The spectral and luminescent characteristics of a solution of 10-phenyl-5,15-di(4,6-dichloropyrimidinyl)-corrole at 77 K were studied. Effective NH-tautomerization was found to occur in the lower T1 triplet state of the long-wavelength T1-tautomer, resulting in phosphorescence being emitted only from the short-wavelength T2-tautomer. A shift of the acid–base equilibrium and deprotonation of a certain fraction of the molecules were observed at 77 K. The fluorescence and phosphorescence spectra of the deprotonated form were identified. The energy gap ΔE(S1–T1) = 5570 cm–1 for the deprotonated form was found to be as large as that for the free bases. The molecular conformations of NH-tautomers for a series of corroles with various peripheral substitution architectures were optimized and their electronic absorption spectra and energy gap ΔE(S1–T1) were calculated by the density functional theory method. An increase in the energy gap ΔE(S1–T1) was established to be due to an increase in the energy mismatch ΔE(LUMO–LUMO+1). The observed trend was common for all types of studied molecular systems, i.e., both NH-tautomers of the free base and the deprotonated form. It was proposed that such a trend is an inherent property of the contracted corrole macrocycle, which has an excess of electron density as compared to the porphine system.
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V. N. Knyukshto is deceased.
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 90, No. 3, pp. 385–393, May–June, 2023.
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Knyukshto, V.N., Gladkov, L.L., Maes, W. et al. Photoexcitation-Energy Deactivation in a Solution of 10-Phenyl-5,15-di-(4,6-Dichloropyrimidinyl)-Corrole at 77 K. J Appl Spectrosc 90, 507–514 (2023). https://doi.org/10.1007/s10812-023-01560-4
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DOI: https://doi.org/10.1007/s10812-023-01560-4