【作者】 刘浪；

【导师】 贾殿赠；

【作者基本信息】 新疆大学 ， 物理化学， 2001， 硕士

【摘要】 本文合成了三类以吡唑啉酮环为变色主体的新型有机光致变色化合物，通过对其晶体结构的研究，深入分析了它们的变色机理，并总结了结构与光致变色性能之间的关系，全文共分五大部分。 第一部分合成了两个具有光致变色性的化合物，（1’-苯基-3’-甲基-4’-苯甲酰基-吡唑啉酮-5’）缩4-甲基-氨基硫脲（PMBP-MTSC）和（1’-苯基-3’-甲基-4’-苯甲酰基-吡唑啉酮-5’）缩4-苯基氨基硫脲（PMBP-PTSC），采用单晶XRD法及其它光谱分析技术确定了PMBP-MTSC变色前后的结构，通过紫外漫反射光谱对它的光致变色及热褪色性质进行了表征，并测出了光致变色反应的动力学常数，根据结构解析，提出了分子间质子转移机理。由于它的变色主体在吡唑环上，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[Co（PMBP-TSC）₂.2DMF.2H₂O]配合物，采用单晶衍射法确定了其绝对构型，并用热重和差热分析技术讨论了它的热分解过程，晶体结构研究表明，Co²⁺为六配位，且成略为畸变的八面体，水分子通过氢键将邻近的结构单元桥连起来，形成了三维网络结构的超分子化合物。同时，分析了它不具有光致变色性的原因。 第三部分合成了一系列含吡唑啉酮酰肼类光致变色化合物，并用元素分析，IR，¹HNMR，单晶XRD衍射法进行了表征。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）-皮克啉酸酰肼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）-烟酰肼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。 第四部分合成并表征了N-（1-苯基-3-甲基-4-苯亚甲基-吡唑啉酮-5）-对甲氧基苯甲酰肼（PMBP-PAH）及其过渡金属配合物。分析了这类配体和配合物不具有光致变色的原因，从而应证了第三部分中提出的结论：当吡唑啉酮酰肼类衍生物在侧链芳环的邻位上没有杂原子或取代基时，可能不具有光致变色性。 第五部分首次合成了一种新的光致变色杂环化合物卜苯基－3－甲基．4（6H－4氨基．5．硫杂－2，3－毗噎）－毗哇琳酮－5（PMCP－TSC），通过晶体结构和紫外可见光谱对其光致变色性质进行了表征，并测出了光致变色反应的一级动力学常数，发现它的变色机理为醇式向顺酮式的异构化过程。同时，讨论了电子效应和溶剂对其光致变色性能的影响。更多还原

【Abstract】 In this paper, three kinds of novel organic photochromic compounds containing pyrazolone-ring have been synthesized and characterized. Their photochromic properties have been studied by their crystal structure analyses. The relation between the structure and V properties has been obtained. The paper consists of five parts. In the first part, two new photochromic compounds, (I?-phenyl-3?-methyl-4?- benzoformyl-pyrazolone-5?)-4-methyl-thiosemicarbazone (PMBP-MTSC) and (I?-phenyl- 3?梞ethyl-4?-benzoformyl-pyrazolone-5?)-4-phenyl-thiosemicarbazone (PMBP-PTSC), have been synthesized and characterized by elemental analyses, MS, UV spectra, single- crystal XRD. The photochromic properties and photochemical kinetics of PMBP-MTSC have been studied by powder 桿V reflectance spectra under irradiation of 365nrn light. The crystal structure of colorless product of PMBP-MTSC shows the photochromism is due to the photoisomerization from keto form to enol form. According to the results of structure analyses. an intermolecular proton transfer mechanism of the photochromism is proposed. In the second part, the complex [Co (PMBP-TSC) 2?DMF?H20] has been synthesized and the structure has been determined by X-ray crystallography. 2~ is six coordinated with a distorted octahedral coordination sphere. The studies of crystal structure indicate that the water molecules bridge the molecules of the adjacent stacks through hydrogen bonds, which leads to the supramolecular of three-dimension network structure. Moreover, the reason of the complex without photochromic properties has been analyzed. In the third part, derivants of hydrazide photochromic compounds containing pyrazolone have been synthesized and characterized by elemental analyses, IR spectra, 慔NMR, single- crystal XRD. The structure of two compounds, the photochromic N-( I -phenyl-3-methyl-4- benzoformyl-pyrazolone-5 )-picolinlyhydrazide (PMBP-PCH) and non-photochromic N-( I - phenyl-3-methyl-4-benzoformyl-pyrazolone-5)- nicotinoylhydrazide (PMBP-NTH) have been studied. The results show H-transfer phototautomerism from enol form to cis-keto form occurs in PMBP-PCH. In the fourth part, N- (1-phenyl-3-methyl-4-benzoforinyl-pyrazolone-5)-p-anisic hydrazide (PMBP-PAH) and its complexes have been synthesized and characterized by V elemental analyses, JR spectra, UV spectra, X-ray ciystallography. These studies of the non- photochromic compounds confirm hypothesis in the third part. In the fifth part, a novel photochromic heterocyclic compound (PMCP-TSC) has been synthesized and characterized by elemental analyses, MS. UV spectra, IR spectra, 慔 NMR, single-crystal XRD. The photochromic properties have been studied by UV spectra under irradiation of 365nrn light. First-order rate constant of the photochemical reaction was calculated. The crystal structure shows the photochromism is due to the photoisomerization from enol form to keto form. An intramolecular proton transfer mechanism of the photochromism is proposed.更多还原