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Title: | Photoexcitation-Energy Deactivation in a Solution of 10-Phenyl-5,15-di-(4,6-Dichloropyrimidinyl)-Corrole at 77 K | Authors: | Knyukshto, V. N. Gladkov, L. L. MAES, Wouter Kruk, M. M. |
Issue Date: | 2023 | Publisher: | SPRINGER | Source: | Journal of Applied Spectroscopy, 90 (3) , p. 507 -514 | Abstract: | 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 T-1 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 & UDelta;E(S-1-T-1) = 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 & UDelta;E(S-1-T-1) were calculated by the density functional theory method. An increase in the energy gap & UDelta;E(S-1-T-1) was established to be due to an increase in the energy mismatch & UDelta;E(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. | Notes: | Kruk, MM (corresponding author), Belarusian State Technol Univ, Minsk, BELARUS. llglad@tut.by; wouter-maes@uhasselt.be; m.kruk@belstu.by |
Keywords: | corrole free base;NH-tautomers;deprotonated form;luminescence;molecular orbitals | Document URI: | http://hdl.handle.net/1942/40649 | ISSN: | 0021-9037 | e-ISSN: | 1573-8647 | DOI: | 10.1007/s10812-023-01560-4 | ISI #: | 001015981900001 | Rights: | 2023 Springer Science+Business Media, LLC | Category: | A1 | Type: | Journal Contribution |
Appears in Collections: | Research publications |
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При тушении флуоресценции молекул порфирина энергетический интервал меньше 7800 см-1.pdf | Peer-reviewed author version | 614.03 kB | Adobe PDF | View/Open |
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