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Phenazineoxonium chloranilatomanganate and chloranilatoferrate: synthesis, structure, magnetic properties, and Mössbauer spectra

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Abstract

Crystalline compounds (H3O)2(phz)3M2(C6O4Cl2)3·(CH3COCH3) n ·(H2O) n (n = 0−2, M = Mn (1), Fe (3)) were obtained in an acetone-water-tetrahydrofuran medium by the reaction of metal sulfates with chloranilic acid and phenazine (phz). The molecular and crystal structure of 1 was studied by X-ray diffraction at 300, 200, and 150 K. The crystal structure is composed of polymeric cationic [(H3O)2(phz)3] n 2n+ and anionic [Mn2(C6O4Cl2)3] n 2n− layers having honeycomb structure and stacked in such a way that open-ended through-going channels accommodating H2O and CH3COCH3 solvent molecules are formed; the H3O+ cations in the crystal structure are disordered. Magnetic studies indicate antiferromagnetic coupling of Mn2+ ions through chloranilate ligands; transition to a magnetically ordered state occurs at T = 5 K. According to powder X-ray diffraction data, complex 3 is isostructural with compound 1 but differs crucially from 1 in the electronic structure. According to Fe57 Mössbauer spectroscopy, complex 3 exists in delocalized mixed-valence Fe2+/Fe3+ state and, as a consequence, shows ferromagnetic character of magnetic correlations and semiconductor type of electrical conductivity. These features were ascribed to the valence tautomerism Fe2+ + (C6O4Cl2)2− → Fe3+ + (C6O4Cl2)·3−, which was observed for the first time for iron in a honeycomb structure.

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References

  1. V. I. Ovcharenko, R. Z. Sagdeev, Usp. Khim., 1999, 68, 381 [Russ. Chem. Rev. (Engl. Transl.), 1999, 68].

    Google Scholar 

  2. Z. J. Zhong, N. Matsumoto, H. Okawa, S. Kida, Chem. Lett., 1990, 87.

  3. H. Tamaki, M. Mitsumi, K. Nakamura, N. Matsumoto, S. Kida, H. Okawa, S. Ijima, Chem. Lett., 1992, 1975.

  4. H. Tamaki, Z.J. Zhong, N. Matsumoto, S. Kida, M. Koikawa, N. Achiva, Y. Nachimoto, H. Okawa, J. Am. Chem. Soc., 1992, 114, 6974.

    Article  CAS  Google Scholar 

  5. L. O. Atovmyan, G. V. Shilov, R. N. Lyubovskaya, E. I. Zhilyaeva, N. S. Ovanesyan, S. I. Pirumova, I. G. Gusakovskaya, Pis’ma v Zh. Eksp. Teor. Fiz., 1993, 58, 818 [JETP Lett. (Engl. Transl.), 1993, 58, 766].

    CAS  Google Scholar 

  6. C. Mathoniere, S. G. Carling, Y. Dou, P. Day, Chem. Commun., 1994, 1551.

  7. C. Mathoniere, C. J. Nutall, S. G. Carling, P. Day, Inorg. Chem., 1996, 35, 1201.

    Article  CAS  Google Scholar 

  8. N. S. Ovanesyan, G. V. Shilov, L. O. Atovmyan, R. N. Lyubovskaya, A. A. Pyalling, Mol. Cryst. Liq. Cryst., 1995, 273, 175.

    Article  Google Scholar 

  9. S. Decurtins, H. W. Schmalle, P. Schneuly, J. Ensling, P. Gutlich, J. Am. Chem. Soc., 1994, 116, 9521.

    Article  CAS  Google Scholar 

  10. E. Coronado, J. R. Galan-Mascaros, C. G. Gomez-Garcia, E. Martinez-Ferrero, M. Almeida, Eur. J. Inorg. Chem., 2005, 2064.

  11. S. Benard, P. Yu, J. P. Audiere, E. Riviere, R. Clement, J. Guilhem, L. Tchertanov, K. Nakatani, J. Am. Chem. Soc., 2000, 122, 9444.

    Article  CAS  Google Scholar 

  12. E. Coronado, J. R. Galan-Mascaros., C. J. Gomez-Garcia, V. Laukhin, Nature (London), 2000, 408, 447.

    Article  CAS  Google Scholar 

  13. M. Gruselle, C. Train, K. Boubekeur, P. Gredin, N. S. Ovanesyan, Coord. Chem. Rev., 2006, 250, 2491.

    Article  CAS  Google Scholar 

  14. S. M. Aldoshin, L. A. Nikonova, G. V. Shilov, E. A. Bikanina, N. K. Artemova, V. A. Smirnov, Mol. Struct., 2006, 794, 103.

    Article  CAS  Google Scholar 

  15. C. G. Pierpont, L. C. Francesconi, D. H. Hendickson, Inorg. Chem., 1977, 16, 2367.

    Article  CAS  Google Scholar 

  16. D. F. Xiang, C. Y. Duan, X. S. Tan, Y. J. Liu, W. X. Tang, Polyhedron, 1998, 17, 2647.

    Article  CAS  Google Scholar 

  17. M. Kawahara, M. K. Kabir, K. Yamada, K. Adachi, H. Kumagai, Y. Narumi, K. Kindo, S. Kitagawa, S. Kawata, Inorg. Chem., 2004, 43, 92.

    Article  CAS  Google Scholar 

  18. A. Dei, D. Gatteschi, L. Pardi, U. Russo, Inorg. Chem., 1991, 30, 2589.

    Article  CAS  Google Scholar 

  19. K. S. Min, A. G. DiPasquale, J. A. Golen, A. L. Rheingold, J. S. Miller, J. Am. Chem. Soc., 2007, 129, 2360.

    Article  CAS  Google Scholar 

  20. J. T. Wrobleski, D. B. Brown, Inorg. Chem., 1979, 18, 498.

    Article  CAS  Google Scholar 

  21. S. Kawata, S. Kitagawa, H. Kumagai, T. Ishiyama, K. Honda, H. Tobita, K. Adachi, M. Katada, Chem. Mater., 1998, 10, 3902.

    Article  CAS  Google Scholar 

  22. B. F. Abrahams, K. D. Lu, B. Moubaraki, K. S. Murray, R. Robson, J. Chem. Soc., Dalton Trans., 2000, 1793.

  23. S. Kawata, S. Kitagawa, I. Furuchi, C. Kudo, H. Kamesaki, M. Kondo, M. Katada, M. Munakata, Mol. Cryst. Liq. Cryst., 1995, 274, 179.

    Article  Google Scholar 

  24. S. Kawata, S. Kitagawa, M. Kondo, I. Furuchi, M. Munakata, Angew. Chem., Int. Ed., 1994, 33, 1759.

    Article  Google Scholar 

  25. H. Kumagai, S. Kawata, S. Kitagawa, Inorg. Chim. Acta, 2002, 337, 387.

    Article  CAS  Google Scholar 

  26. M. K. Kabir, M. Kawahara, H. Kumagai, K. Adachi, S. Kawata, T. Ishii, S. Kitagawa, Polyhedron, 2001, 20, 1417.

    Article  CAS  Google Scholar 

  27. S. Kawata, S. Kitagawa, H. Kumagai, C. Kudo, H. Kamaesaki, T. Ishiyama, R. Suzuki, M. Kondo, M. Katada, Inorg. Chem., 1996, 35, 4449.

    Article  CAS  Google Scholar 

  28. M. K. Kabir, S. Kawata, K. Adachi, H. Tobita. N. Miyazaki, H. Kumagai, M. Katada, S. Kitagawa, Mol. Cryst. Liq. Cryst., 2000, 341, 491.

    Article  CAS  Google Scholar 

  29. K. Nagayoshi, M. D. Kabir, H. Tobita, K. Honga, M. Kawahara, M. Katada, K. Adachi, H. Nishikawa, I. Ikemoto, H. Kumagai, Y. Hosokoshi, K. Inoue, S. Kitagawa, S. Kawata, J. Am. Chem. Soc., 2003, 125, 221.

    Article  CAS  Google Scholar 

  30. Tzuoo-Tsair Luo, Yen-Hsiang Liu, Hui-Lien Tsai, ChanCheng Su, Chuen-Her Ueng, Kuang-Lieh Lu, Eur. J. Inorg. Chem., 2004, 4253.

  31. P. E. Riley, S. F. Haddad, K. N. Raymond, Inorg. Chem., 1983, 22, 3090.

    Article  CAS  Google Scholar 

  32. B. F. Abrahams, J. Coleiro, K. Ha, B. F. Hoskins, S. D. Orehard, R. Robson, J. Chem. Soc., Dalton Trans., 2002, 1586.

  33. Z. K. Nikitina, V. D. Makhaev, N. S. Ovanesyan, G. V. Shilov, S. M. Aldoshin, Int. Conf. Organometallic and Coord Chem. (Russia, N. Novgorod, 2008, 2–8 September), Book of Abstracts, N. Novgorod, 2008, 74.

  34. Z. K. Nikitina, N. S. Ovanesyan, V. D. Makhaev, G. V. Shilov, S. M. Aldoshin, Dokl. Akad. Nauk, 2011, 437, 778 [Dokl. Chem. (Engl. Transl.), 2011, 437, Pt. 2, 129].

    Google Scholar 

  35. G. M. Sheldrick, SHELXTL v. 6.14, Structure Determination Software Suite, Bruker AXS, Madison, Wisconsin, USA, 2000.

    Google Scholar 

  36. K. P. Butin, E. K. Beloglazkina, N. V. Zyk, Usp. Khim., 2005, 74, 585 [Russ. Chem. Rev. (Engl. Transl.), 2005, 74].

    Google Scholar 

  37. K. S. Min, A. L. Reingold, J. S. Miller, J. Am. Chem. Soc., 2006, 128, 40.

    Article  CAS  Google Scholar 

  38. X.-Q. Ding, E. L. Bominar, E. Bill, H. Winkler, A. X. Trautwein, S. Drueke, P. Chaudhuri, K. Wieghardt, J. Chem. Phys., 1990, 92, 178.

    Article  CAS  Google Scholar 

  39. D. Lee, C. Krebs, B. H. Huynh, M. P. Hendrich, S. J. Lippard, J. Am. Chem. Soc., 2000, 122, 5000.

    Article  CAS  Google Scholar 

  40. X.-Q. Ding, E. Bill, A. X. Trautwein, H. Winkler, A. Kostikas, V. Papaefthymiou, A. Simopoulos, P. Beardwood, J. F. Gibson, Chem. Phys., 1993, 99, 6421.

    CAS  Google Scholar 

  41. C. Zener, Phys. Rev., 1951, 81, 403.

    Article  Google Scholar 

  42. P. W. Anderson, H. Hasegawa, Phys. Rev., 1955, 100, 675.

    Article  CAS  Google Scholar 

  43. G. H. Jonker, J. H. Van Santen, Physica, 1950, 16, 599.

    Article  Google Scholar 

  44. J. S. Miller, K. S. Min, Angew. Chem., Int. Ed., 2008, 47, 2.

    Article  Google Scholar 

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 prosp. Akad. Semenova, 142432, Chernogolovka, Moscow Region, Russian Federation

    G. V. Shilov, Z. K. Nikitina, N. S. Ovanesyan, S. M. Aldoshin & V. D. Makhaev

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  1. G. V. Shilov
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  2. Z. K. Nikitina
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  3. N. S. Ovanesyan
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  4. S. M. Aldoshin
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  5. V. D. Makhaev
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Correspondence to G. V. Shilov.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1183–1193, June, 2011.

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Shilov, G.V., Nikitina, Z.K., Ovanesyan, N.S. et al. Phenazineoxonium chloranilatomanganate and chloranilatoferrate: synthesis, structure, magnetic properties, and Mössbauer spectra. Russ Chem Bull 60, 1209–1219 (2011). https://doi.org/10.1007/s11172-011-0190-z

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  • DOI: https://doi.org/10.1007/s11172-011-0190-z

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