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Time-Resolved Continuous-Wave and Pulse EPR Investigation of Photoinduced States of Zinc Porphyrin Linked with an Ethylenediamine Copper Complex

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Abstract

Electron spin dynamics of the photoexcited state of a new porphyrin system built of a zinc porphyrin molecule with a linked complex of copper ion (ZnPCu) was studied using electron paramagnetic resonance (EPR) methods. The time-resolved continuous-wave and echo-detected EPR data show that electron spins of the ZnPCu system are polarized. The shape of the EPR spectrum and the echo-detected nutation spectroscopy data indicate that there is a relatively small spin–spin interaction between two subunits, namely, less than the zero-field splitting parameter of the excited triplet ZnP molecule. Results have been interpreted assuming that the S = 1 Zn porphyrin subunit electron spins are polarized via the triplet mechanism and this polarization is transferred to the S = 1/2 copper subunit via a flip-flop process induced by the exchange interaction between these subunits. The formation of the integral spin polarization in the triplet–doublet system as a function of the value and type of the triplet–doublet interaction was analyzed.

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References

  1. P. Beletskaya, V.S. Tyurin, A.Yu. Tsivadze, R. Guilard, C. Stern, Chem. Rev. 109, 1659–1713 (2009)

    Article  Google Scholar 

  2. L.B. Josefsen, R.W. Boyle, Theranostics 2(9), 916–966 (2012)

    Article  Google Scholar 

  3. M.G. Walter, A.B. Rudine, C.C. Wamser, J. Porphyrins Phthalocyanines 14, 759–792 (2010)

    Article  Google Scholar 

  4. E.A. Mikhalitsyna, V.S. Tyurin, V.N. Khrustalev, I.S. Lonin, I.P. Beletskaya, Dalton Trans. 43, 3563–3575 (2014)

    Article  Google Scholar 

  5. C. Corvaja, M. Maggini, M. Prato, G. Scorrano, M. Venzin, J. Am. Chem. Soc. 117, 8857 (1995)

    Article  Google Scholar 

  6. K. Ishii, J. Fujisawa, Y. Ohba, S. Yamauchi, J. Am. Chem. Soc. 118, 13079 (1996)

    Article  Google Scholar 

  7. N. Mizuochi, Y. Ohba, S. Yamauchi, J. Phys. Chem. A 101, 5966 (1997)

    Article  Google Scholar 

  8. N. Mizuochi, Y. Ohba, S. Yamauchi, J. Phys. Chem. A 103, 7749 (1999)

    Article  Google Scholar 

  9. Y. Teki, S. Miyamoto, K. Iimura, M. Nakatsuji, Y. Miura, J. Am. Chem. Soc. 122, 984–985 (2000)

    Article  Google Scholar 

  10. K. Ishii, T. Ishizaki, N. Kobayashi, J. Chem. Soc. Dalton Trans. 3227–3231 (2001)

  11. K. Ishii, Y. Hirose, H. Fujitsuka, O. Ito, N. Kobayashi, J. Am. Chem. Soc. 123, 702–708 (2001)

    Article  Google Scholar 

  12. Y. Teki, M. Nakatsuji, Y. Miura, Mol. Phys. 100, 1385–1394 (2002)

    Article  ADS  Google Scholar 

  13. L. Franco, M. Mazzoni, C. Corvaja, V.P. Gubskaya, L.S. Berezhnaya, I.A. Nuretdinov, Appl. Magn. Reson. 30, 577–590 (2006)

    Article  Google Scholar 

  14. L. Franco, M. Mazzoni, C. Corvaja, V.P. Gubskaya, L.S. Berezhnaya, I.A. Nuretdinov, Mol. Phys. 104, 1543–1550 (2006)

    Article  ADS  Google Scholar 

  15. Y. Teki, H. Tamekuni, K. Haruta, J. Takeuchi, Y. Miura, J. Mater. Chem. 18, 381–391 (2008)

    Article  Google Scholar 

  16. V.F. Tarasov, I.S.M. Saiful, Y. Ohba, K. Takahashi, S. Yamauchi, Spectrochim. Acta A 69, 1327–1330 (2008)

    Article  ADS  Google Scholar 

  17. P.K. Poddutoori, M. Pilkington, A. Alberola, V. Polo, J.E. Warrenand, A. van der Est, Inorg. Chem. 49, 3516–3524 (2010)

    Article  Google Scholar 

  18. M. Gouterman, R.A. Mathies, B.E. Smith, W.S. Caughey, J. Chem. Phys. 52, 3795–3802 (1970)

    Article  ADS  Google Scholar 

  19. W.A.J.A. van der Poel, A.M. Nuijs, J.H. van der Waals, J. Phys. Chem. 90, 1537–1540 (1986)

    Article  Google Scholar 

  20. V. Rozenshtein, A. Berg, H. Levanon, U. Krueger, D. Stehlik, Y. Kandrashkin, A. van der Est, Isr. J. Chem. 43(3–4), 373–381 (2003)

    Article  Google Scholar 

  21. M. Asano-Someda, A. van der Est, U. Kruger, Y. Kaizu, H. Levanon, J. Phys. Chem. A 103, 6704–6714 (1999)

    Article  Google Scholar 

  22. A. Est, M. Asano-Someda, P. Ragogna, Y. Kaizu, J. Phys. Chem. A 106, 8531–8542 (2002)

    Google Scholar 

  23. S.P. McGlynn, T. Azumi, M. Kinoshita, Molecular Spectroscopy of the Triplet State (Prentice-Hall, Inc., Englewood Cliffs, 1969)

    Google Scholar 

  24. S.K. Wong, D.A. Hutchison, J.K.S. Wan, J. Am. Chem. Soc. 95, 622 (1973)

    Article  Google Scholar 

  25. M.S. De Groot, I.A.M. Hesselmann, J.H. van der Waals, Mol. Phys. 12, 259 (1967)

    Article  ADS  Google Scholar 

  26. K.M. Salikhov, YuN Molin, R.Z. Sagdeev, A.L. Buchachenko, Spin Polarization and Magnetic Effect in Radical Reactions (Elsevier, Amsterdam, 1984)

    Google Scholar 

  27. E.A. Mikhalitsyna, V.S. Tyurin, S.E. Nefedov, S.A. Syrbu, A.S. Semeikin, O.I. Koifman, I.P. Beletskaya, Eur. J. Inorg. Chem. 36, 5979 (2012)

    Article  Google Scholar 

  28. T. Maly, T.F. Prisner, J. Magn. Reson. 170, 88–96 (2004)

    Article  ADS  Google Scholar 

  29. S. Stoll, A. Schweiger, J. Magn. Reson. 178(1), 42–55 (2006)

    Article  ADS  Google Scholar 

  30. R. Kaptein, L.J. Oosterhoff, Chem. Phys. Lett. 4, 195 (1969)

    Article  ADS  Google Scholar 

  31. C. Blaetter, F. Jent, H. Paul, Chem. Phys. Lett. 166, 375(1990)

  32. A. Carrington, A.D. McLachlan, Introduction to Magnetic Resonance with Applications to Chemistry and Chemical Physics (Harper and Row, New York, 1967)

    Google Scholar 

  33. К.M. Salikhov, Appl. Magn. Reson. 26, 135–144 (2004)

    Article  Google Scholar 

  34. O.I. Gnezdilov, A.E. Mambetov, A.A. Obynochny, K.M. Salikhov, Appl. Magn. Reson. 25, 157–198 (2003)

    Article  Google Scholar 

  35. A. Abragam, Nuclear Magnetism (Oxford at the Clarendon Press. Ch.VIII, Eqs. (VIII.128, VIII.128a), 1961)

  36. K.M. Salikhov, Appl. Magn. Reson. 38(2), 237–256 (2010)

    Article  Google Scholar 

  37. M. Mazzoni, F. Conti, C. Corvaja, Appl. Magn. Reson. 18, 351–362 (2000)

  38. K.M. Salikhov, A. van der Est, D. Stehlik, Appl. Magn. Reson. 16, 101–134 (1999)

    Article  Google Scholar 

  39. V.S. Iyudin, YuE Kandrashkin, V.K. Voronkova, V.S. Tyurin, E.N. Kirichenko, Appl. Magn. Reson. 40, 75–89 (2011)

    Article  Google Scholar 

  40. D. Gatteschi, A. Bencini, Electron Paramagnetic Resonance of Exchange Coupled Systems (Springer, Berlin, 1990)

    Google Scholar 

  41. Yu.V. Yablokov, V.K. Voronkova, L.V. Mosina, Paramagnetic Resonance of Exchange Clusters (Nauka, Moscow, 1988)

    Google Scholar 

  42. M. Asano-Someda, N. Toyama, Y. Kaizu, Appl. Magn. Reson. 23, 393–407 (2003)

    Article  Google Scholar 

  43. C.W.M. Kay, G. Elger, K. Möbius, Phys. Chem. Chem. Phys. 1, 3999–4002 (1999)

    Article  Google Scholar 

  44. A. Schweiger, G. Jeschke, Principles of Pulse Electron Paramagnetic Resonance (Oxford University Press, Oxford, 2001)

    Google Scholar 

Download references

Acknowledgments

We are grateful to Professor Art van der Est for the comments. This work was supported in part by the Russian Foundation for Basic Research (project no. 12-03-97078-p), the Government of the Republic of Tatarstan and the Division of Physical Sciences, Russian Academy of Sciences (II.4) and the President of the Russian Federation “Leading scientific schools” (project no. NSh-4653.2014.2).

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Authors and Affiliations

  1. Zavoisky Physical-Technical Institute, Russian Academy of Sciences, Sibirsky trakt 10/7, 420029, Kazan, Russia

    A. A. Sukhanov, K. B. Konov, K. M. Salikhov & V. K. Voronkova

  2. A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky prospect 31-4, 119071, Moscow, Russia

    E. A. Mikhalitsyna & V. S. Tyurin

Authors
  1. A. A. Sukhanov
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  2. K. B. Konov
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  3. K. M. Salikhov
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  4. V. K. Voronkova
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  5. E. A. Mikhalitsyna
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  6. V. S. Tyurin
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Correspondence to V. K. Voronkova.

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Sukhanov, A.A., Konov, K.B., Salikhov, K.M. et al. Time-Resolved Continuous-Wave and Pulse EPR Investigation of Photoinduced States of Zinc Porphyrin Linked with an Ethylenediamine Copper Complex. Appl Magn Reson 46, 1199–1220 (2015). https://doi.org/10.1007/s00723-015-0705-0

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  • DOI: https://doi.org/10.1007/s00723-015-0705-0

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