长链烷基二茂铁取代卟啉的合成与性质

Synthesis and Properties of Porphyrin Containing Long Chain Alkylferrocene

合成了两类长链烷基二茂铁取代的卟啉及其金属锌卟啉,其中一类二茂铁通过酰胺键与卟啉相连,长链在外围（卟啉5与锌卟啉6）;另一类二茂铁通过长链与卟啉相连（卟啉7与锌卟啉8）.研究了两类卟啉及其金属锌卟啉的光谱与电化学性质.两类卟啉配体的吸收位置几乎相同,与卟啉配体相比,两类金属锌卟啉的最大吸收均收发生了7 nm的红移.荧光光谱中,酰胺键桥连的卟啉5与锌卟啉6的荧光猝灭程度相对增大,量子产率降低.电化学研究表明,当卟啉配体与金属锌离子配位后,卟啉环及二茂铁的氧化还原半波电位均发生负移.此外,将连接二茂铁与卟啉的酰胺键换成长链烷基后,卟啉配体及配合物的第一氧化电势略有降低（13~18 m V）,而二茂铁的第一氧化电势却降低182~194m V左右.

Two series of porphyrins and their Zn（II） complexes modified with long chain alkylferrocene were designed. One was close conjugate connection of porphyrin and ferrocene containing long chain alkyl group by an amide linkage in meso site of porphyrin（porphyrin 5 and its Zn（II） complex 6）, the other was placed ferrocene on the skirt of meso-tetraphenylporphyrin with long chain alkoxy group（porphyrin 7 and its Zn（II） complex 8）. The spectroscopic and electrochemistry properties of two series of compounds were investigated. The absorption bands of free porphyrins were almost the same, but those of their Zn（II） complexes were red-shifted by 7 nm. Porphyrins 5 and 6 with an amide linkage exhibited strong fluorescence quenching with a low quantum yield compared with those containing a long chain alkoxy group linkage（7 and 8）. Compared with the free porphyrins, the negative potential shifts of the Zn（II） complexes were observed in cyclic voltammetry experiments. In addition, the first oxidation potentials of porphyrin in 7 and 8 were slight negative shifts relative to 5 and 6, but the first oxidation potentials of ferrocene in 7 and 8 shifted about 182~194 m V.