四苯基卟啉化合物结构与性质研究——Ⅰ.四苯基卟啉及其衍生物的光谱和碱性软硬的分析

STUDIES ON STRUCTURES AND PROPERTIES OF TETRAPHENYLPORPHYRIN AND ITS DERIVATIVES Ⅰ.Spectra and properties of hard and soft of bases for tetraphenylporphyrin and its derivatives

用 HMO 方法计算了—H、—F、—Cl、—Br、—OH 和—OCH_3基取代的四苯基卟啉分子,将它们的前线轨道能级差(ΔE)与实测的最大吸收峰波长λmax 进行线性拟合,相关系数为0.985.还计算了—NH_2基不同数目取代的四苯基卟啉分子,将其计算的ΔE 值代入拟合的关系式中,得出的波长λmax,cale 与实测值相吻合。应用群论对不同数目氨基取代四苯基卟啉的光谱带进行了分析,并将—NH_2不同数目取代对卟啉的四吡咯大环上 N 原子电荷密度进行了比较,指出它们对金属离子的配位能力。预示了三个卟啉衍生物的最大吸收蜂波长。

The molecules of the tetraphenylporphyrin and its derivatives were calculated by HMO method.The linear relationship between observed maximum wavelengths of absorptions and the energy differences of the frontier orbitals was obtained.According to the relationship the calculated maximum wavelengths of the amino tetraphenylporphyrins consist with experiments.In addition,six molecules of the amino tetraphenylporphyrin compounds were calculated by group theory and HMO method.In the light of eight-orbital model and spectrographic selection rules the absorption spectrum bands of the amino tetraphenylporphyrins were explained.The four nitrogen atoms of the porphyrin rings increased in π charges and E_(HOMO) with the increase of the amino-substituted numbers.The compounds are changed more soft bases with the increase of the amino-substituted numbers.The maximum wavelengths of absorptions of three derivative molecules of tetra- phenylporphyrins were predicted.