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

References

  1. Бучаченко А.Л., Сагдеев Р.З., Салихов К.М. Магнитные и спиновые эффекты в химических реакциях. Новосибирск: Наука, 1978. С. 296.
  2. Химия органических соединений серы. Общие вопросы / Под ред. Л.И. Беленького. М.: Химия, 1988. 329 с.
  3. Кондрор И.И. Автореф. дис. … докт. хим. наук. М., 1985. 303 с.
  4. Degl’Innocenti A., Capperucci A., Mordini A., Reginata G., Ricci F., Cerreta F. // Tetrahedron Lett. 1993. Vol. 34. Р. 873. doi: 10.1016/0040-4039(93)89036-P
  5. Ishii A., Hoshimo M., Nakayama K. // Pure Appl. Chem. 1996. Vol. 68. Р. 869. doi: 10.1351/pac199668040869
  6. Block E., Bayer T., Naganathan S., Zhao S. // J. Am. Chem. Soc. 1996. Vol. 118. Р. 2799. doi: 10.1021/ja953444h.
  7. Фролов Ю.Л., Синеговская Л.М., Кейко В.В., Гусарова Н.К., Ефремова Г.Г., Турчанинова Л.П., Трофимов Б.А. // Изв. АН СССР. Сер. хим. 1986. № 9. С. 1992.
  8. Фролов Ю.Л., Синеговская Л.М., Гусарова Н.К., Потапов В.А., Трофимов Б.А. // Изв. АН СССР. Сер. хим. 1985. № 8. С. 1780.
  9. Liu Z.-Y., Hu J.-W., Huang C.-H., Huang T.-H., Chen D.-G., Ho S.-Y., Chen K.-Y., Li E.Y., Chou P.-T. // J. Am. Chem. Soc. 2019. Vol. 141. Р. 9885. doi: 10.1021/jacs.9b02765
  10. Lévesque S., Gendron D., Bérubé N., Grenier F., Leclerc M., COté M. // J. Phys. Chem. (C). 2014. Vol. 118. Р. 3953. doi: 10.1021/jp411300h
  11. Jayaraj N., Murthy V.S.N., Maddipatla, Rajeev P., Jockusch S., Turro N. J., Ramamurthy V. // J. Phys. Chem. (B). 2010. Vol. 114. P. 14320. doi: 10.1021/jp911698s
  12. Szymanski M. // J. Phys. Chem. (A). 1998. Vol. 102. P. 677. doi: 10.1021/jp9723978
  13. Newman A.K., Henry A.M., Madriaga J.P., Sieffert J.M., Heinrich S.E., Jarboe J.T., Swift V.M., Cheong A.Y.Y., Haynes M.T., Zigler D.F. // Photochem. Photobiol. Sci. 2022. Vol. 21. P. 303. doi: 10.1007/s43630-021-00144-5
  14. Coyle J.D. // Tetrahedron. 1985. Vol. 41. P. 5393. doi: 10.1016/s0040-4020(01)91341-9
  15. Morozova O.B., Yurkovskaya A.V., Tsentalovich Yu.P., Forbes M.D., Khor P.J., Sagdeev R.Z. // Mol. Phys. 2002. Vol. 100. P. 1187. doi: 10.1080/00268970110109970
  16. Grosse S., Yurkovskaya A.V., Lopez J., Viet H.M. // J. Phys. Chem. (А). 2001. Vol. 105. P. 6311. doi: 10.1021/jp004582i
  17. Morozova O.B., Korchak S.E., Viet H.M., Yurkovskaya A.V. // J. Phys. Chem. (B). 2009. Vol. 113. P. 7398. doi: 10.1021/jp8112182
  18. Morozova O.B., Korchak S.E., Sagdeev R.Z. Yurkovskaya A.V. // J. Phys. Chem. (А). 2005. Vol. 109. P. 10459. doi: 10.1021/jp053394v
  19. Morozova O.B., Ivanov K.L., Kiryutin A.S., Sagdeev R.Z., Kehling T., Viet H.M., Yurkovskaya A.V. // Chem. Phys. 2011. Vol. 13. P. 6619. doi: 10.1039/C0CP02449J
  20. Polyakov N.E., Taraban M.B., Leshina T.V. // J. Photochem. Photobiol. (A). 2004. Vol. 80. P. 565. doi: 10.1111/j.1751-1097.2004.tb00130.x
  21. Polyakov N.E., Khan V.K., Taraban M.B., Leshina T.V., Luzina O.A., Salakhutdinov N.F., Tolstikov G.A. // Org. Biomol. Chem. 2005. Vol. 3. P. 881. doi: 10.1039/B416133E
  22. Ageeva A.A., Kruppa A.I., Magin M., Babеnko S.V., Leshina T.V., Polyakov N.E. // Antioxidants. 2022. Vol. 11. P. 1591. doi: 10.3390/antiox11081591
  23. Leshina T.V., Polyakov N.E. // J. Phys. Chem. 1990. Vol. 94. Р. 4379. doi: 10.1021/j100374a001
  24. Юрковская А.В. Автореф. дис. … докт. физ.-мат. наук. Казань, 1997. 241 с.
  25. Порхун В.И., Аристова Ю.В. // Изв. АН. Сер. хим. 2019. Т. 3. С. 565; Porkhun V.I., Aristova Yu.V. // Russ. Chem. Bull. 2019. Vol. 68. N 3. P. 565. doi: 10.1007/s11172-019-2455-x
  26. Leshina T.V., Polyakov N.E. // J. Phys. Chem. 1990. Vol. 94. Р. 4379. doi: 10.1021/j100374a001
  27. Порхун В.И., Аристова Ю.В., Шаркевич И.В. // ЖФХ. 2017. Т. 91. № 6. С. 1001; Porkhun V.I., Aristova Yu.V., Sharkevich I.V. // Russ. J. Phys. Chem. (A). 2017. Vol. 91. N 7. P. 1358. doi: 10.1134/S003602441707024X
  28. Grampp G., Landgraf S., Fasmussen K. // Chem. Soc. Perkin Trans. 2. 1999. Vol. 9. P. 1897. doi: 10.1039/A903394G
  29. Johson J., Inbaraj R.J. // Photochem. Photobiol. (A). 1999. Vol. 124. P. 95. doi: 10.1016/S1010-6030(99)00040-4
  30. Порхун В.И., Аристова Ю.В., Гоник И.Л. // ЖФХ. 2018. Т. 92. С. 1663; Porkhun V.I., Aristova Yu.V., Gonik I.L. // Russ. J. Phys. Chem. (A). 2018. Vol. 92. P. 2092. doi: 10.1134/S0036024418100242
  31. Ivanov K.L., Pravdivtsev A.N., Yurkovskaya A.V., Kaptein R. // Progr. Nucl. Magn. Reson. Spectrosc. 2014. Vol. 81. P. 1.
  32. Porkhun V.I., Rakhimov A.I. // J. Phys. Chem. 2012. Vol. 86. N 11. P. 1915. doi: 10.1134/S0036024412120242
  33. Порхун В.И., Кузнецова Н.А., Подопригора А.Г., Гоник И.Л. // ЖФХ. 2022. Т. 96. № 11 С. 1679; Porkhun V.I., Kuznetsova N.A., Podoprigora A.G., Gonik I.L. // Russ. J. Phys. Chem. (A). 2022. Vol. 96. N 11. P. 2547. doi: 10.1134/S0036024422110243
  34. Порхун В.И., Кузнецова Н.А., Савельев Е.Н. // ЖФХ. 2023. Т. 97. № 3. С. 434. doi: 10.31857/S0044453723030226.
  35. Порхун В.И., Аристова Ю.В., Гоник И.Л. // Изв. АН. Сер. хим. 2018. № 8. С. 1364; Porkhun V.I., Aristova Yu.V., Gonik I.L. // Russ. Chem. Bull. 2018. Vol. 67. N 8. P. 1364. doi: 10.1007/s11172-018-2225-1
  36. Порхун В.И. // Изв. вузов. Приборостроение. 2010. Т. 53. № 10. С. 27.
  37. Калверт Дж., Питтс Дж. Фотохимия. М.: Мир, 1968. 672 с.
  38. Бучаченко А.Л., Вассерман А.М. Стабильные радикалы. М.: Химия, 1973. 408 c.
  39. Электронный ресурс: https://www.msg.chem.iastate.edu
  40. Электронный ресурс: http://avogadro.cc
  41. Tomasi J., Mennucci B., Cammi R. // Chem. Rev. 2005. Vol. 105. N 8. P. 2999. doi: 10.1021/cr9904009
  42. Laali K.K., Sarca V.D., Okazaki T., Brocka A., Der P. // Org. Biomol. Chem. 2005. N 3. P. 1034. doi: 10.1039/B416997B
  43. van den Ende C.A.M., Nyikos L., Sowada U., Warman J.M., Hummel A. // J. Electrostatics.1982. Vol. 12. Р. 97.
  44. Cox J.M., Bain M., Kellogg M., Bradforth S.E., Lopez S.A. // J. Am. Chem. Soc. 2021. Vol. 143. P. 7002. doi: 10.1021/jacs.1c01506
  45. Vyaz H.M., Wan J.K.S. // Chem. Phys. Lett. 1975. Vol. 34. N 3. Р. 470. doi: 10.1016/0009-2614(75)85541-2
  46. Hutton R.S., Roth H.D. // J. Chem. Phys. 1980. Vol. 72. P. 4368. doi: 10.1063/1.439727
  47. Adrian F.J., Vyaz H.M., Wan J.K.S. // J. Chem. Phys. 1976. Vol. 65. P. 1454. doi: 10.1063/1.433199

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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