CAJ | 학술논문

采用实验与密度泛函理论计算（DFT ）相结合，研究了不同电子取代基修饰的5-邻羟基苯基-10，15，20-三苯基卟啉（TPPOH）和5-邻羟基苯基-10，15，20-三（对甲氧基）苯基卟啉[（p-OCH3）TPPOH]化合物的吸收光谱及其电化学性质。结果表明，相对于 T PPO H ，由于对位甲氧基（-OC H3）给电子能力强致使（ p-OCH3）TPPOH的卟啉环电子云密度增加，从而引起吸收光谱红移（3 nm）、氧化还原电位发生明显的负移，最高占据分子轨道（HOMO）和最低空轨道（LUMO）能级差降低0.06 eV。DFT 理论分析分子前线轨道电子分布结果显示（p-OCH3）TPPOH的 HOMO和LUMO轨道能量均增加，而能级差却比 TPPOH 能级差小0.05 eV。理论结果与电化学和光谱实验结论一致，并进一步阐明了光谱和电化学性质变化机理，为揭示不同取代基卟啉化合物的设计与应用提供重要依据。
채용실험여밀도범함이론계산（DFT ）상결합，연구료불동전자취대기수식적5-린간기분기-10，15，20-삼분기계람（TPPOH）화5-린간기분기-10，15，20-삼（대갑양기）분기계람[（p-OCH3）TPPOH]화합물적흡수광보급기전화학성질。결과표명，상대우 T PPO H ，유우대위갑양기（-OC H3）급전자능력강치사（ p-OCH3）TPPOH적계람배전자운밀도증가，종이인기흡수광보홍이（3 nm）、양화환원전위발생명현적부이，최고점거분자궤도（HOMO）화최저공궤도（LUMO）능급차강저0.06 eV。DFT 이론분석분자전선궤도전자분포결과현시（p-OCH3）TPPOH적 HOMO화LUMO궤도능량균증가，이능급차각비 TPPOH 능급차소0.05 eV。이론결과여전화학화광보실험결론일치，병진일보천명료광보화전화학성질변화궤리，위게시불동취대기계람화합물적설계여응용제공중요의거。
UV-Vis absorption spectra and electrochemical properties of 5-(o-hydroxyphenyl)-10 ,15 ,20-tri-(p-phenyl)porphyrin (TPPOH) and 5-(o-hydroxyphenyl)-10 ,15 ,20-tri-(p-methoxyphenyl)porphyrin [(p-OCH3 )TPPOH] with different electron groups were investigated by experiments and density functional theory (DFT ) .Due to the introduction of para-methoxyl group (-OCH3 ) ,obvious red shift of 3 nm in the maximum absorbance of the UV-Vis spectra ,negative shift in redox potential of (p-OCH3 )TPPOH ,and the decrease (0 .06 eV) in the energy gap (DE) of the frontier highest occupied molecular orbital (HO-MO) and the lowest unoccupied molecular orbital (LUMO) (of (p-OCH3 )TPPOH occurred as compared to those of TPPOH . The results are due to that electron donating groups of -OCH3 increase the electron density of porphyrin ring in (p-OCH3 )TP-POH .Electron distributions of the frontier orbital calculated by DFT showed that the increase in the energy levels of HOMO and LUMO ,while the decrease of 0 .05 eV in the energy gap .The agreement between experimental result and theoretical value and the further illustration of the mechanism for the spectral change and electrochemical properties provide important bases for the design and application of the porphyrin derivatives with different electron groups .