journal of

physics

PRAMANA

c Indian Academy of Sciences

Vol. 63, No. 2 August 2004 pp. 239244

Magnetic structure of molecular magnet Fe[Fe(CN)6 ]4H2 O

AMIT KUMAR and S M YUSUF
Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085, India Corresponding author E-mail: [email protected] Abstract. We have studied the magnetic structure of Fe[Fe(CN)6 ]4H2 O, prepared by precipitation method, using neutron diraction technique. Temperature dependent DC magnetization study down to 4.2 K shows that the compound undergoes from a high temperature disordered (paramagnetic) to an ordered magnetic phase transition at 22.6 K. Rietveld analysis of neutron diraction pattern at 60 K (in its paramagnetic phase) revealed a face centred cubic structure with space group Fm3m. The structure contains three-dimensional network of straight Fe3+ CNFe3+ chains along the edges of the unit cell cube. Fe3+ ions occupy 4a (0, 0, 0) and 4b (1/2, 1/2, 1/2) positions. Fe3+ (0, 0, 0) is surrounded octahedrally by six nitrogen atoms and Fe3+ (1/2, 1/2, 1/2) is surrounded octahedrally by six carbon atoms. Magnetic Rietveld renement of neutron diraction data at 11 K shows a ferromagnetic coupling between the two inequivalent Fe 3+ sites. Renement yielded an ordered moment of 4.4(6) and 0.8(6) B per Fe ion located at (0, 0, 0) and (1/2, 1/2, 1/2), respectively. Ordered moments are found to align along the face diagonal. The observed net moment from low temperature neutron diraction study is consistent with DC magnetization results. Keywords. Molecular magnet; neutron diraction; DC magnetization; ferromagnet. PACS Nos 75.50.Xx; 61.12.Ld; 75.50.Dd

1. Introduction Molecular magnetic materials [1] are the subject of an active research in recent years because of their possible applications in future information processing and storing devices. Prussian Blue [2] analogues represented by the general formula, An [B(CN)6 ]m xH2 O [38] where A and B are transition metals, are one of the most promising candidates in this regard [911]. One of the salient features of these materials is the easy route for their synthesis. These materials can be prepared by mild chemistry methods at room temperature e.g. co-precipitation method. An easy control of their magnetic properties like transition temperature, saturation magnetization, coercive eld etc., is possible simply by changing the concentration of magnetic ions [11] or by replacing a magnetic ion by another magnetic ion [48].

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Amit Kumar and S M Yusuf Ferri-ferricyanide, Fe[Fe(CN)6 ]xH2 O, is one of the basic compounds in the Prussian Blue family. Bozorth et al [12] reported the results of DC magnetization study on the ferri-ferricyanide (TC = 22 K, saturation magnetization = 3.8 B per (CN)6 ). But their evidences suggested that the sample had contained some impure phase and the correct composition of ferri-ferricyanide was not known. However, ferri-ferricyanide being one of the important basic compounds in the Prussian Blue family, it is very much essential to know the chemical structure and the true nature of magnetic ordering in this compound. With this motivation, we have prepared single-phase ferri-ferricyanide and studied by DC magnetization and neutron diraction techniques. Neutron diraction, being a microscopic technique, can measure the magnitude and direction of site moments in ordered ferri-ferricyanide molecular magnet and hence unveils its microscopic magnetic structure. In this paper we report the chemical and magnetic structure of ferriferricyanide, Fe[Fe(CN)6 ]xH2 O. Here, for the rst time by using neutron diraction technique, we have shown the existence of low-spin and high-spin Fe 3+ ions in Fe[Fe(CN)6 ]xH2 O. 2. Experimental Ferri-ferricyanide was prepared by the co-precipitation method. In this method 100 ml 0.1 M K3 Fe(CN)6 aqueous solution was slowly added to 200 ml 0.1 M FeCl3 aqueous solution and the resulting solution was heated up to 53 C. Hot solution was allowed to cool at room temperature and diluted to double of its initial volume after cooling. Dark green precipitate, so obtained, was ltered, washed many times with demineralized water and acetone and nally allowed to dry in air. The sample was ground to very ne powder. Neutron diraction pattern of the prepared polycrystalline sample was recorded using a 1-D position sensitive detector based neutron powder diractometer ( = 1.249 ) at Dhruva reactor, Trombay. For low temperA ature measurements the sample was mounted in a closed cycle helium refrigerator with lowest possible temperature of 11 K. DC magnetization measurements were carried out using a vibrating sample magnetometer (Oxford Instruments model) as a function of temperature and magnetic eld. 3. Results and discussion Figure 1 shows the neutron diraction pattern of the prepared polycrystalline sample at 60 K. The diraction pattern was analysed by Rietveld renement technique using FULLPROF program [13]. The pattern could be indexed with the Fm3m space group. Starting values for the positions of carbon, nitrogen and water molecules were taken from ref. [2]. Owing to the high background and limitations of powder diraction, we treated water molecules as pseudoatoms {H2 O} with an average scattering length b(H2 O) = b(O) + 2b(H) = 1.68 fm. In our renement the best tting was achieved by taking four water molecules per formula unit. Results of the analysis are listed in table 1. The distances between various atoms A A obtained from the analysis are Fe1 N = 2.003(6) , Fe2 C = 1.941(6) , CN =

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Magnetic structure of molecular magnet Fe[Fe(CN)6 ]4H2 O

Figure 1. Observed and tted neutron diraction patterns and their dierence at 60 K. Open circles: observed data; solid line: Rietveld tted curve; short vertical lines: position of Bragg peaks.

1.16(2) , Fe1 Fe2 = a/2 = 5.1095(5) and Fe1 Fe1 = Fe2 Fe2 = a = 10.219(1) A A , where Fe1 and Fe2 are Fe3+ ions at (0, 0, 0) and (1/2, 1/2, 1/2), respectively A (see table 1). The calculated values of interatomic distances are close to the values reported for the parent Prussian Blue compound, Fe4 [Fe(CN)6 ]3 14H2 O [2]. Structure of the ferri-ferricyanide contains three-dimensional network of Fe 1 NCFe2 chains along the edges of the unit cell cube. The four water molecules present in the formula unit are uncoordinated and may be considered as zeolitic water. Fe1 and Fe2 are surrounded octahedrally by N and C atoms, respectively. Octahedral crystalline eld splits the 3d orbitals of Fe3+ (d5 ) ion into low energy t2g (dxy , dyz , dzx ) and high energy eg (dz2 , d(x2y2) ) orbitals. It is evident from the interatomic distances that nitrogen octahedra is slightly bigger (3%) than the carbon octahedra. It is, therefore, expected that Fe2 should be aected by a stronger ligand eld than Fe1 . The ligand eld inuences the spin conguration of the Fe3+ ions directly.
Table 1. Structural parameters of Fe[Fe(CN)6 ]4H2 O at 60 K. Space group = Fm3m, a = 10.219(1) , Z = 4 A Atoms Fe1 Fe2 C N {H2 O} {H2 O} x y z p 1 1 6 6 2 2 B ( 2 ) A 0.5(1) 0.5(1) 1.6(2) 1.6(2) 18(1) 18(1)

0 0 0 1/2 1/2 1/2 0.310(1) 0 0 0.196(1) 0 0 1/4 1/4 1/4 0.331(9) 0.331(9) 0.331(9) Rp = 1.82%, Rwp = 2.46%, Rexp = 2.27% p = occupancy, B = temperature factor

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Figure 2. DC vs. T curve at 200 Oe eld and virgin DC magnetization curves at 10 and 2.3 K.

Figure 3. Observed and Rietveld rened (magnetic) neutron diraction patterns at 11 K.

Figure 2 shows the DC susceptibility vs. temperature curve and virgin magnetization curves for the ferri-ferricyanide. The compound undergoes a disorder (paramagnetic) to ordered magnetic phase transition at 22.6 K. Magnetization at 2.3 K under 50 kOe eld was found to be 5.8 B per formula unit. Assuming high spin (S = 5/2) for Fe3+ at (0, 0, 0) and low spin (S = 1/2) for Fe3+ at (1/2, 1/2, 1/2), the theoretically expected spin only ordered moment value is 6 B per formula unit for parallel ordering between the two Fe3+ ions. In order to measure the site moments we carried out the magnetic renement of low temperature neutron diraction pattern. Figure 3 shows the diraction pattern of ferri-ferricyanide at 11 K. This pattern is similar to pattern at 60 K except some intensity enhancement in low-angle Bragg peaks (table 2) indicating ferro or ferrimagnetic type ordering. Renement of 60 and 11 K data did not give any evidence of structural phase transition between

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Magnetic structure of molecular magnet Fe[Fe(CN)6 ]4H2 O

Table 2. Observed integrated intensities at 60 and 11 K for the rst few Bragg reections and their dierences showing magnetic contributions. (h k l) 111 200 311 222 400 331 2 ( ) 12.15 14.04 23.38 24.44 28.29 30.89 I60
K

I11

I11

K I60 K

3 2648 6 711 1202 27

92 2789 35 741 1230 51

89 141 29 30 28 24

60 and 11 K. From magnetic renement we obtained 4.4(6) B moment for Fe3+ at (0, 0, 0) and 0.8(6) B moment for Fe3+ at (1/2, 1/2, 1/2). The theoretically expected values of ordered moments for high-spin and low-spin Fe3+ are 5 and 1 B , respectively. The neutron diraction study, therefore, conrms the existence of high-spin Fe3+ at (0, 0, 0) and low-spin Fe3+ at (1/2, 1/2, 1/2) which is due to the inuence of ligand elds on the splitting of 3d orbitals of Fe3+ ions. The net moment derived from the renement was 5.2 B per formula unit. This is close to the magnetization value 5.24 B at 10 K under 50 kOe eld, obtained from DC magnetization data (gure 2). The observed moments are found to align along the face diagonals. The present study also indicates the total quenching of orbital moments. 4. Conclusions Ferri-ferricyanide, Fe[Fe(CN)6 ]4H2 O possesses a fcc structure with space group Fm3m. There exists straight chain of atoms containing Fe3+ CNFe3+ along the edges of the unit cell cube. Fe3+ ion at (0, 0, 0) is surrounded octahedrally by N atoms and Fe3+ at (1/2, 1/2, 1/2) is surrounded by C octahedra. The compound undergoes a paramagnetic to ferromagnetic transition at 22.6 K. Magnetic renement of 11 K neutron diraction data yielded 4.4(6) B and 0.8(6) B ordered moments for Fe3+ ions at (0, 0, 0) and (1/2, 1/2, 1/2), respectively. The moments are found to align along the face diagonals. The net magnetic moment extracted from the magnetic renement of 11 K neutron diraction data agrees well with DC magnetization results. Present study conrms the ferromagnetic ordering between high-spin Fe3+ (S = 5/2) and low-spin Fe3+ (S = 1/2) ions.

References
[1] [2] [3] [4] [5] O Kahn, Molecular magnetism (VCH, New York, 1993) Herren et al, Inorg. Chem. 19, 956 (1980) J V Yakhmi, Physica B321, 204 (2002) S Ferlay et al, Nature 378, 701 (1995) O Sato et al, Science 271, 49 (1996)

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[6] [7] [8] [9] [10] [11] [12] [13] V Gadet et al, J. Am. Chem. Soc. 114, 9213 (1992) W R Entley et al, Inorg. Chem. 33, 5165 (1994) M Verdaguer et al, Coordination Chem. Rev. 190192, 1023 (1999) S Ohkoshi et al, Phys. Rev. Lett. 82, 1285 (1999) S Ohkoshi et al, Appl. Phys. Lett. 70, 1040 (1997) S Ohkoshi et al, Phys. Rev. B56, 11642 (1997) R M Bozorth et al, Phys. Rev. 103, 572 (1956) J Rodriguez-Carvajal, FULLPROF version 3.0.0, LLB CEA-CNRS (1995)

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