbers of cycles of deposition. The increasingly enhanced magnetic property mainly lies inthree aspects: the relative saturation magnetization, Curie-Weiss temperature and S shapehysteresis loop. It is noteworthy that the relative saturation magnetization (M_s=9.6 emu.g^-1) ofthe multilayer film （PSSNi/PMPMA）_20×2 was about 30 times as high as that of the film（PSSNi/PMPMA）_3×2. The differences observed in the magnetic ordering temperature reflect thespecific structural arrangements of the compounds on the substrate surface. Such behavior ismainly caused by the stronger ferromagnetic interactions among paramagnetic spins in theregular three-dimensional framework than in planar structure.With the increasing number ofassembled bilayer, the multilayer films show different magnetic properties, which changes from diamagnetic property, magnetic switch with a transition temperature to ferromagnetic property.The system containing Ni²⁺ displays higher relative saturation magnetization and lowerCurie-Weiss temperature, not only for the supramolecules but also for the multilayer films. Forthe twenty bilayers film （PSSCu/PMPMA）_20×2 and （PSSNi/PMPMA）_20×2, the relative saturationmagnetization and Curie-Weiss temperature are both higher than those of the bulksupramolecular powders （PSSCu/PMPMA）_powder and （PSSNi/PMPMA）_powder.By comparing the magnetic properties of all the systems, we can also find that the relativesaturation magnetization of the supramolecules and films containing P3MAAP, P4MAAP andPMAMP is discovered at high level, even higher than the previous report, but the value is lowerthan that of the supramolecules and multilayer films containing DABT, coming from the highmolecular weigh of the PSS, P3MAAP, P4MAAP and PMPMA.更多还原