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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 types of long-chain alkyl ferrocene-substituted porphyrins and their metallic zinc porphyrins were synthesized. One type of ferrocene was linked to the porphyrin through an amide bond, and the long chain was at the periphery (porphyrin 5 and zinc porphyrin 6) ; The other type of ferrocene was linked to the porphyrin (porphyrin 7 and zinc porphyrin 8) by long chains. The spectroscopic and electrochemical properties of two types of porphyrins and their metallic zinc porphyrins were investigated. Two types of porphyrin ligands Of the absorption sites were almost the same, compared with the porphyrin ligand, the maximum absorption of the two types of metal zinc porphyrin received a red shift of 7 nm fluorescence spectra, the amide bond bridged porphyrin 5 and zinc porphyrin 6 The fluorescence quenching degree is relatively increased, and the quantum yield is reduced.Electrochemical studies show that when the porphyrin ligand and metal zinc ions coordinate, the porphyrin ring and ferrocene redox half-wave potential shift. In addition, when the amide bond between ferrocene and porphyrin is replaced by long chain alkyl, the first oxidation potential of porphyrin ligands and complexes decreases slightly (13-18 mV) The oxidation potential is reduced by about 182 ~ 194mV.