The optical spectra of NiP, NiPz, NiTBP, and NiPc: Electronic effects of meso-tetraaza substitution and tetrabenzo annulation
| Autor: | S. J. A. van Gisbergen, Evert Jan Baerends, Giampaolo Ricciardi, Angela Rosa |
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| Přispěvatelé: | Theoretical Chemistry |
| Jazyk: | angličtina |
| Rok vydání: | 2001 |
| Předmět: | |
| Zdroj: | Rosa, A, Ricciardi, G, Baerends, E J & van Gisbergen, S J A 2001, ' The optical spectra of NiP, NiPz, NiTBP, and NiPc: Electronic effects of meso-tetraaza substitution and tetrabenzo annulation ', Journal of Physical Chemistry A, vol. 105, no. 13, pp. 3311-3327 . https://doi.org/10.1021/jp003508x Journal of Physical Chemistry A, 105(13), 3311-3327. American Chemical Society |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/jp003508x |
| Popis: | Time-dependent density functional calculations have been performed on the symmetry and spin-allowed Eu excited states of the nickel tetrapyrrole series, NiP, NiPz, NiTBP, and NiPc. Optical spectra collected in noncoordinating solvents are presented for NiTBP, for the newly synthesized octaethyl nickel porphyrazine, NiOEPz, and for MgOEPz. The theoretical results prove to agree very well with the experimental data, providing an accurate description of the UV−vis spectra. The effects on the optical spectra of introducing in the basic porphyrinic ring, aza bridges, benzo rings, both aza bridges and benzo rings, and a transition metal are highlighted and interpreted on the basis of the electronic structure changes occurring along the series. The following results were found: (i) The near-degeneracy of the configurations (a1ueg) and (a2ueg) of the four-orbital model leads to strong mixing in NiP. The resulting low-energy state corresponds to the Q band with low intensity due to opposing transition dipoles of ... |
| Databáze: | OpenAIRE |
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