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Article

Phosphorescence and Photophysical Parameters of Porphycene in Cryogenic Matrices

by
Barbara Golec
1,
Aleksander Gorski
1 and
Jacek Waluk
1,2,*
1
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
2
Faculty of Mathematics and Science, Cardinal Stefan Wyszyński University, Dewajtis 5, 01-815 Warsaw, Poland
*
Author to whom correspondence should be addressed.
Photochem 2022, 2(1), 217-224; https://doi.org/10.3390/photochem2010016
Submission received: 22 February 2022 / Revised: 3 March 2022 / Accepted: 7 March 2022 / Published: 9 March 2022
(This article belongs to the Special Issue Photochemistry of Organic Molecules and of Matrix-Isolated Reactive Intermediates: Themed Issue Honoring Professor Rui Fausto for His Contributions to the Field)
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Abstract

Matrix isolation studies were carried out for porphycene, an isomer of porphyrin, embedded in solid nitrogen and xenon. The external heavy atom effect resulted in nearly a 100% population of the triplet state and in the appearance of phosphorescence, with the origin located at 10163 cm−1. This energy is much lower than that corresponding to the T1 position in porphyrin. This difference could be explained by postulating that the orbital origin corresponds in both isomers to the second excited singlet state, which lies much closer to S1 in porphycene. Most of the vibrational frequencies observed in the phosphorescence spectrum correspond to totally symmetric modes, but several ones were assigned to the out-of-plane Bg vibrations. These bands are not observed in fluorescence, which suggests their possible role in vibronic-spin-orbit coupling.
Keywords: phosphorescence; triplet state origin; singlet-triplet energy gap; vibrational frequencies; porphyrin isomers phosphorescence; triplet state origin; singlet-triplet energy gap; vibrational frequencies; porphyrin isomers

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MDPI and ACS Style

Golec, B.; Gorski, A.; Waluk, J. Phosphorescence and Photophysical Parameters of Porphycene in Cryogenic Matrices. Photochem 2022, 2, 217-224. https://doi.org/10.3390/photochem2010016

AMA Style

Golec B, Gorski A, Waluk J. Phosphorescence and Photophysical Parameters of Porphycene in Cryogenic Matrices. Photochem. 2022; 2(1):217-224. https://doi.org/10.3390/photochem2010016

Chicago/Turabian Style

Golec, Barbara, Aleksander Gorski, and Jacek Waluk. 2022. "Phosphorescence and Photophysical Parameters of Porphycene in Cryogenic Matrices" Photochem 2, no. 1: 217-224. https://doi.org/10.3390/photochem2010016

APA Style

Golec, B., Gorski, A., & Waluk, J. (2022). Phosphorescence and Photophysical Parameters of Porphycene in Cryogenic Matrices. Photochem, 2(1), 217-224. https://doi.org/10.3390/photochem2010016

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