【作者】 吉亚丽；

【导师】 贾殿赠；

【作者基本信息】 新疆大学 ， 物理化学， 2002， 硕士

【摘要】 本文合成了两类含吡唑啉酮环结构的新型有机光致变色化合物，通过对其晶体结构的分析，初步探讨了它们的结构与光致变色性能之间的关系，全文共分为四大部分。　第一部分合成了两个具有光致变色性的化合物1，3－二苯基－4－苯亚甲基－5－吡唑啉酮缩氨基硫脲（PPBP－TSC）和1－苯基－3－甲基－4－苯亚甲基－5－吡唑啉酮缩硫甲基氨基硫脲（PMBP－smtsc），采用单晶XRD及其它光谱分析技术确定了它们变色前后的结构，通过粉末紫外可见漫反射对它们的光致变色性质进行了表征，并测出了光致变色反应动力学常数，根据结构数据，提出了分子间质子转移机理。由于它的变色主体为吡唑啉酮环，与Schiff碱的特征部分－C＝N－无关，故它不属于Schiff碱类光致变色化合物。　第二部分合成了一系列吡唑啉酮酰肼类化合物，并用元素分析，IR光谱，1H　NMR谱，单晶XRD衍射法进行表征。通过对具有光致变色性的N－(1－苯基－3－甲基－4－苯亚甲基吡唑啉酮－5)－水杨酰肼（PMBP－SAL），和不具有光致变色性的N－(1－苯基－3－甲基－4－苯亚甲基吡唑啉酮－5)－呋喃甲酰肼（PMBP－FNH），N－(1－苯基－3－甲基－4－苯亚甲基吡唑啉酮－5)－对硝基苯甲酰肼（PMBP－PNH）和N－(1－苯基－3－甲基－4－乙酰基吡唑啉酮－5)－水杨酰肼（PMEP－SAL）等晶体结构的对比研究，初步探讨了前者的光致变色机理，并分析了其它化合物不具有光致变色性的原因及其对光致变色性能的影响因素。　第三部分合成了[Ni(PMBP-SAL)(py)]和[Co(PMBP-smtsc)2]·2H2O配合物，采用单晶XRD确定了其结构，并用TG－DSC技术讨论了它的热分解过程。晶体结构研究表明，[Ni(PMBP-SAL)(py)]为一混配配合物，吡啶作为第二配体以N原子参与配位，Ni(Ⅱ)为四配位，且呈略为畸变平面方形；在[Co(PMBP-smtsc)2]·2H2O配合物中，Co(Ⅱ)为六配位，<WP=3>且呈略为畸变的八面体。水分子通过分子间氢键将邻近结构单元桥连起来，形成一维锯齿状链结构的超分子配合物。同时分析了它们不具有光致变色性的原因。　第四部分合成了一种双吡唑啉酮化合物，采用单晶XRD及其它光谱技术确定了它的结构，初步探讨了其反应的机理。更多还原

【Abstract】 Abstract In this paper, two kinds of new organic photochromic compounds containing pyrazolone-ring have beem synthesized and characterized. Their photochromic mechanisms have been discussed by analysis of their crystal structure. The relation between the structure and photochromic properties has been obtained. The paper consists of four parts. In the first part, two new photochromic compounds, 1, 3-phenyl-4-benzylidene-pyrazolone- 5 thiosemicarbazone (PPBP-TSC) and 1-phenyl-3-methyl-4-benzylidene-pyrazolone-5 S-methyl thiosemicarbazone (PMBP-smtsc) have been synthesized and characterized by elemental analysis, MS, UV spectrum, single crystal XRD. The photochromic properties and photochemical kinetics of the two compounds have been studied by powder-UV reflection spectrum under irradiation of 365 nm light. According to analysis of the crystal structure, the intermolecular proton transfer mechanism of photochromism was proposed, which is different from the Schiff base photochromic compounds. The photochromic compounds of this kind take on pyrazolone-ring as photochromic moiety, while the Schiff base photochromic compounds take on -C=N- as photochromic moiety. In the second part, a series of derivants of hydrazide containing pyrazolone have been synthesized and characterized by elemental analysis, IR spectrum, 1H NMR spectrum, MS, UV spectrum and single crystal XRD. In comparison with the photochromic compound N- (1-phenyl-3-methyl-4-benzylidene-pyrazolone-5)-salicylhydrazide and other non-photochromic compounds of N-(1-phenyl-3-methyl-4-benzylidene-pyrazolone-5)-furoylhydrazide, N- (1-phenyl-3-methyl-4-benzylidene-pyrazolone-5)-p-nitrobenzhydrazide and N-(1-phenyl-3- methyl-4-methylidene-pyrazolone-5)-salicylylhydrazide, the photochromic mechanism of the former was proposed. In the third part, two complexes [Ni(PMBP-SAL)(py)] and [Co(PMBP-smtsc)2]·2H2O have <WP=5>been synthesized and characterized by elemental analysis, IR spectrum, TG-DSC and single crystal XRD. According to the crystal structures, [Ni(PMBP-SAL)(py)] is a mix-ligand complex, in which pyridine is the secondary ligand with donor atom of N. Ni(Ⅱ) is slightly deformed four-coordinated square-planar geometry; in the [Co(PMBP-smtsc)2]·2H2O complex, Co(Ⅱ) is slightly distorted octahedron, and water molecules bridge the molecules of adjacent stacks through hydrogen bonds, yielding one-dimensional supramolecular chain structure. In the last part, a new compound containing two pyrazolone-rings has been synthesized and characterized by single crystal XRD and other spectral analysis techniques. The reaction mechanism of the compound was discussed.更多还原