Department of Chemistry and Biochemistry, University of Minnesota-Duluth, Duluth, Minnesota 55812, USA.
J Phys Chem A. 2010 Nov 18;114(45):12062-6. doi: 10.1021/jp1083828. Epub 2010 Oct 27.
The vertical excitation energies of H(2)TPP [TPP = 5,10,15,20-tetraphenylporphyrin(2-)], H(2)FcPh(3)P [FcPh(3)P = 5-ferrocenyl-10,15,20-triphenylporphyrin(2-)], cis-H(2)Fc(2)Ph(2)P [cis-Fc(2)Ph(2)P = 5,10-bisferrocenyl-15,20-diphenylporphyrin (2-)], trans-H(2)Fc(2)Ph(2)P [trans-Fc(2)Ph(2)P = 5,15-bisferrocenyl-10,20-diphenylporphyrin(2-)], H(2)Fc(3)PhP [H(2)Fc(3)PhP = 5,10,15-trisferrocenyl-20-phenylporphyrin(2-)], and H(2)TFcP [TFcP = 5,10,15,20-tetraferrocenylporphyrin(2-)] were investigated using a time-dependent density functional theory (DFT) approach and compared to their experimental UV-vis spectra in the 10,000-30,000 cm(-1) region. It was shown that the lowest energy transitions in meso(ferrocenyl)-containing porphyrins have predominantly ferrocene-to-porphyrin charge transfer character, while the porphyrin-centered π-π* transitions predicted by the Gouterman's classic four-orbital model still have the largest intensities in the UV-vis region. The number of predominantly ferrocene-to-porphyrin charge transfer transitions increases with the number of ferrocene substituents and becomes dominant in H(2)TFcP.
采用含时密度泛函理论（DFT）方法研究了 H(2)TPP[TPP=5,10,15,20-四苯基卟啉（2-）]、H(2)FcPh(3)P[FcPh(3)P=5-二茂铁基-10,15,20-三苯基卟啉（2-）]、cis-H(2)Fc(2)Ph(2)P[cis-Fc(2)Ph(2)P=5,10-二茂铁基-15,20-二苯基卟啉（2-）]、trans-H(2)Fc(2)Ph(2)P[trans-Fc(2)Ph(2)P=5,15-二茂铁基-10,20-二苯基卟啉（2-）]、H(2)Fc(3)PhP[H(2)Fc(3)PhP=5,10,15-三茂铁基-20-苯基卟啉（2-）]和 H(2)TFcP[TFcP=5,10,15,20-四茂铁基卟啉（2-）]的垂直激发能，并将其与 10,000-30,000cm(-1) 区域的实验 UV-vis 光谱进行了比较。结果表明，含二茂铁基卟啉中最低能量跃迁主要具有二茂铁基到卟啉的电荷转移特征，而 Gouterman 经典四轨道模型预测的卟啉中心π-π*跃迁在 UV-vis 区域仍具有最大强度。主要为二茂铁基到卟啉的电荷转移跃迁的数量随二茂铁基取代基的数量增加而增加，并在 H(2)TFcP 中占主导地位。
