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Magnetic properties of electrochemically prepared crystalline films of Prussian blue-based molecular magnets K j CrII k [CrIII(CN)6] l  · mH2O

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Abstract

Crystalline films (thickness ∼1 μm) of Prussian blue-based molecular magnets, synthesized using electrochemical method at two different reduction potentials −0.5 and −0.9 V, result into K0.1CrII 1.45[CrIII(CN)6] · mH2O (film 1) and K0.8CrII 1.1[CrIII(CN)6] · mH2O (film 2), respectively. The structural and magnetic properties of such films are investigated using atomic force microscopy (AFM), X-ray diffraction (XRD), infrared (IR) spectroscopy, and dc magnetization measurements. The film morphology, examined using AFM, shows uniformly distributed triangular crystallites over the substrate surface. The presence of CrIII–C≡N–CrII sequence, in the range of 1,900 to 2,300 cm−1 in IR spectra, confirms formation of Prussian blue analogues. The XRD results reveal information about the crystalline nature of the films and the relative intensities of the Bragg peaks change with the K+ ions. The exchange interaction between Cr ions through C≡N ligand confirms that the electron transfer from C≡N molecule to Cr ions is ferrimagnetic in nature. The high Curie temperatures (T C) are found to be ∼195 and ∼215 K for film 1 and film 2, respectively. The higher value of T C is attributed to the inclusion of more K+ ions for film 2, resulting decreases in the CrIII(C≡N)6 vacancies and increases in the number of nearest neighbors of CrII ions. The branching in the zero field-cooled and field-cooled magnetization data below Curie temperature is explained in terms of kinetic behavior of magnetic domains with different cooling conditions and the presence of water molecule vacancies in the lattice.

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References

  1. Sato O, Lyoda T, Fujishima A, Hashimoto K (1996) Photoinduced magnetization of a cobalt–iron cyanide. Science 272:704–705

    Article  CAS  Google Scholar 

  2. Shimamoto N, Ohkoshi S, Sato O, Hashimoto K (2002) Control of charge-transfer-induced spin transition temperature on cobalt−iron Prussian blue analogues. Inorg Chem 41:678–684

    Article  CAS  Google Scholar 

  3. Coronado E, Giménez-López MC, Korzeniak T, Levchenko G, Romero FM, Segura A, García-Baonza V, Cezar JC, de Groot FMF, Milner A, Paz-Pasternak M (2008) Pressure-induced magnetic switching and linkage isomerism in K0.4Fe4[Cr(CN)6]2.8 · 16H2O: X-ray absorption and magnetic circular dichroism studies. J Am Chem Soc 130:15519–15532

    Article  CAS  Google Scholar 

  4. Tokoro H, Ohkoshi S-i (2011) Novel magnetic functionalities of Prussian blue analogs. Dalton Trans 40:6825–6833

    Article  CAS  Google Scholar 

  5. Mallah T, Thiebaut S, Verdaguer M, Veillet P (1993) High-Tc molecular-based magnets: ferrimagnetic mixed-valence chromium(lil)-chromium(ll) cyanides with Tc at 240 and 190 Kelvin. Science 262:1554–1557

    Article  CAS  Google Scholar 

  6. Ferlay S, Mallah T, Ouhes R, Veillet P, Verdaguer M (1995) A room-temperature organometallic magnet based on Prussian blue. Nature 378:701–703

    Article  CAS  Google Scholar 

  7. Sato O, Lyoda T, Fujishima A, Hashimoto K (1996) Electrochemically tunable magnetic phase transition in a high-Tc chromium cyanide thin film. Science 271:49–51

    Article  CAS  Google Scholar 

  8. Sato O, Hayami S, Einaga Y, Gu Z-Z (2003) Control of the magnetic and optical properties in molecular compounds by electrochemical, photochemical and chemical methods. Bull Chem Soc Jpn 76:443–470

    Article  CAS  Google Scholar 

  9. Buschmann WE, Paulson SC, Wynn CM, Girtu MA, Epstein AJ, White HS, Miller JS (1998) Reversed (negative) magnetization for electrochemically deposited high-Tc thin films of chromium hexacyanide magnets. Chem Mater 10(5):1386–1395

    Article  CAS  Google Scholar 

  10. Coronado E, Makarewicz M, Prieto-Ruiz JP, Prima-García H, Romero FM (2011) Magneto-optical properties of electrodeposited thin films of the molecule-based magnet Cr5.5 (CN)12 · 11.5H2O. Adv Mater 23:4323–4326

    Article  CAS  Google Scholar 

  11. Nakanishi S, Lu G, Kothari HM, Bohannan EW, Switzer JA (2003) Epitaxial electrodeposition of Prussian blue thin films on single-crystal Au(110). J Am Chem Soc 125:14998–14999

    Article  CAS  Google Scholar 

  12. http://www.nanotec.es/products/wsxm/index.php.

  13. Horcas I, Fernandez R, Gomez-Rodriguez JM, Colchero J, Gomez-Herrero J, Baro AM (2007) WSXM: a software for scanning probe microscopy and a tool for nanotechnology. Rev Sci Instrum 78:013705–013712

    Article  CAS  Google Scholar 

  14. Bleuzen A, Lomenech C, Escax V, Villain F, Varret F, Cartier dit Moulin C, Verdaguer M (2000) Photoinduced ferrimagnetic systems in prussian blue analogues CIxCo4[Fe(CN)6]y (CI = alkali cation). 1. Conditions to observe the phenomenon. J Am Chem Soc 122(28):6648–6652

    Article  CAS  Google Scholar 

  15. Bhatt P, Yusuf SM, Mukadam MD, Yakhmi JV (2010) Enhancement of Curie temperature in electrochemically prepared crystalline thin films of Prussian blue analogs K j FeII k [CrIII(CN)6] l  ⋅ mH2O. J Appl Phys 108:023916–023921

    Article  Google Scholar 

  16. Rodriguez-Carvajal J FULLPROF, November 2007, website: http://www.ill.eu/sites/fullprof/.

  17. Nakamoto K (1997) Infrared and raman spectra of inorganic and coordination compounds. Part B: applications in coordination, organometallic and bioinorganic chemistry, 5th edn. Wiley-Interscience, New York

    Google Scholar 

  18. Kumar A, Yusuf SM, Keller L, Yakhmi JV, Srivastava JK, Paulose PL (2007) Variation of structural and magnetic properties with composition in the (CoxNi1−x)1.5[Fe(CN)6] • zH2O series. Phys Rev B 75:224419–224429

    Article  Google Scholar 

  19. Brown DB, Shriver DF, Schwartz LH (1968) Solid-state reactions of iron(II) hexacyanochromate(III). Inorg Chem 7:77–83

    Article  CAS  Google Scholar 

  20. Ohkoshi S-i, Lyoda T (1997) Magnetic properties of mixed ferro-ferrimagnets composed of Prussian blue analogs. Phys Rev B 56:11642–11652

    Article  CAS  Google Scholar 

  21. Mukadam MD, Kumar A, Yusuf SM, Yakhmi JV, Tewari R, Dey GK (2008) Spin-glass behavior in ferromagnetic Fe[Fe(CN)6] • xH2O nanoparticles. J Appl Phys 103:123902–123907

    Article  Google Scholar 

  22. Mukadam MD, Yusuf SM, Sharma P, Kulshreshtha SK, Dey GK (2005) Dynamics of spin clusters in amorphous Fe2O3. Phys Rev B 72:174408–174414

    Article  Google Scholar 

  23. Kosaka W, Tozawa M, Hashimoto K, Ohkoshi S-i (2006) Synthesis and superparamagnetic property of a Co–Cr Prussian blue analogue nanoparticles inside Nafion membrane. Inorg Chem Commun 9:920–922

    Article  CAS  Google Scholar 

  24. Catala L, Gloter A, Stephan O, Rogez G, Mallah T (2006) Superparamagnetic bimetallic cyanide-bridged coordination nanoparticles with TB = 9 K. Chem Commun (9) 1018-1020

  25. Kumar A, Yusuf SM, Keller L (2005) Structural and magnetic properties of FeFeCN6 · 4H2O. Phys Rev B 71:054414–054420

    Article  Google Scholar 

Download references

Acknowledgment

Authors would like to thank Mr. P. Jha for the IR measurements.

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Author notes

  1. Ranu Bhatt

    Present address: Technical Physics Division, Bhabha Atomic Research Center, Mumbai, 400 085, India

Authors and Affiliations

  1. Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai, 400 085, India

    Pramod Bhatt & S. M. Yusuf

  2. Max Planck Institute for Intelligent Systems (formerly Max Planck Institute for Metals Research), Heisenbergstr. 3, 70569, Stuttgart, Germany

    Ranu Bhatt & G. Schütz

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  1. Pramod Bhatt
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  2. S. M. Yusuf
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  3. Ranu Bhatt
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Correspondence to Pramod Bhatt.

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Bhatt, P., Yusuf, S.M., Bhatt, R. et al. Magnetic properties of electrochemically prepared crystalline films of Prussian blue-based molecular magnets K j CrII k [CrIII(CN)6] l  · mH2O. J Solid State Electrochem 17, 1285–1293 (2013). https://doi.org/10.1007/s10008-012-1995-x

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