Competing mechanisms for the formation of chemical nuclear polarization effects during photolysis of 1-(4-methylphenyl)-3-phenylpropane-2-thione in different solvents

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Abstract

According to the Kloss–Kaptein–Oosterhoff model of radical pairs, the formation of chemical nuclear polarization occurs at the stage of recombination of radicals during singlet-triplet transitions S–T0 in radical pairs or according to the triplet mechanism during electron-nuclear cross-relaxation transitions. In this work, the competition between the formation of the nuclear polarization mechanism during the photolysis of CH3C6H4CH2CSCH2Ph thione in various solvents was experimentally proven.

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About the authors

V. I. Porkhun

Volgograd State Technical University

Email: arisjulia@yandex.ru
Russian Federation, 400005, Volgograd

D. V. Zavyalov

Volgograd State Technical University

Email: arisjulia@yandex.ru
Russian Federation, 400005, Volgograd

Е. N. Savelyev

Volgograd State Technical University

Email: arisjulia@yandex.ru
Russian Federation, 400005, Volgograd

Yu. V. Bogdanova

Volgograd State Technical University

Author for correspondence.
Email: arisjulia@yandex.ru
Russian Federation, 400005, Volgograd

N. A. Kuznetsova

Volgograd State Technical University

Email: arisjulia@yandex.ru
Russian Federation, 400005, Volgograd

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Supplementary files

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2. Fig. 1. 1H NMR spectra of the starting thione in d-acetonitrile: (a) dark spectrum; (b) during photolysis, one flash of the lamp. 1 – signal of CH3 (2.34 ppm); 2 – signal of CH2 of the tolylmethyl group (4.18 ppm); 3 – signal of CH2 of the benzyl group of thione (4.28 ppm); 4 – signal of aromatic protons of the benzyl group (7.29 ppm); 5 – signal of aromatic protons of the tolylmethylene group (7.15 ppm); * – solvent signal.

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3. Fig. 2. 13C NMR spectrum of the starting thione in d-acetonitrile: (a) dark spectrum; (b) during photolysis with one lamp flash. 1 – signal of CH3 (21.46 ppm); 2 – signal of CH2 of the tolylmethylene group (47.3 ppm); 3 – signal of CH2 of the benzyl group of thione (48.6 ppm); 4 – signal of the aromatic carbon (127–129 ppm); 5, 6 – signal of quaternary carbons (135.99, 137.45 ppm); 7 – signal of C=S; * – solvent signal.

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4. Fig. 3. Energy ΔG‡ of the transition state of formation of two radical pairs 2 and 3 in the triplet state.

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5. Fig. 4. 1H NMR spectra of the initial thione in hexafluorobenzene: (a) dark spectrum; (b) after the first flash; (c) during photolysis for 60 s. 1 – signal of CH3 (2.45 ppm); 2 – signal of CH2 of the tolylmethylene group (4.24 ppm); 3 – signal of CH2 of the benzyl group of thione (4.35 ppm); 4 – signal of aromatic protons of the benzyl group (3.2 ppm); 5 – signal of aromatic protons of the tolylmethylene group (7.16 ppm); 6 – aromatic protons of the formed dibenzyl (6.9 ppm); 7 – signal of CH2 of the formed dibenzyl (2.9 ppm).

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6. Fig. 5. The upfield part of the 13C NMR spectrum of thione 1 after 60 s of irradiation in C6F6. The 13C signals of the solvent are superimposed on the 13C signals of the aromatic carbons. 1 – signal of CH3 of dibenzyl (19.0 ppm); 2 – signal of CH3 of the initial thione (22.6 ppm); 3 – signal of CH2 of the formed dibenzyl (37.9 ppm); 4 – signal of CH2 of the tolylmethyl group (47.2 ppm); 5 – signal of CH2 of the benzyl group of thione (48.5 ppm).

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