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DOI: 10.1002/ejic.201101220

Functional Heterometallic Layered Hybrid Magnets by Double Ion-Exchange

Emilie Delahaye,[a][] Sraphin Eyele-Mezui,[a] Mayoro Diop,[a] Cdric Leuvrey,[a] Dominique Foix,[b] Danielle Gonbeau,[b] Pierre Rabu,*[a] and Guillaume Rogez*[a]
Keywords: Salen / Hybrid materials / Ion exchange / Layered simple hydroxides / Magnetic properties / Transition metals
New hybrid compounds have been synthesized by functionalization of cobalt and copper layered hydroxides by salen complexes. Two kinds of compounds have been obtained from [M(SalenSO3Na2)] (M = Cu2+, Ni2+, Co2+ and Zn2+) and the preintercalated copper and cobalt hydroxides Cu2(OH)3(DS) and Co2(OH)3(DS0) [SalenSO3Na2 = N,N-bis(5-sulfonatosalicylidene)-1,2-diaminoethane disodium salt, DS = dodecylsulfate, DS0 = dodecylsulfonate]. The reaction of [M(SalenSO3Na2)] with layered copper hydroxide led to the anion-exchanged compounds Cu2(OH)3.00(CuSalenSO3)0.50 0.20H2O [Cu(SalenSO3)Cu (1)] and Cu2(OH)3.24(NiSalenSO3)0.382.6H2O [Ni(SalenSO3)Cu (2)] where M = Cu2+ or Ni2+. Similarly, the reaction with layered cobalt hydroxide leads to the exchanged compounds Co2(OH)3.18(NiSalenSO3)0.414.0H2O [Ni(SalenSO3)Co (6)] and Co2(OH)3.44(CoSalenSO3)0.283.7H2O [Co(SalenSO3)Co (8)] where M = Ni2+ or Co2+. The reaction of [M(SalenSO3)Na2] with layered copper hydroxide where M = Co2+ or Zn2+ and that of layered cobalt hydroxide where M = Cu2+ or Zn2+ resulted in the modification of the host structure because of concomitant partial cation exchange between the salen complex and the inorganic layers. Mixed-ion-exchanged compounds were obtained, Cu1.16Co0.84(OH)3.28(CoSalenSO3)0.366.4H2O [Co(SalenSO3)Cu/Co (4)], Cu0.7Zn1.30(OH)3.20(ZnSalenSO3)0.40 2.11H2O [Zn(SalenSO3)Cu/Zn (3)], Co1.72Cu0.28(OH)3.28(CuSalenSO3)0.363.20H2O [Cu(SalenSO3)Co/Cu (5)] and Co0.80Zn1.20(OH)3.20(ZnSalenSO)0.402.25H2O [Zn(SalenSO3)Co/Zn (7)]. The magnetic behaviour of the compounds is drastically modified depending on the structure of the inorganic layers induced by the functionalization and partial cation exchange. The hybrid copper layered hydroxides show antiferromagnetic (for 3) or weak ferromagnetic (for 1, 2 and 4) behaviour. The cobalt analogues 5, 6 and 8 are ferrimagnets with ordering temperatures at ca. 6 K, whereas the Co/ Zn heterometallic layered simple hydroxide 7 presents dominant antiferromagnetic interactions.

Introduction
The synthesis of organicinorganic functional heterostructures is one of the most efficient ways to obtain multifunctional compounds.[1] The properties of such systems result from the addition of the properties of their components, and synergy effects are expected to lead to tailormade applications and new devices. Various functional building blocks can be imagined to design hybrid materials, and it is necessary to learn how to make hybrid compounds, to modify and adapt their functionalities and to quantify and understand their uniquely diverse, yet highly specialized, properties. Several approaches have been developed to promote multifunctionality in hybrid systems, among which intercalation chemistry isimportant.[26] Layered insertion com[a] IPCMS, UMR CNRS-UdS 7504, 23 rue du Loess, B. P. 43, 67034 Strasbourg cedex 2, France Fax: +33-3-88107247 E-mail: rabu@ipcms.u-strasbg.fr rogez@ipcms.u-strasbg.fr [b] IPREM-ECP (UMR5254), 2, avenue du Prsident Angot, 64053 Pau cedex 9, France [] Current address: Institut de Chimie Molculaire et des Matriaux dOrsay, CNRS, Universit Paris Sud 11, 91405 Orsay, France Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/ejic.201101220.
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pounds such as dimetallic trioxalatometalates, hexathiohypodiphosphates or magnetic layered double hydroxides are particularly interesting, because they offer the possibility to be functionalized with various ligands or to form original multifunctional multilayers by versatile reactions. Recent achievements concern catalysis,[7] photovoltaics,[8] improved mechanical properties,[9] and multifunctional materials that combine magnetism with photochromism,[10] nonlinear optical properties,[11] conductivity[12] and superconductivity.[13] Most of the foregoing layered functional materials are characterized by weak bonds between subnetworks, which may limit synergy between properties. In this respect, we and others have developed an alternative approach based on the insertion and grafting of functional molecules into magnetic layered transition-metal hydroxides Mx(OH)2x(ny)(Xn)y (M2+ = Co2+, Cu2+, Ni2+, Mn2+M; Xn = carboxylate, sulfate, sulfonate).[14,15] The Xn anion located in the interlayer space may be replaced by an anionic exchange reaction.[15] Due to the connection to the inorganic layers, the interleaved species may be pillars or connectors and can bring their own physical properties. In that case, coordination to the inorganic layers favours an interaction between the subnetworks.[16,17] We recently reported the insertion of new sulfonato nonchiral and chiral salen nickel complexes, designed to be
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grafted into layered simple hydroxides.[18,19] In particular, the insertion of chiral (R,R)- or (S,S)-N,N-bis(5-sulfonatosalicylidene)-1,2-diaminocyclohexane (cysalen) nickel(II), [Ni(CySalenSO3)]2, showed the possibility that the chirality of the inserted complexes could be transferred to the whole hybrid structure.[19] This approach constitutes an elegant way to design magnetochiral systems. Moreover, a great variety of properties can be envisioned, such as luminescence, chirality, enantioselective catalysis and nonlinear optical properties, provided that it is possible to extend our approach to other salen metal complexes. This report describes the synthesis of an extended series of copper and cobalt layered hydroxides functionalized by the insertion of salen Co2+, Ni2+, Cu2+ and Zn2+ complexes. Obtaining hybrid compounds with cobalt, copper or zinc complexes was less straightforward than in the previous case of salen and cysalen nickel complexes due to a specific reactivity with the hydroxide host. Nevertheless, we were able to obtain well-characterized hybrids, which elicited essential synthetic parameters for ion exchange. The magnetic properties of the compounds were also investigated.

P. Rabu, G. Rogez, et al.

Scheme 1. The salen metal complexes used in this work (M2+ = Co2+, Ni2+, Cu2+, Zn2+).

Results and Discussion

Synthesis The best synthetic conditions for all of the compounds are presented in the experimental section. The salen metal complexes used in this work are shown in Scheme 1. The [N,N-bis(5-sulfonatosalicylidene)-1,2-diaminoethane]metal(II) disodium salts, [M(SalenSO3)Na2] (M2+ = Cu2+,[18] Ni2+,[18,20] Zn2+),[18] were synthesized according to published procedures. Similar procedures were adapted to synthesize [Co(SalenSO3)Na2].

The hybrid compounds Cu(SalenSO3)Cu (1), Ni(SalenSO3)Cu (2), Zn(SalenSO3)Cu/Zn (3), Co(SalenSO3) Cu/Co (4), Cu(SalenSO3)Co/Cu (5), Ni(SalenSO3)Co (6), Zn(SalenSO3)Co/Zn (7) and Co(SalenSO3)Co (8) were prepared by an anion-exchange reaction[3,2127] from the preintercalated compounds Cu2(OH)3(DS) (DS = dodecylsulfate) and Co2(OH)3(DS0) (DS0 = dodecylsulfonate) and an excess (about 1.5 equiv.) of the sodium salt of the salen sulfonate complexes. This preintercalation strategy was developed for layered simple hydroxides to insert azo dyes into copper layered hydroxide.[28] Indeed, when we started directly from the acetate analogues Cu2(OH)3(OAc) H2O and Co2(OH)3(OAc)H2O, we systematically observed partial or total hydrolysis of the salen complexes along with the formation of multiphasic compounds.[19] Therefore, preintercalation of the starting acetate hydroxide by sulfate or sulfonate alkyl chains, not only facilitates the insertion of large molecules into the interlamellar space, but also creates a more hydrophobic local environment, which prevents hydrolysis of the complexes during the insertiongrafting reaction. It was also necessary to work in a water/ethanol (1:1, v/v) medium, contrary to classical anionic exchange where only water is used.

XRD The powder XRD patterns of the starting compounds and all hybrid derivatives are shown in Figure 1.

Figure 1. Powder XRD patterns of 14 (left) and 58 (right) (Cu-K1 = 0.15406 nm). 2732
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Functional Heterometallic Layered Hybrid Magnets by Double Ion-Exchange

At low angle (2 35), the diffraction patterns of all compounds show intense 00l diffraction lines up to at least the third harmonic, which evidences their lamellar character. After reaction with [M(SalenSO3)]2, no diffraction lines from Cu2(OH)3(DS) (d = 2.67 nm), Co2(OH)3(DS0) (d = 2.50 nm) or from another phase were observed in the diffraction patterns of 18. Moreover, the basal spacing (Table 1) is wholly modified with respect to the starting materials, which indicates the completeness of the reaction.
Table 1. Interlamellar distances of Cu2(OH)3(DS), Co2(OH)3(DS0) and 18. d [nm] Cu2(OH)3(DS) 1 2 3 4 2.67 1.69 1.76 2.08 2.23 Co2(OH)3(DS0) 5 6 7 8 d [nm] 2.50 2.24 2.22 2.22 2.24

The hybrid compounds based on copper hydroxides can be separated in two groups from the basal spacing. Compounds 1 and 2 show a similar interlamellar distance of ca. 1.7 nm. The size of the salen complexes can be estimated from the crystal structure of [Ni(SalenSO3Na2)], of ca. 1.51 nm.[18] We were unable to obtain crystal structures of the other salen complexes. However, simple molecular simulations show that the distance between the opposite SO3 groups is nearly the same as for [Ni(SalenSO3Na2)]. The copper hydroxide layers in the starting materials consist of planar triangular arrays of Cu2+ ions in octahedral sites. A thickness of ca. 0.3 nm can be estimated from the structure of Gerhardtite Cu2(OH)3NO3.[2931] Hence, the interlamellar distance of 1 and 2 is consistent with an insertion grafting of [M(SalenSO3)]2 that connects the inorganic layers with a small tilt angle with respect to the normal to the inorganic layers (about 23 for 1 and 15 for 2). The elemental analyses support this structural description, and the formulations of 1 and 2 are Cu2(OH)3.00[Cu(SalenSO3)]0.50 0.20H2O and Cu2(OH)3.24[Ni(SalenSO3)]0.382.6H2O, respectively. Conservation of the basic structure of the hydroxide layers during anion exchange is the most common situation encountered in the literature.[3] Compounds 3 and 4 present larger interlamellar distances of 2.08 and 2.23 nm, respectively. Considering the size of the complexes, these distances seem incompatible with complexes that simply connect the parent copper hydroxide layers. Moreover, elemental analyses of these two compounds indicate an excess of Zn (for 3) or Co (for 4) compared to that expected for the insertiongrafting of the salen complexes between the copper hydroxide layers. Actually, the interlamellar distance observed for 3 is close to those obtained for 58, in which the inorganic layer structure consists of a triple-decker sheet derived from the structure of the analogous Zn5(OH)8(NO3)22H2O[25,32,33] or CoOh10.5xCoTd0.5x(OH)2(Cl)xnH2O compounds.[34] In this case, some of the octahedral sites of the planar triangular array are unoccupied, and tetrahedral metal sites are present on each side of the layers at the point of the vacancies.
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We propose that the inorganic layer of 3 (and therefore 4) consists of a triple-decker layer, which is formed of a monolayer of copper hydroxide with metal vacancies counterbalanced by ZnII in tetrahedral sites (or CoII in 4). The ZnII or CoII ions present in the inorganic layers come from the salen complexes, which degrade during the insertion reaction (we have previously shown that these complexes are sensitive to hydrolysis and that the nickel complex is more stable).[18] The interpretation of elemental analysis on this structural basis leads to the consistent formulations Cu0.7Zn1.30(OH)3.20[Zn(SalenSO3)]0.402.11H2O and Cu1.16Co0.84(OH)3.28[Co(SalenSO3)]0.366.4H2O for 3 and 4, respectively. In 58, all of the interlamellar distances are similar, in accordance with an inorganic triple-decker sheet such as that in the parent dodecylsulfonate compound. Considering the thickness of the cobalt hydroxide triple layer (ca. 0.73 nm),[25] the interlamellar distance of 6 and 8 is consistent with an insertiongrafting of [M(SalenSO3)]2 that connects the inorganic layers with a very small tilt angle with respect to the normal to the inorganic layers (about 9 for 6 and 0 for 8). For 6 and 8, the elemental analysis corresponds to the insertiongrafting of the salen sulfonate complexes into cobalt hydroxide triple layers with the formulations Co2(OH)3.18(NiSalenSO3)0.414H2O and Co2(OH)3.44(CoSalenSO3)0.283.7H2O for 6 and 8, respectively. As in 3 and 4, elemental analyses of 5 and 7 indicate an excess of Cu (for 5) or Zn (for 7) with respect to that expected for the simple insertiongrafting of the salen complexes between the cobalt hydroxide layers. For 7, the same analysis as above leads us to consider the partial decomplexation of [Zn(SalenSO3)]2 to form a mixed layered hydroxide, for which the inorganic layers consist of triple layers made of a mixed monolayer of CoII and ZnII ions in octahedral sites, which exhibit metal vacancies counterbalanced by tetrahedral ZnII and CoII ions beside the central monolayer. For 5, the same situation occurs except that the CuII ions released by the decomplexation of [Cu(SalenSO3)]2 are unlikely to occupy tetrahedral sites.[35] Therefore, we have to consider a mixed CoII and CuII octahedral hydroxide layer and tetrahedral CoII ions only. In these kinds of cobalt hydroxide based hybrid compounds, it is generally assumed that the exchange reactions proceed by a dissolutionrecrystallization mechanism.[25,33] Such a mechanism, associated with a release of CuII ions, may allow the formation of such heterometallic inorganic layers. The elemental analyses, in accordance with the structural description, led to the formulations Co1.72Cu0.28(OH)3.28(CuSalenSO3)0.363.20H2O and Co0.80Zn1.20(OH)3.20(ZnSalenSO3)0.402.25H2O for 5 and 7, respectively.

X-ray Photoelectron Spectroscopy In order to refine our hypothesis that concerns possible cation exchange and formation of mixed heterometallic layered simple hydroxides, X-ray photoelectron spectroscopy (XPS) was performed on the hybrid compounds functionwww.eurjic.org

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alized by 3 and 7. The quantitative analysis for 3 is in good agreement with the result from the elemental analysis (Cu0.7Zn1.2O5.05S0.8N0.6C7.1 from XPS and Cu0.7Zn1.7O8.5S0.8N0.8C6.4 from elemental analysis). For 7, the XPS quantitative analysis shows a larger proportion of C and S than found by elemental analysis of the powder and a concomitantly smaller proportion of N (Co0.7Zn1.9O6.6S0.84N0.41C9.0 from XPS and Co0.8Zn1.6O8.7S0.8N0.8C6.4 from elemental analysis). This probably indicates a small contamination of the surface by residual DS0 anions. Nevertheless, its proportion was too small to be detected by bulk techniques such as IR spectroscopy (see below). Finally, in both 3 and 7, the excess of Zn compared to that expected for simple anion exchange was clearly evidenced. The energy of the Zn2p3/2 component is 1022.2 and 1021.8 eV for the reference samples [Zn(SalenSO3Na2)] and Zn5(OH)8(OAc)22H2O, respectively. In 3 and 7, the Zn2p3/2 binding energy is modified with respect to the starting salen complex (1021.7 and 1021.6 eV, respectively; Figure S1). Without excluding the simultaneous presence of both types of environments (salen and hydroxide), this indicates that the Zn environment is modified upon insertion of the [Zn(SalenSO3Na2)] complex. Most of the ZnII ions acquire an environment close to that encountered in Zn5(OH)8(OAc)22H2O, which is in line with the hypothesis made from the X-ray diffraction results, of partial migration of Zn2+ ions into the hydroxide layers. In addition, the shape of the Cu2p peak is modified in 3 compared to Cu2(OH)3(DS) (Figure S2). This may indicate a change in the environment of the CuII ions due to the presence of ZnII in the inorganic layer. On the contrary, the Co2p peak is identical in 7 and Co2(OH)3(DS0), which may indicate that the modification of the environment of CoII is less pronounced (Figure S3).

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Figure 2. TGA (solid lines) and TDA (dotted lines) curves for 1 (red), 2 (black), 3 (green) and 4 (purple).

Figure 3. TGA (solid lines) and TDA (dotted lines) curves 5 (red), 6 (black), 7 (green) and 8 (purple).

Thermal Analysis The thermogravimetric and thermal desorption analyses (TGA/TDA) were obtained in air with a heating rate of 5 C min1 (Figures 2 and 3). The TGA curves of 18 are similar and show multistep decomposition. The first weight loss between 25 and 200 C is associated with a slightly endothermic TDA peak. This first event is attributed to the loss of absorbed and/or hydrogen-bonded interlayer water molecules. The quantities of water determined from TGA experiments are in good agreement with those determined by elemental analysis [1: 1.0 % (0.9 % from elemental analysis), 2: 10.5 % (11.4 %), 3: 9.3 % (9.1 %), 4: 14.8 % (23.5 %), 5: 16.1 % (16.8 %), 6: 13.9 % (16.3 %), 7: 8.9 %(9.7 %), 8: 16.1 % (16.8 %)]. The second event, between 200 and 600 C, is associated with poorly resolved exothermic peaks (sometimes strongly exothermic) and is ascribed to the decomposition of the organic part of the intercalated complex and the dehydroxylation of the inorganic layers. The final step between 600 and 800 C corresponds to the complete elimination of the
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residues derived from the pyrolysis of the initial sulfonate groups.[36,37] The final products correspond to the formation of CuO in 1, Co3O4 in 8 and mixed Cu/M or Co/M oxides in 24 or 57, as identified by X-ray diffraction. The Cu/M and Co/M ratios are identical to those of initial 18 as confirmed by energy-dispersive X-ray spectroscopy (EDX).

IR Spectroscopy All [M(salenSO3)]Na2 and 18 were analyzed by FTIR spectroscopy (Figure S4 and Table 2). All of the spectra show a broad band between 3600 and 3000 cm1, i.e. in the hydroxy stretching region. This broad band can be attributed to the water lattice[38] in agreement with the chemical analysis and TGA/TDA.
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Functional Heterometallic Layered Hybrid Magnets by Double Ion-Exchange Table 2. Positions of some vibration modes for [M(salenSO3)] and 18 [cm1].
(C=N) [Cu(SalenSO3Na2)] 1 5 [Ni(SalenSO3Na2)] 2 6 [Zn(SalenSO3Na2)] 3 7 [Co(SalenSO3Na2)] 4 8 1641 1601 1639 1600 1640 1602 1650 1617 1624 1633 1641 1601 1637 1601 1604 1649 1604 1636 1602 1644 1601 asym(SO3) sym(SO3) 1174 1187 1192 1173 1168 1171 1169 1188 1173 1174 1190 1175 1033 1021 1032 1042 1031 1032 1045 1034 1034 1038 1032 1033 141 166 160 131 137 139 124 154 143 136 158 142

104 m2 area with several 1 m2 spot analyses) shows the homogeneity of the different compounds and is in accordance with the composition determined by elemental analysis.

Figure 4. SEM images of 3 (left) and 6 (right).

At ca. 2900 cm , weak bands are present in the IR spectra, which can be attributed to the elongation of the CH2 groups present in the ethylene bridge of the salen complexes. No intense bands at 2919 and 2851 cm1 are visible in the IR spectra of the hybrid compounds, which is in accordance with the complete replacement of the dodecylsulfate or dodecylsulfonate chains by the [M(salenSO3)] complexes. The fingerprint of the [M(salenSO3)] complexes appears between 1700 and 400 cm1. In this region, the IR spectra of the hybrid compounds show nearly the same vibration bands as the corresponding complexes. However, small shifts are observed, particularly for the vibration bands of the imine group (ca. 1630 cm1) and the CO bond (ca. 12601180 cm1). These modifications can be attributed to an effect of the inorganic host on the stiffness of the complexes, which has been observed with the insertion of salen complexes in different inorganic hosts.[7,3943] Finally, the identification of the asymmetric and symmetric vibrations of the sulfonate groups is of particular importance in order to precisely assign the coordination mode of the ligands.[31,36,44,45] The stretching of the sulfonate moieties occurs at ca. 12301120 cm1 for the asymmetric mode (as) and at ca. 10801025 cm1 for the symmetric mode (s). The difference, , between as and s, gives information on the mode of coordination of the sulfonate. In this case, for the hybrid compounds is in the range 140 170 cm1 (ca. 160 cm1 for 1 and 5, 140 cm1 for 2 and 6, 150 cm1 for 3 and 7 and 150 cm1 for 4 and 8), which is higher than the values for the corresponding [M(salenSO3)] complexes and suggests a monodentate coordination mode for the sulfonate groups probably with an additional oxygen atom involved in a hydrogen bond.[18,31,36,44,45]

UV/Vis Spectroscopy The UV/Vis spectra of the hybrid compounds and the starting complexes are shown in Figure S5. These spectra confirm the insertion of the complexes into the layered hydroxides. The spectra of 18 show intense absorptions in the UV region, which can be attributed to OM (M = Cu or Co) charge transfer of the inorganic layers and to *, n* and d* transitions of the salen complexes.[18,19] In the visible/NIR region, the spectra of 14 show a broad band attributed to CuII ions in octahedral sites (ca. 570 nm for 1, 680 nm for 2, 560 nm for 3 and 540 nm for 4). The less energetic (and much broader) transition for 2 remains unexplained at this stage. In addition, some bands characteristic of the salen complexes are observed. In 2, a shoulder at 520 nm is attributed to the dxydx2y2 transition characteristic of square-planar NiII Schiff base complexes (1A11B1 assuming a C2v symmetry).[46] In 4, two bands of the salen complex are observed at 490 and 610 nm. In 1, the dd transition of the CuII ions of the inorganic layer hides the dd transition of [Cu(Salen)]. For 58, in addition to the bands attributed to the salen complexes, two absorptions bands at ca. 1200 and 1500 nm can be identified and attributed to d7 CoII ions in octahedral sites [4T1g(F)4T2g(F)] and d7 CoII in tetrahedral sites [4A2(F)4T1(F)], respectively, in accordance with the proposed structure and magnetic behaviour. In 68, the two associated transitions [4T1g(F)4T1g(P)] for d7 octahedral CoII ions and 4A2(F)4T1(P) for d7 tetrahedral CoII ions are observed at ca. 580 and 630 nm, respectively. In 5, these transitions are hidden by transitions from the inserted [Cu(Salen)] complex.

SEM SEM images of 3 and 6 are shown in Figure 4 and are representative of all the compounds. These pictures show the large, thin, plate-like morphology of the hybrids, which is in agreement with the lamellar character of their structures. Moreover, the EDX analysis (cartography of a
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Magnetic Properties The T = f(T) curves for 14 are shown in Figure 5. The Curie constants (1.00 emu K mol1 for 1, 0.95 emu K mol1 for 2, 0.24 emu K mol1 for 3 and 3.77 emu K mol1 for 4)
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determined from the fit of the 1/ = f(T) curves above 150 K by using the CurieWeiss law are in agreement with the expected values.

P. Rabu, G. Rogez, et al.

Figure 6. Field dependence at T = 1.8 K of the magnetization of 1 (open red lozenges), 2 (open black circles), 3 (open green squares) and 4 (open purple triangles). The solid lines are a guide. Figure 5. T vs. T plots for 1 (red), 2 (black), 3 (green) and 4 (purple).

Different behaviour can be distinguished. For 1, 2 and 3, the T product decreases consistently from room temperature, which indicates dominant antiferromagnetic interactions. For 3, the decrease of the T product is continuous down to 1.8 K, and for 1 and 2, the T product reaches a minimum (at ca. 5 K for 1 and 30 K for 2) before increasing at temperatures down to 1.8 K. This behaviour suggests uncompensated antiferromagnetic interactions that lead to ferrimagnetism or canted antiferromagnetism. This interpretation is supported by the magnetization vs. field measurements at 1.8 K (Figure 6), which show a sharp increase at low fields and a magnetization value at high field close to saturation, but relatively low and far from the expected value for full alignment of copper ions of the layer (in 1, by the copper ions of the inserted complex). Moreover, the low-temperature ac susceptibility measurements show only the basis of growing peaks in the and signals, which indicates that long-range weak ferromagnetic order is not yet fully established at 1.8 K (Figure 7). This behaviour is similar to that observed in other copper hydroxide based hybrids,[28] and is in agreement with the fact that the structure of the inorganic layers for 1 and 2 remains relatively unchanged. For 3, the low magnetic moment and the quasilinear shape of the magnetization vs. field measurement confirm the antiferromagnetic coupling. The magnetic behaviour of 4 is totally different to that of 13 and very similar to that of 6 and 8 (see below). Upon cooling, the T product decreases consistently to a minimum at ca. 65 K. This small decrease is well understood on the basis of spinorbit coupling of CoII ions and/or antiferromagnetic interactions between the in-plane spin carriers. Below this minimum, the T product exhibits a steep increase to a maximum at 8 K. This increase can be related to the occurrence of long-range ferromagnetic-type ordering, as evidenced by the occurrence of peaks in the real and imaginary parts of the susceptibility (Figure 7). The ordering temperature is determined from the maximum of the real part of the ac susceptibility (Tordering = 4.8 K).
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Figure 7. In-phase (, open symbols) and out-of-phase (, full symbols) magnetic susceptibilities measured in an ac field of 0.35 mT at 100 Hz for 1 (red lozenges), 2 (black circles), 3 (green squares) and 4 (purple triangles). The solid lines are a guide.

The ferromagnetic-type behaviour of 4 is confirmed by the magnetization vs. field curve at low temperature (Figure 6), which shows a coercive field of ca. 25 mT. The magnetization is not saturated at high field (3.5 B at 5 T). It is not possible to know the ratio between CoII in tetrahedral and octahedral sites. Therefore, the high-field value does not allow the discrimination between ferromagnetic and ferrimagnetic ordering. The T = f(T) curves for 58 are shown in Figure 8. The Curie constants (4.36 emu K mol1 for 5, 5.89 emu K mol1 for 6, 1.43 emu K mol1 for 7 and 6.50 emu K mol1 for 8) determined from the fit of the 1/ = f(T) curves above 150 K are in agreement with the values expected from their chemical compositions. The magnetic behaviour of 5, 6 and 8 is similar to that of 4 and typical of cobalt hydroxide based hybrid compounds.[15,25] The T product of 5, 6 and 8 decreases slightly down to a minimum at ca. 60 K due to spinorbit coupling and/or antiferromagnetic interactions between the moments. Below this minimum, the T product increases
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Functional Heterometallic Layered Hybrid Magnets by Double Ion-Exchange

Figure 8. T vs. T plots for 5 (red), 6 (black), 7 (green) and 8 (purple).

Figure 10. Field dependence at T = 1.8 K of the magnetization of 5 (open red lozenges), 6 (open black circles), 7 (open green squares) and 8 (open purple triangles). Solid lines are a guide.

strongly to a maximum value at ca. 8 K. This increase can be related to the occurrence of long-range ferromagnetictype order. The ordering temperatures were determined by ac susceptibility measurements (f = 100 Hz, 0Hac = 0.35 mT, Figure 9). The maximum of the real part leads to TN = 5.7 K for 5, 6.1 K for 6 and 6.7 K for 8. The fact that TN hardly changes for 6 and 8, which present the same interlayer distance and the same structure and composition of the inorganic layers, is consistent with an interlayer coupling through dipolar interactions.[15,25,29,47] The magnetization vs. field curves at 1.8 K (Figure 10) show the presence of hysteresis loops with coercive fields of 30 mT for 5, 60 mT for 6 and 50 mT for 8. The high-field values are lower than those expected for a total alignment of the moments, which suggests ferrimagnetic ordering.

different to that of the other cobalt hydroxide based hybrids 5, 6 and 8. The T product of 7 decreases continuously from room temperature to 1.8 K, which indicates dominant antiferromagnetic behaviour. This behaviour is further confirmed by the shape of the magnetization vs. field curve, which is typical of antiferromagnetically coupled systems. The ac susceptibility measurements show no evidence of magnetic ordering.

Conclusions
The present compounds constitute new examples of heterometallic simple layered hydroxides and the first examples of layered simple hydroxides made of two different MII ions and functionalized in the interlamellar spacing by a metal complex. Heterometallic simple hydroxides that display similar triple-decker layer structures have already been described for small anions: layered NiIIZnII hydroxyacetate obtained by coprecipitation[50] or hydrothermal methods,[5053] layered NiIICoII hydroxyacetate obtained by hydrolysis in polyol medium.[54] Copper-containing NiII hydroxide, Ni1xCux(OH)2, has also been obtained by coprecipitation, although in this case, the inorganic layer of the heterometallic hydroxide is made of metal ions in octahedral sites only.[55] In our new series of hybrid compounds, the modification of the inorganic layers is induced by the functionalization of copper or cobalt layered simple hydroxides by salen-type complexes. When the complexes are sufficiently labile (CuII, CoII and ZnII), partial decomplexation releases free ions into the reaction mixture, which leads to the formation of heterometallic inorganic layers. For copper hydroxide based materials, the inorganic layers, initially simple (made of CuII ions in Oh sites), are modified into heterometallic triple-decker layers made of CuII ions in Oh sites and MII ions in Oh and/or Td sites. Thus, 3, 4, 5 and 7 result from a double ion-exchange reaction, i.e. anion exchange between DS or DS0 and the salen sulfonates, and cation exchange between the salen complex and the inorganic layers. This is not observed in 2 and 6 due to the higher stability of the Ni salen complex. Such a double ionwww.eurjic.org

Figure 9. In-phase (, open symbols) and out-of-phase (, full symbols) magnetic susceptibilities measured in an ac field of 0.35 mT at 100 Hz for 5 (red lozenges), 6 (black circles), 7 (green squares) and 8 (purple triangles). Solid lines are a guide.

The presence of Zn as a dominant constitutive element of the inorganic triple layers in 7 disturbs the magnetic network made of Oh and Td CoII ions, which leads to disruption of the long-range interaction of the spin carriers. Magnetic dilution either by diamagnetic centres or by metal vacancies is known to induce a drastic change of the magnetic behaviour of lamellar compounds. However, it is difficult to rationalize.[48,49] Actually, the magnetic behaviour of 7 is
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exchange phenomenon is reminiscent of the synthesis of (Zn,M)5(OH)8Cl2 (M = Co or Ni), which were obtained by the reaction of zinc hydroxide nitrate with aqueous solutions of the metal salts CoCl2 or NiCl2.[56] Double ion-exchange reactions are particularly unusual in hydroxides, and the situation is more intricate in this work as the salen complexes are the source of the divalent metal that enters the inorganic layers and is also exchanged as a whole with an alkyl anion to lead to immobilized metal centres between the hydroxide layers. The consequences on the magnetic properties are very important as the behaviour of the copper hydroxide based compounds changes from weak ferromagnetic behaviour at very low temperature (below 1.8 K) for the compounds functionalized with Ni, Cu and Zn salen complexes to ferrimagnetic ordering at 4.8 K for the compound functionalized with cobalt salen. For the cobalt hydroxide based compounds, ferrimagnetic ordering (below 6 K) or antiferromagnetic behaviour (without order) was observed, which depends on the magnetic dilution of the heterometallic hydroxide layers. This approach illustrates the richness of the insertion chemistry of layered simple hydroxides and opens new possibilities in terms of versatility and functionalities, not only by the functionalization of the interlamellar spacing, but also by the modification of the composition and structure of the inorganic layers.

P. Rabu, G. Rogez, et al. peaks were analysed by using a nonlinear Shirley-type background.[57] The peak positions and areas were optimized by a weighted least-squared fitting method using 70 % Gaussian, 30 % Lorentzian lineshapes. Quantification was performed on the basis of Scofields relative sensitivity factors.[58] The magnetic studies were carried out with a SQUID magnetometer (Quantum Design MPMS-XL), which covered the temperature and field ranges 2 300 K, 5 T. Ac susceptibility measurements were performed in a 0.35 mT alternating field (100 Hz). Magnetization measurements at different fields at room temperature confirmed the absence of ferromagnetic impurities. Cu2(OH)3(DS)[29] and Co2(OH)3(DS0)[33] were prepared as described previously. All experiments were conducted under argon, and solvents were degassed prior to use. Yields of the hybrid compounds were around 5070 %. Synthesis of Complexes: 5-Sulfonatosalicylaldehyde sodium salt (A),[20,59] N,N-bis(5-sulfonatosalicylidene)-1,2-diaminoethane disodium salt [(SalenSO3)Na2][18] and N,N-bis(5-sulfonatosalicylidene)-1,2-diaminoethane metal(II) disodium salt [M(SalenSO3)Na2] (M = Cu,[18] Ni[18,20] and Zn[18]) were synthesized according to published procedures. [N,N-Bis(5-sulfonatosalicylidene)-1,2-diaminoethane]cobalt(II) Disodium Salt [Co(SalenSO3)Na2]: Ethylenediamine (99 L, 1.5 mmol) was added to a degassed mixture of water (4.5 mL) and ethanol (30 mL). Bis(5-sulfonatosalicylaldehyde)cobalt(II) disodium salt[60] (839 mg, 1.5 mmol) was introduced, and the mixture was stirred at 90 C for 1 h. The brown solid was collected by filtration, washed with ethanol and dried under vacuum. Yield 70 %. [Co(salenSO3Na2)]4H2O: C16H20CoN2Na2O12S2 (600.96): calcd: C 31.96, H 3.35, Co 9.8, N 4.66, Na 7.65, S 10.66; found C 32.13, H 3.30, Co 10.17, N 4.43, Na 8.10, S 11.37. IR (KBr): = 3441 (s), 1648 (s), 1605 (s), 1525 (s), 1467 (s), 1467 (s), 1403 (m), 1379 (m), 1331 (m), 1206 (s), 1171 (s), 1116 (s), 1040 (s), 922 (w), 900 (w), 839 (w), 746 (w), 678 (m), 609 (m), 566 (w), 527 (w), 471 (w) cm1. Synthesis of Hybrid Compounds Cu(SalenSO3)Cu (1): [Cu(SalenSO3Na2)] (528 mg, 0.85 mmol) was dissolved in water/ethanol (160 mL, 1:1, v:v). Cu2(OH)3(DS) (260 mg, 0.59 mmol) was added, and the mixture was stirred under argon at 90 C for 3 h. The blue powder was collected by filtration and washed with water and ethanol. Yield 6070 %. Cu2(OH)3.00[Cu(SalenSO3)]0.500. 20H2O: C8.00H9.40N1.00S1.00O11.20Cu2 (425.5): calcd. C 22.56, H 2.11, Cu 37.33, N 3.29, S 7.53; found C 22.82, H 2.29, Cu 37.09, N 3.13, S 6.57. IR (KBr): = 3559 (m), 3453 (m), 2959 (w), 2920 (w), 2858 (w), 1639 (s), 1600 (m), 1559 (w), 1530 (m), 1462 (s), 1385 (m), 1224 (s), 1187 (m), 1130 (s), 1021 (s), 955 (w), 831 (m), 731 (w), 669 (m), 617 (m), 587 (m), 553 (w), 507 (w), 452 (w) cm1. Ni(SalenSO3)Cu (2): Compound 2 was synthesized according to a published procedure.[19] Zn(SalenSO3)Cu/Zn (3): [Zn(SalenSO3Na2)] (534 mg, 0.88 mmol) was dissolved in water/ethanol (220 mL, 1:1, v:v). Cu2(OH)3(DS) (260 mg, 0.59 mmol) was added, and the mixture was stirred under argon at 70 C for 1.5 h. The violet powder was collected by filtration andwashedwithwaterandethanol.Yield6070 %.Cu0.7Zn1.30(OH)3.20[Zn(SalenSO3)]0.402.11H2O: C4.80H12.22Cu0.70N0.80O8.51S0.80Zn1.70 (417.6): calcd. C 18.39, H 2.93, Cu 10.65, N 2.68, S 6.14, Zn 26.61; found C 18.62, H 2.92, Cu 10.61, N 2.12, S 6.72, Zn 26.25. IR (KBr): = 3489 (s), 2961 (w), 2923 (w), 2858 (w), 1637 (s), 1601 (s), 1530 (m), 1463 (m), 1385 (m), 1322 (m), 1188 (s), 1117 (s), 1033 (s), 983 (w), 903 (w), 831 (m), 741 (m), 619 (m), 594 (m), 532 (w), 472 (m) cm1. Co(SalenSO3)Cu/Co (4): [Co(SalenSO3Na2)] (528 mg, 0.88 mmol) was dissolved in water/ethanol (160 mL, 1:1, v:v). Cu2(OH)3(DS)
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Experimental Section
General Remarks: Salicylaldehyde, aniline, ethylenediamine and metal salts were purchased from Alfa-Aesar, Acros and Fluka and were used as received. Elemental analyses for C, H, N, S, Co and Cu were carried out at the Service Central dAnalyse of the CNRS (USR-59). The powder XRD patterns were collected with a Bruker D8 diffractometer (Cu-K1 = 1.540598 ) equipped with a SolX detector discriminating in energy. 1H NMR spectra were recorded with a Bruker Avance 300 (300 MHz) spectrometer. The spectra were referenced to the residual protic solvent peaks. SEM images were obtained with a JEOL 6700F (SEM equipped with a fieldemission gun, operating at 3 kV in the SEI mode) instrument. FTIR spectra were collected with a Digilab FTS 3000 computerdriven instrument (0.1 mm thick powder samples in KBr). UV/Vis/ NIR spectroscopy was performed with a PerkinElmer Lambda 950 spectrometer (spectra recorded in the reflection mode by using a 150 mm integrating sphere, with a mean resolution of 2 nm and a sampling rate of 300 nm min1). TGA/TDA experiments were performed by using a Setaram TG92 instrument (heating rates of 5 C min1, air stream). XPS measurements were carried out with a Kratos Axis Ultra spectrometer by using a focused monochromatized Al-K radiation (h = 1486.6 eV). The XPS spectrometer was directly connected through a transfer chamber to an argon dry box to avoid moisture/air exposure of the samples. For the Ag3d5/2 line, the full width at half maximum was 0.58 eV under the recording conditions. The analysed area of the samples was 300 700 m2, and the electrons escape from the very top surface (510 nm depth). Peaks were recorded with a constant pass energy of 20 eV. The pressure in the analysis chamber was ca. 5 109 mbar. The binding energy scale was calibrated from hydrocarbon contamination by using the C1s peak at 285.0 eV. Core 2738
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Functional Heterometallic Layered Hybrid Magnets by Double Ion-Exchange (260 mg, 0.59 mmol) was added, and the mixture was stirred under argon at 85 C for 4 h. The brownish powder was collected by filtration and washed with water and ethanol. Yield 6070 %. Cu1.16Co0.84(OH)3.28[Co(SalenSO3)]0.366.4H2O: C4.3H20.38Co0.84Cu1.16N0.72O12.55S0.72 (467.4): calcd. C 14.72, H 4.40, Co 15.11, Cu 15.77, N 2.15, S 4.91; found C 14.61, H 3.84, Co 15.11, Cu 15.25, N 1.83, S 4.1. IR (KBr): = 3448 (s), 2974 (w), 2926 (w), 2857 (w), 1639 (s), 1602 (s), 1533 (m), 1465 (m), 1382 (m), 1333 (w), 1311 (w), 1190 (s), 1116 (s), 1032 (s), 974 (w), 929 (w), 896 (w), 833 (w), 793 (w), 736 (w), 671 (m), 622 (m), 602 (m), 517 (w), 457 (w) cm1. Cu(SalenSO3)Co/Cu (5): [Cu(SalenSO3Na2)] (528 mg, 0.85 mmol) was dissolved in water/ethanol (160 mL, 1:1, v:v). Co2(OH)3(DS0) (260 mg, 0.62 mmol) was added, and the mixture was stirred under argon at 90 C for 6 h. The bluish powder was collected by filtration andwashedwithwaterandethanol.Yield6070 %.Co1.72Cu0.28(OH)3.28C5.76H14.00Co1.72Cu0.64N0.72O9.36S0.72 (CuSalenSO3)0.363.20H2O: (408.10): calcd. C 16.94, H 3.43, Co 24.84, Cu 9.96, N 2.47, S 5.66; found C 17.49, H 3.50, Co 24.14, Cu 9.72, N 2.35, S 5.78. IR (KBr): = 3447 (s), 2923 (w), 2854 (w), 1640 (s), 1602 (m), 1557 (w), 1538 (m), 1467 (m), 1438 (w), 1382 (m), 1335 (w), 1307 (m), 1192 (s), 1170 (s), 1117 (s), 1302 (s), 973 (w), 832 (w), 735 (w), 670 (m), 623 (m), 600 (m), 558 (w), 520 (w) cm1. Ni(SalenSO3)Co (6): Compound 6 was synthesized according to a published procedure.[19] Zn(SalenSO3)Co/Zn (7): [Zn(SalenSO3Na2)] (270 mg, 0.44 mmol) was dissolved in water/ethanol (80 mL, 1:1, v:v). Co2(OH)3(DS0) (130 mg, 0.31 mmol) was added, and the mixture was stirred under argon at 90 C for 3.5 h. The orange powder was collected by filtration and washed with water and ethanol. Yield 6070 %. Co0.80Zn1.20(OH)3.20(ZnSalenSO3)0.402.25H2O: C6.40H12.50Co0.80N0.80O8.65S0.80Zn1.60 (416.3): calcd. C 18.33, H 3.05, Co 11.32, N 2.67, S 6.12, Zn 25.12; found C 18.90, H 3.02, Co 11.47, N 2.55, S 6.29, Zn 25.65. IR (KBr): = 3516 (s), 3490 (s), 3364 (m), 3216 (m), 2971 (w), 2926 (w), 1604 (s), 1529 (m), 1460 (m), 1379 (m), 1316 (w), 1197 (s), 1181 (s), 1116 (s), 1304 (s), 825 (m), 750 (m), 678 (m), 632 (m), 606 (m), 541 (w), 521 (w), 479 (w) cm1. Co(SalenSO3)Co (8): [Co(SalenSO3Na2)] (528 mg, 0.88 mmol) was dissolved in water/ethanol (160 mL, 1:1, v:v). Co2(OH)3(DS0) (260 mg, 0.62 mmol) was added, and the mixture was stirred under argon at 85 C for 3 h. The brown powder was collected by filtration and washed with water and ethanol. Yield 6070 %. Co2(OH)3.44(CoSalenSO3)0.283.72H2O: C4.48H7.544Co2.28N0.56O9.4S0.56 (378.5): calcd. C 14.20, H 3.76, Co 35.50, N 2.07, S 4.74; found C 14.29, H 3.31, Co 35.01, N 1.79, S 4.31. IR: = 3444 (s), 1644 (s), 1601 (s), 1559 (w), 1535 (m), 1468 (s), 1423 (w), 1382 (m), 1332 (w), 1314 (w), 1175 (s), 1114 (s), 1033 (s), 972 (w), 928 (w), 835 (w), 735 (w), 676 (m), 632 (m), 605 (m), 568 (w), 521 (w) cm1. Supporting Information (see footnote on the first page of this article): FTIR and UV/Vis spectra.

Acknowledgments
The authors thank the Centre National de la Recherche Scientifique (CNRS), the Universit de Strasbourg, the Agence Nationale de la Recherche (ANR contract numbers ANR-06-JCJC0008 and ANR-06-BLAN-0117-02) for funding. S. E.-M. thanks the French Ministry for Education and Research for his PhD grant. M. D. thanks the Agence Universitaire de la Francophonie (Senegal) for a visiting grant. The authors thank A. Derory and D. Burger for technical assistance.
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