Nemykin, Victor N. and Hadt, Ryan G. (2010) 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, 114 (45). pp. 12062-12066. ISSN 1089-5639. doi:10.1021/jp1083828. https://resolver.caltech.edu/CaltechAUTHORS:20180612-154059709
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Abstract
The vertical excitation energies of H_2TPP [TPP = 5,10,15,20-tetraphenylporphyrin(2-)], H_2FcPh_3P [FcPh_3P = 5-ferrocenyl-10,15,20-triphenylporphyrin(2-)], cis-H_2Fc_2Ph_2P [cis-Fc_2Ph_2P = 5,10-bisferrocenyl-15,20-diphenylporphyrin (2-)], trans-H_2Fc_2Ph_2P [trans-Fc_2Ph_2P = 5,15-bisferrocenyl-10,20-diphenylporphyrin(2-)], H_2Fc_3PhP [H_2Fc_3PhP = 5,10,15-trisferrocenyl-20-phenylporphyrin(2-)], and H_2TFcP [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_2TFcP.
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| Additional Information: | © 2010 American Chemical Society. Received: September 2, 2010; Revised Manuscript Received: October 7, 2010. Generous support from NSF (CHE-0809203) and Minnesota Supercomputing Institute is greatly appreciated. We also would like to thank Dr. Rodion Belosludov and Dr. Douglas Fox for help with several TDDFT calculations. | |||||||||
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| Issue or Number: | 45 | |||||||||
| DOI: | 10.1021/jp1083828 | |||||||||
| Record Number: | CaltechAUTHORS:20180612-154059709 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20180612-154059709 | |||||||||
| Official Citation: | 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? Victor N. Nemykin and Ryan G. Hadt The Journal of Physical Chemistry A 2010 114 (45), 12062-12066 DOI: 10.1021/jp1083828 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 87034 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | George Porter | |||||||||
| Deposited On: | 12 Jun 2018 23:01 | |||||||||
| Last Modified: | 15 Nov 2021 20:44 |
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