Original article
Structure and magnetic property of bimetallic hexanuclear cluster based on 5-chlorosalicylaldehyde oxime

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Abstract

The bimetallic hexanuclear cluster [Mn4Ni2O2(Cl-Sao)6·(CH3OH)8]·10CH3OH (1) was synthesized. Single-crystal X-ray analysis reveals that 1 consists of two [Mn2Ni(μ3-O)(Cl-Sao)3] subunits linked together via two pairs of long Nisingle bondO bonds involving two oximate oxygen atoms and two phenolate oxygen atoms. Each Mn and Ni center achieves six-coordination with axial methanol molecules. The spin centers of the MnIII and NiII ions exchange magnetic coupling through O2−, Ophenolate and single bondNsingle bondOsingle bond bridges. The magnetic properties of the cluster have been investigated.

Graphical abstract

The bimetallic hexanuclear cluster [Mn4Ni2O2(Cl-Sao)6·(CH3OH)8]·10CH3OH was synthesized. The crystal structure and magnetic properties of the cluster have been investigated.

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Introduction

Molecule-based magnetic materials, such as single-molecular magnets (SMMs), photomagnets, magneto-optical materials, magnetic conductors, ferroelectromagnets, chiral magnets, and multifunctional materials have attracted increasing interest over the last few years [1]. The design and synthesis of SMMs is of particular interest, for their magnetic bistability potentially allows devices for ultimate high-density memory storage and quantum computing [2], [3]. Manganese based SMMs have been studied the most, with focus on the paramagnetic nature of the manganese ion in various oxidation states, which provides interesting magnetic properties [4], [5], [6]. Detailed studies of the solid state and frozen solution magnetic properties of a family of oxime-based hexanuclear Mn(III) SMMs (Mn6 SMMs) led to the first established solid state magnetostructural correlations for any SMM, demonstrating that their solid state magnetic properties are crucially dependent on very small changes in geometry; in particular, the Mn–N–O–Mn torsion angles of the metal oxime core [7], [8].

We are interested in introducing other transition metal ions into the Mn6 system and studying how structure change affecting the magnetic properties. In this paper, we report the synthesis, structural characterization, and magnetic properties study of a bimetallic hexanuclear cluster based on 5-chlorosalicylaldehyde oxime (Cl-H2Sao), [Mn4Ni2O2(Cl-Sao)6·(CH3OH)8]·10CH3OH.

Section snippets

Experimental

All chemicals and solvents were commercial products and used without further purification. Elemental analyses of C, H, and N were performed by a Carlo Erba 1106 elemental analyzer. Metal analyses of Mn and Ni were performed by ICP-AES. IR spectra were recorded as KBr pellets on a Nicolet 750 FTIR spectrophotometer. Magnetic data were recorded using a Quantum Design SQUID magnetometer. To avoid orientation in the magnetic field, the samples were pressed in a home-made Teflon sample holder

Results and discussion

Single crystal X-ray diffraction analysis reveals that the complex 1 (Fig. 1), like most Mn6-Sao systems, consists of two off-set [Mn2NiO]6+ triangles lined together via two oximate oxygen atoms from two η1:η2:η1:μ3 Cl-Sao2− ligands and two phenolate oxygen atoms derived from two η2:η1:η1:μ3 Cl-Sao2− ligands. The remaining two oximato(−2) ligands each bridge one NiII ion in an η1:η1:η1:μ fashion, thus forming a [MnIII4Ni2(μ3-O)2(μ3-ONR)2(μ-ONR)4(μ-OR′)2]4+ core. The remaining axial coordination

Conclusion

In summary, the bimetallic hexanuclear cluster based on 5-chlorosalicylaldehyde oxime has similar structure [M6O2] core to Mn6-Sao system. Magnetic investigation reveals that 1 exhibits an antiferromagnetism behavior. No SMMs properties were found in complex 1.

Supplementary materials

Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Center, CCDC 961675, for complex 1. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html.

Acknowledgments

We are grateful for financial support from the Natural Science Foundation of China (NSFC) (No. 21171021), Beijing National Laboratory for Molecular Sciences (BNLMS) and Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry.

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