卟啉衍生物π离子自由基二聚体的电子光谱研究

Electronic Spectra of π Ion-radical Dimer of Porphyrin Derivatives

根据四甲基吡啶铜叶啉（CuTMPyP）的光谱电化学和部分质子化的5，10，15-三（4-羟基苯基）-20－（4-十六烷氧苯基）卟啉（P31）LB膜的荧光光谱，研究了卟琳衍生物离子自由基二聚体的电子光谱．电还原产生的CuTMPyP负离子自由基与基态分子通过SOMO’-LUMO作用形成面对面二聚体，在480nm处出现二聚体的Q带，在820nm处出现π*→π*带．质子化产生的P31正离子自由基与基态分子通过SOMO-HOMO作用形成面对面二聚体，在470～515nm处出现二聚体的Q带吸收，在710nm出现π→π带．与单体Q带相比这些Q带发生蓝移．

The electronic spectra of K ion-radical dimer of porphyrin derivatives were studiedbased on the spectroelectrochemistry of copper (Ⅱ)meso-tetrakis (4-N-methylpyridyl) por-phyrin tetrachloride salt(CuTMPyP) and the fluorescence spectra of partly protonized 5, 10,15-(4-hydroxy phenyl)-20-(4-hexadecyloxy pheny1 ) porphyrin (P31 ) LB film. The face-to-face dimer formed through the SOMO'-LUMO interaction between the electroreducedCuTMPyP anion-radical and the ground state molecule shows Q band at 480 nm and π -πband at 820 nm. The face-to-face dimer produced by the SOMO-HOMO interaction betweenthe protonized P31 cation-radical and the ground state molecule shows the Q band absorptionat the range of 470~515 nm; and the π-π band at 710 nm. These Q bands are blue-shifted.