【作者】 陈杰；

【导师】 林展如； 林云；

【作者基本信息】 四川师范大学 ， 材料学， 2008， 硕士

【摘要】 8-羟基喹啉金属配合物与二茂铁聚合物是一类新型的功能材料,在光、电、磁等方面表现出许多特殊的性能,具有广泛的应用前景和重要的基础理论研究。为此,我们在分子设计和性能裁剪的思路上,合成了一系列的二茂铁型双(8-羟基喹啉)席夫碱高分子材料,并探索其结构与性能的关系。本课题研究中,以1,1′-二甲酰氯二茂铁与双(8-羟基喹啉)席夫碱为原料,按照分子设计和性能裁剪的思路,通过缩聚反应得到了二茂铁-8-羟基喹啉型缩聚物,再与不同金属离子M(Fe, Co, Ni, Cu等)配位,获得了一类新型的聚二茂铁-双(8-羟基喹啉)金属配合物。由于被配位的金属原子M和二茂铁中的铁原子间有一定的电子离域,这使它成为既含“磁性”基元的金属原子离域结构,又有“导电”基元的茂环和共轭取代基组成的大共轭体系的新一类高分子化合物。并且对8-羟基喹啉-二茂铁高分子材料采用元素分析、红外光谱(IR)、热重分析(TGA)、固体荧光光谱、X射线粉末衍射(XRD)、磁性分析等对聚合物的结构与性能进行了表征。研究结果表明,合成出的最终产物其化学结构基本符合预期结果,但结构相当复杂,产物中金属配位形式存在多种方式;限于目前的条件与技术水平,高聚物也尚难制成单晶,其化学结构及纯度并不十分明确。同时,我们还发现几个系列的化合物均具有较好的热稳定性,尤其是8-羟基喹啉—二茂铁型金属铜(Cu)聚合物的热稳定性。而金属配聚物较未配位金属的配体高温热稳定性提高不大,可能是由于金属离子与配体之间形成配位键的键能与配位体内的共价键键能相比要小得多,当金属配聚物受热裂解时,首先从配位键开始,因此对高温热稳定性的影响甚微。与无机物的XRD存在明显的尖锐峰不同,配合物(Fc-DD8Q-M)的XRD由于结晶很不完善,晶粒尺寸有限,因此其衍射峰由晶态衍射峰和非晶态的漫散射宽峰组成。配位聚合物的固体荧光测试表明化合物的发射谱出现在425~550nm之间,并且呈现三重荧光性质,在配体与金属离子配合后,荧光强度也有所增强,这可能是配位后体系的共轭程度增大,刚性增强的结果。磁性分析结果表明,在T=300K时,配体与金属配位聚合物的磁化率均大于零,且都在10-2~10-6数量级之间,说明配体和配合物在T=300K时为顺磁性材料;金属配位聚合物与配体相比较,矫顽力Hc,剩余磁化强度Mr都有增大了。我们认为这是由于过渡族金属Co为一种顺磁性粒子,而配体Fc-DD8Q作为一个弱Lewis碱,与过渡金属离子形成配合物,这样通过合理调控自旋中心间的耦合作用,使配体内部所含的铁Fe与配合金属Co之间产生相互交换作用。此外,对N-(8-羟基5-喹啉甲基)蛋氨酸锌配合物的合成与性能研究还处于探索阶段,许多测试工作还正在进行中,将为后续研究奠定基础。更多还原

【Abstract】 Metal-coordination polymer containing 8-hydroxyquinoline and Ferrocenyl polymer served as a new class of functional polymer with lots of special electronic, electrochemical, optical and magnetic properties had extensive application prospects and important values in academic research. Then, on the basis of molecular designs and functional designs, we synthesized a series of metal-coordinated polymers based on ferrocenyl-dis(8-hydroxyquinoline schiff base), and its structures and some performances were studied too.In this paper, a novel compound of dis(8-hydroxyquinoline schiff base) containing ferrocenyl group was prepared by polycondensation between dis(8-hydroxyquinoline schiff base) and 1,1′-dichroloformyl- ferrocene by means of special molecular designs. Then metal-coordinated polymers containing ferrocenyl group and 8-hydroxyquinoline were obtained by self-assembly property. At the same time, because of certaining electronic delocalization between the coordinated metallic atom M (Fe, Co, Ni, Cu, et al) and the iron atom in the ferrocene, these polymeric compound contained both metallic atom delocalization structure of“magnetic”group and the great conjugated system consisted of cyclopentadienide ring and conjugated substituent of the“conductive”group. In the meanwhile, the structure and performance of the composite were characterized by means of elementary analysis, infrared absorption spectrum(IR), thermal gravimetry analysis(TGA), fluorescent spectroscopy, X-ray power diffraction method(XRD), and so on. And the magnetic properties of some compounds were studied under applied magnetic intensity in frequency 0~1.5GHz.Results showed that the final products were just the objects we wanted, but its chemical structures were comparatively complex, and many ways existed in the type of metallic coordinate linkage. We couldn’t ascertain their purity and chemical structure absolutely for the moment, because the polymer hardly cultivated single crystal restricted by our condition and technical level.Meanwhile, we found that all series of compounds were provided with fine thermal stability, especially metal(Cu)-coordinated polymers containing ferrocenyl group and 8-hydroxyquinoline. For the type compounds of dis(8-hydroxyquinoline schiff base) containing ferrocenyl group, the thermal decomposition temperature of 1,1’-divinylferrocenyl polymer could be enhanced by means of introducing dis-(8-hydroxyquinoline) group into the polymer. However, the thermal stability of metallic coordination polymer hardly enhanced in comparison with its ligands. It was possible that the energy of coordinate bond formed between metallic ion and polymer was trival in comparison with that of covalent bond in polymer. It started with coordinate bond when the coordinate polymer decomposed under high temperature, so it engendered little for the thermal stability at high temperature.The researches on X-ray diffraction showed metal-coordination polymers and its ligands took on minicrystal (microcrystalline) with short-range order, but its crystallinity was not quite ideal. Compared with spiculate diffraction peak of inorganic compound, X-ray diffraction of these compounds was formed by speculate crystalline diffraction peak and amorphous-state diffuse scattering peak.The emission fluorescence spectra of all the compounds ranged from 425nm to 550nm when excited by the light of maximal excitation wavelength(390nm) at the room temperature. Metal-coordination polymers and its ligands exhibited stronger solid tripartite-peaks fluorescence properties, and the fluorescence intensity of metal-coordination polymers got better improvement compared with that of its ligands. It might be that when its ligands was coordinated with another metallic atom M(Fe, Co, Ni, Cu), being formed new ring structure make molecule inflexibility better.The result of magnetic anlysis confirmed that magnetic susceptibility of all compounds is positive value, and its value ranged from 10-2 to 10-6. This is a proof that metal-coordination polymers and its ligands is paramagnetic complex at room temperature. Compared with that of its ligands, the coercive force and the remanence of metal-coordination polymers become stronger. The reason might be come from electron exchange of the coordinated metallic atom M (Fe, Co, Ni, Cu, et al) and the iron atom in the ferrocene.In addition, the researches on N-(8-hydroxy-5-quinolinemethyl) methionine zinc-coordinated complex are still at the exploratory stage, and lots of testing works are on the march which will lay the groundworks for continued studies.更多还原