【作者】 刘广飞；

【导师】 贾殿赠；

【作者基本信息】 新疆大学 ， 物理化学， 2003， 硕士

【摘要】 有机光致变色化合物及其相关的化学已研究并发展了有一百多年的历史。例如螺旋化合物，像俘精酸酐，螺噁嗪类，由于它们在信息记录，信息处理，各种发射材料和分子开关等领域有广阔的应用前景，已经进行了深入的研究。有些研究者对含有光致变色配体的过渡金属及稀土配合物也进行了大量的研究，如螺吡喃、螺噁嗪等，但对含吡唑啉酮缩氨基硫脲类光致变色化合物的研究还鲜有报道。 本文在前几届研究生的工作基础上，合成了一系列以吡唑啉酮环为变色主体的新型有机光致变色化合物及相关衍生物，通过对它们变色性质和晶体结构的研究，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。 第一部分合成了四个具有光致变色性质的化合物，1-苯基-3-甲基-4-对溴苯甲酰基-5-吡唑啉酮缩氨基硫脲(PM4BrBP-TSC)、1-苯基-3-甲基-4-对溴苯甲酰基-5-吡唑啉酮缩4-甲基-氨基硫脲(PM4BrBP-MTSC)、1-苯基-3-甲基-4-邻氯苯甲酰基-5-吡唑啉酮缩4-甲基-氨基硫脲(PM2CBP-MTSC)、1，3-二苯基-4-苯甲酰基-5-吡唑啉酮缩4-甲基-氨基硫脲(PPBP-MTSC)。用元素分析、IR、~1HNMR确定了它们的结构，用固体时间相关紫外—可见光普法(所谓时间相关光谱法，就是每隔一定的时间，测定样品的光谱，比较不同时间的光谱的不同，即可清楚地看到光致变色的变化)表征了它们的光致变色性质，并计算出了光致变色的动力学反应级数，采用单晶XRD法及其它光谱分析技术得到了PM4BrBP-MTSC及PM4BrBP-TSC的结构，根据结构解析，我们推测，其变色机理可能是分子结构由一种酮式变为一种酮式，发生了构象变化。 第二部分合成了1-苯基-3-甲基-4-丙酰基-5-吡唑啉酮(PMPP)类及1．苯基．3一甲基一4苯乙酸基一5一毗哇晰酮（PMPaP）类的毗哗啦酮衍生物，采用单晶衍射法确定了l一苯基一3一甲基一4苯乙酸基一5一毗哩琳酮缩氨基晚（PMPPSC）及 卜苯基上一甲基个苯乙酸基6J 哇咐酮缩氨基脱叩MPaP七C）的绝对构型，并用其它光谱技术确定了另外几种衍生物的结构。通过对结构的分析，说明了它们不具有光致变色性的原因，从而得出：当毗哩琳酮4位取代基不是给电子共扼大的基因如苯环等时，所合成的化合物不具有光致变色性，或者说它们的光致变色过程已在溶液中完成，析出的产物本身就是一种比较稳定的结构，即使增加能量也不会使其发生框架结构的变化，所以观察不到光致变色现象。 第三部分合成了一系列含NNS杂环的毗哇咐酮衍生物，并用元素分析，IR’HNMR单晶XRD衍射法进行了表征。对三个测出晶体结构的杂环化合物进行了细致的分析，初步探讨了它们的反应机理，并通过与PMCP—TSC结构的对比，分析了化合物不具有光致变色性的原因。更多还原

【Abstract】 Organic photochromic compounds and their chemistry have been developed and studied comprehensively for over a hundred years. For example, spirocompounds, fulgides, spirooxazines have been much studied due to their potential wide application in information recording and processing, variable transmitting materials and molecular switching devices. There is certain interest in the photochromism of transition metal and rare earth complexes which have photochromic ligands such as spiropyrans and spirooxazines. But little attention is paid to those thiosemicarbazones(TSCs) photochromic compounds which contain pyrozolone ring.On the basis of the work of previous graduate students, a series of new photochromic compounds and their relevant derivatives containing pyrozolone-ring have been synthesized. The photochromic mechanism was analyzed and presumed by studying the properties and crystal struture of the photochromic compounds. The relation between the structure and properties has been obtained.In the first part, four new photochromic compounds, l-Phenyl-3-methyl-4-(4-bromobenzal)pyrazol-5-one N(4)-methyl-3-thiosemi-carbazone(PM4BrBP-MTSC), 1-Phenyl-3-methyl-4-(4-bromobenzal)pyrazol-5-one thiosemicarbazone(PM4BrBP-TSC), l-Phenyl-3-methyl-4-(2-chlorobenzal) pyrazol-5-one N(4)-methyl-3-thiosemicarbazone (PM2C1BP-MTSC), 1,3-phenyl-4-benzoformyl-pyrazol-5-one N(4)-methyl-3-thiosemi-carbazone(PPBP-MTSC) have been synthesized and characterized by elemental analyses, UV spectra, single-crystal XRD. The photochromic properties and photochemical kinetics of these compounds have been studiedby solid Time-dependent UV-vis absorption spectra under irradiation of 365nm light. The crystal structure of colorless product of PM4BrBP-TSC and yellow product of PM4BrBP-MTSC shows the photochromism is due to the photoisomerization only from one keto form to another keto form. According to the results of structure analyses, the mechanism of conformation change for photochromism is proposed.In the second part, l-phenyl-3-methyl-4-propropionyl-5-pyrazol-one(PMPP) and l-phenyl-3-methyl-4-phenylacet-5-pyrazolone(PMPaP) including their derivatives have been prepared. The conformation of l-phenyl-3-methyl-4-propropionyl-pyrazol-5-one semicarbazone(PMPP-SC) and l-phenyl-3-methyl-4-phenylacet-pyrazol-5-one semicarbazone(PMPaP-SC) were determined by X-ray crystallography, other molecular structure of the derivatives were obtained by the techniques of elemental analyses, IR and 1HNMR. We have envisioned the reason of non-photochromism for these compounds by analyzing their structure, and then acquired the conclusion that, if the 4-position of pyrazolone-ring is the conjugate group of electron contributing, for example, phenyl and other substituted phenyl, the compounds synthesized possess the properties of photochromism, to the contrary, there is no photochromism. In the other words, their process of photochromism have been completed in solution, and the structures of compounds participated from solution are stable, and their conformation cannot be changed, even though the energy(e.g. Uv-visible light) were added. So, the photochromism cannot be observed.In the third part, a series of novel heterocyclic compounds PMCP-MTSC [l-phenyl-3-methyl-4-(6-hydro-4-methylamino-5-sulfo-2,3-pyrazine)-pyrazole-5-one], PMCP-PTSC, PPCP-TSC, PPCP-MTSC, PPCP-PTSC, PPCP-SHN have been synthesized and characterized by elemental analyses, IR spectra, 1H NMR spectra and single-crystal XRD. Three structures of them were confirmed exactly by X-ray crystallography and analyzed meticulously. The mechanism of reaction was discussed preliminarily and the reason of non-photochromism is obtained by contrast the structure of PMCP-TSC.更多还原