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Large magnetic anisotropy of chromium(III) ions in a bis(ethylenedithio)tetrathiafulvalenium salt of chromium bis(dicarbollide), (ET)2[3,3′-Cr(1,2-C2B9H11)2]

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Abstract

The synthesis of a radical-cation salt based on a derivative of tetrathiafulvalene, (ET)2[3,3′-Cr(1,2-C2B9H11)2] (ET = bis(ethylenedithio)tetrathiafulvalenium), was accomplished by electrochemical anodic oxidation of ET in the presence of (Me4N)[3,3´-Cr(1,2-C2B9H11)2] in the galvanostatic regime. An electric conductivity σ (293 K) = 7 × 10−3 Ohm−1 cm−1 with semiconductor activation energy Ea ≅ 0.1 eV in the range of 127–300 K was observed. The crystal structure of (ET)2[3,3′-Cr(1,2-C2B9H11)2] was determined by X-ray diffraction at 173 K, revealing the presence of structural tetramers in radical-cation stacks. The magnetic properties of the complex were investigated in the temperature range 1.8–300 K using magnetometry and EPR, showing that the magnetic structure of (ET)2[3,3′-Cr(1,2-C2B9H11)2] consists of two independent magnetic subsystems. Cation radicals form a rectangular magnetic lattice in the ab-plane with significant antiferromagnetic exchange interactions. The chromium bis(dicarbollide) anions are characterized by unusually strong positive zero-field splitting of the Cr(III) ions, which was confirmed by ab initio calculations.

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References

  1. Yan YK, Mingos DMP (1995) Chem Soc Rev 24:203–213

    Article  CAS  Google Scholar 

  2. Bregadze VI, Dyachenko OA, Kazheva ON, Kravchenko AV, Sivaev IB, Starodub VA (2015) CrystEngComm 17:4754–4767

    Article  CAS  Google Scholar 

  3. Hosmane NS, Maguire JA (2003) Eur J Inorg Chem 22:3989–3999

    Article  CAS  Google Scholar 

  4. Yan Y-K, Mingos DMP, Williams DJ, Kurmoo M (1995) J Chem Soc Dalton Trans 19:3221–3230

    Article  Google Scholar 

  5. Ruhle HW, Hawthorne MF (1968) Inorg Chem 7:2279–2282

    Article  CAS  Google Scholar 

  6. Sheldrick GM (2008) Acta Crystallogr A 64:112–122

    Article  CAS  PubMed  Google Scholar 

  7. Sheldrick GM (2015) Acta Crystallogr C 71:3–8

    Article  CAS  Google Scholar 

  8. APEX2 Software Package (2005) Bruker AXS. APEX2 Software Package, Madison

    Google Scholar 

  9. Neese F (2017) WIREs Comput Mol Sci 8:e1327

    Article  Google Scholar 

  10. Neese F, ORCA—An Ab Initio, DFT and SCF-MO Program Package, Version 4.0.1

  11. Atanasov M, Ganyushin D, Pantazis DA, Sivalingam K, Neese F (2011) Inorg Chem 50:7460–7477

    Article  CAS  PubMed  Google Scholar 

  12. Angeli C, Borini S, Cestari M, Cimiraglia R (2007) J Chem Phys 121:4043–4049

    Article  CAS  Google Scholar 

  13. Angeli C, Cimiraglia R, Evangelisti S, Leininger T, Malrieu J-P (2001) J Chem Phys 114:10252–10264

    Article  CAS  Google Scholar 

  14. Angeli C, Cimiraglia R, Malrieu J-P (2002) J Chem Phys 117:9138–9153

    Article  CAS  Google Scholar 

  15. Neese F (2005) J Chem Phys 122:034107

    Article  CAS  Google Scholar 

  16. Ganyushin D, Neese F (2006) J Chem Phys 125:024103

    Article  CAS  Google Scholar 

  17. Neese F (2007) J Chem Phys 127:164112

    Article  CAS  PubMed  Google Scholar 

  18. Kazheva ON, Alexandrov GG, Kravchenko AV, Sivaev IB, Kosenko ID, Lobanova IA, Kajňaková M, Buravov LI, Bregadze VI, Feher A, Starodub VA, Dyachenko OA (2012) Inorg Chem Commun 15:106–108

    Article  CAS  Google Scholar 

  19. Butcher RT, Landee CP, Turnbull MM, Xiao F (2008) Inorg Chim Acta 361:3654–3658

    Article  CAS  Google Scholar 

  20. Keith BC, Landee CP, Valleau T, Turnbull MM, Harrison N (2011) Phys Rev B 84:104442

    Article  CAS  Google Scholar 

  21. Myers BE, Berger L, Friedberg S (1969) J Appl Phys 40:1149–1151

    Article  CAS  Google Scholar 

  22. O’Connor CJ (1982) Prog Inorg Chem 29:203–284

    Google Scholar 

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

    Article  CAS  PubMed  Google Scholar 

  24. Ballester L, Gutiérrez A, Perpiñán MF, Sánchez AE, Fonari M, Gdaniec M (2007) Inorg Chem 46:946–3955

    Article  CAS  Google Scholar 

  25. Williams JH, Ferraro JR, Thorn RJ, Carlson KD, Geiser U, Wang HH, Kini AM, Whangbo HM (1992) In Grimes RN (ed) Organic superconductors. synthesis, structure, properties, and theory, Prentice Hall, Englewood Cliffs

  26. Liu W, Christian JH, Al-Oweini R, Bassil BS, van Tol J, Atanasov M, Neese F, Dalal NS, Kortz U (2014) Inorg Chem 53:9274–9283

    Article  CAS  PubMed  Google Scholar 

  27. Miller JS, Drillon M (2006) Magnetism: molecules to materials V. Wiley-VCH Verlag GmbH & Co., Weinheim

    Google Scholar 

  28. Guo F-S, Day BM, Chen Y-C, Tong ML, Mansikkamäki A, Layfield RA (2017) Angew Chem Int Edit 56:11445–11449

    Article  CAS  Google Scholar 

  29. Singh V, Chakradhar RPS, Rao JL, Kim D-K (2009) J Lumin 129:130–134

    Article  CAS  Google Scholar 

  30. Godlewska P, Matraszek A, Kaczmarek SM, Fuks H, Skibiński T, Hermanowicz K, Ptak M, Szczygieł I, Macalik L, Lisiecki R, Ryba-Romanowski W, Hanuza J (2004) J Lumin 146:342–350

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Slovak Research and Development Agency under Contracts Nos. APVV-14-0073 and APVV-14-0078 and by ERDF EU projects under the Contract No. ITMS26220120047. A. V. Fedorchenko thanks P.J. Šafárik University for the opportunity to carry out research.

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Authors and Affiliations

  1. Institute of Physics, Faculty of Science, P. J. Šafárik University, Park Angelinum 9, 041 54, Košice, Slovakia

    Erik Čižmár, Daniela Šoltésová, Alexey V. Fedorchenko & Alexander Feher

  2. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432, Semenov av., 1, Chernogolovka, Moscow District, Russia

    Olga N. Kazheva, Lev I. Buravov & Oleg A. Dyachenko

  3. N.S. Kurnakov Institute of General and Inorganic Chemistry Russian Academy of Sciences, Leninskii av., 31, Moscow, Russia, 119991

    Grigorii G. Alexandrov

  4. V.N. Karazin, Kharkov National University, 4 Svobody Sq, Kharkiv, 61077, Ukraine

    Andrey V. Kravchenko

  5. A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Science, Vavilov Str. 28, Moscow, Russia, 119991

    Lyubov A. Chekulaeva, Irina D. Kosenko, Igor B. Sivaev & Vladimir I. Bregadze

  6. B. Verkin Institute for Low Temperature Physics and Engineering of NAS of Ukraine, Nauky av., 47, Kharkiv, Ukraine

    Alexey V. Fedorchenko

  7. Institute of Chemistry, Jan Kochanowski University, 15 G Świętokrzyska str., 25-406, Kielce, Poland

    Vladimir A. Starodub

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  1. Erik Čižmár
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  2. Daniela Šoltésová
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  3. Olga N. Kazheva
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  4. Grigorii G. Alexandrov
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  5. Andrey V. Kravchenko
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  6. Lyubov A. Chekulaeva
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  7. Irina D. Kosenko
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  8. Igor B. Sivaev
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  9. Vladimir I. Bregadze
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  10. Alexey V. Fedorchenko
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  11. Vladimir A. Starodub
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  12. Lev I. Buravov
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  13. Oleg A. Dyachenko
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  14. Alexander Feher
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Correspondence to Erik Čižmár.

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Čižmár, E., Šoltésová, D., Kazheva, O.N. et al. Large magnetic anisotropy of chromium(III) ions in a bis(ethylenedithio)tetrathiafulvalenium salt of chromium bis(dicarbollide), (ET)2[3,3′-Cr(1,2-C2B9H11)2]. Transit Met Chem 43, 647–655 (2018). https://doi.org/10.1007/s11243-018-0253-1

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  • DOI: https://doi.org/10.1007/s11243-018-0253-1

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