☆ 4.6 Article

Interpretation of the UV-vis Spectra of the meso(Ferrocenyl)-Containing Porphyrins using a TDDFT Approach: Is Gouterman's Classic Four-Orbital Model Still in Play?

JOURNAL OF PHYSICAL CHEMISTRY A (2010)

期刊

JOURNAL OF PHYSICAL CHEMISTRY A

卷 114, 期 45, 页码 12062-12066

出版社

AMER CHEMICAL SOC

DOI: 10.1021/jp1083828

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Chemistry, Physical Physics, Atomic, Molecular & Chemical

资金

NSF [CHE-0809203]
Minnesota Supercomputing Institute

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The vertical excitation energies of H2TPP [TPP = 5,10,15,20-tetraphenylporphyrin(2-)], H2FePh3P [FePh3P = 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 pi-pi* 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.

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