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Lopes, J.M.S.; Sharma, K.; Sampaio, R.N.; Batista, A.A.; Ito, A.S.; Machado, A.E.H.; Araújo, P.T.; Barbosa Neto, N.M.
Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy, 02/2019, Letnik: 209Journal Article
We present novel results on the free base 5,10,15,20-meso-tetra(pyridyl)-21H,23H-porphyrin (H2TPyP). This molecule presents complex electronic and vibrational properties and despite the vast literature reporting the transitions observed in its absorption and fluorescence spectra, a more accurate interpretation has been kept elusive. In particular, we show that the molecule's Q-band develops into many electronic and vibronic transitions, whose the well-known “four orbital model” finds it difficult to reconcile. Using distinct spectroscopy techniques, we conclude that both Qx- and Qy-bands comprise, in fact, two quasi-degenerated electronic states together with their respective vibronic progressions each. The analysis of the Huang-Rhys factors and complementary time- and polarization-resolved measurements reinforce the need for the proposed Q-band multi features remodeling. Display omitted •The asymmetric shape of Qy and Qx absorption bands of H2TPyP is discussed.•Q-band is composed of multi-electronic transitions.•Spectral derivative and deconvolution support remodeling of current description.•The vibrational modes belonging to vibronic progressions are determined.
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