烷基二茂铁取代卟啉及其金属配合物的合成与液晶性研究

Two series of porphyrins modified with ferrocene were designed. One was close conjugate connection of porphyrin and ferrocene containing long chain alkyl groups by ester linkage, triazole ring in meso site of porphyrin; the other was placed ferrocene on the skirt of meso-tetraphenylporphyrin with long chain alkoxy groups. The relationship between mesomorphic properties and different link methods, the distance of ferrocene and porphyrin, the number of long chain were investigated in detail. The optimal aspect ratio of molecule was determined by changing the length of alkyl chain. Then the free base porphyrin coordinated to transition metal ions to give the complexes. The difference of mesomorphic properties between ligands and complexes, and complexes with different metal ions were compared. The photophysical，electrochemical properties and electrical conductivity were studies. The relationship between mesomorphic properties and photoinduced electron or energy transfer were investigated. The organometallic liquid crystalline compounds having low melting point, high clearing points, wide temperature range of mesophase, high stability and high charge fluidity were selected, which was hopeful to add the new number to the family of ferrocene and porphyrin liquid crystalline. The research is also supposed to provide some information for the designing organometallic liquid crystalline materials with new structure, high performance and great practical prospects. So, the research has important significance in theoretical study and potential application.

设计了两类二茂铁修饰的卟啉化合物，其中一类是将长链烷基二茂铁通过酯键、三唑环等方式在四个meso位与卟啉近距离相连接，这类化合物二茂铁与卟啉的共轭性较高，另一类是将二茂铁置于带有长链烷氧基的meso-四苯基卟啉外围。考察不同连接方式、二茂铁距卟啉的远近、长链的多少对卟啉介晶性的影响，通过调节烷基链的长度，确定分子的最佳长径比。然后，将卟啉中心与过渡金属离子配位，得到金属卟啉，比较配位前后以及不同金属卟啉的介晶性差异。对两类化合物的光物理、电化学性质及导电能力进行测试，研究二茂铁与卟啉之间的电子或能量转移与卟啉介晶性的关系，筛选出熔点较低、清亮点高、介晶范围宽、稳定性好、电荷流动性较高的卟啉类金属有机液晶化合物，有望为二茂铁和卟啉类金属有机液晶化合物增添新品种，为设计结构新颖、高性能、有实用前景的金属有机液晶材料提供一定的参考信息。因此，本项目无论在理论研究还是潜在的应用方面都有重要意义。

合成了含有二茂铁、亚氨基和氨基的三类卟啉类盘状有机液晶化合物。含有二茂铁的卟啉以及金属锌卟啉液晶化合物熔点低，电荷流动性较高，而含亚氨基和氨基的卟啉液晶化合物清亮点高、介晶范围宽。本项目还合成了分别含有查尔酮、二氢吡唑杂环和三唑杂环的三类偶氮苯类有机液晶分子，这类液晶分子由于含有偶氮键，在光照下可以发生顺反异构体之间的相互转换，在光开关以及信息存储等领域有一定的研究价值。本项研究为有机液晶及金属有机液晶增添新品种，成为该领域的创新性成果。作为本项目的拓展之一，将含有二茂铁的铜、钴、镍卟啉类金属有机化合物首次尝试应用于固体火箭推进剂燃速催化剂，这类催化剂不但燃速催化性能高，而且不迁移，在航空航天以及军事领域具有广阔的应用前景。