A Polynuclear Lanthanide Single‐Molecule Magnet with a Record Anisotropic Barrier

Abstract

Single-molecule magnets (SMMs) continue to be an attractive research field because of their unique and intriguing properties and potential applications in high-density data storage technologies and molecular spintronics. The anisotropic barrier (U) of an SMM is derived from a combination of an appreciable spin ground state (S) and uniaxial Ising-like magneto-anisotropy (D). The magnet-like behavior can be observed by slow relaxation of the magnetization below the blocking temperature. Since the discovery of SMMs in the early 1990s, this assumption has formed the basis for the understanding of the origin of the anisotropic barrier. However, in recent years the development of novel lanthanide-only SMMs that challenge and defy this theory pose a number of questions: How can slow relaxation of the magnetization be observed in a nonmagnetic state complex? Why are large energy barriers seen for mononuclear lanthanide(III) complexes? To answer such important questions, it is vital to investigate novel SMMs with high magnetoanisotropy for which the influence of the large negative D value could result in higher anisotropic barriers. Clearly lanthanide-based polynuclear systems are an important avenue to explore in the pursuit of SMMs with higher anisotropic barriers, because of the strong spin–orbit coupling commonly observed in 4f systems. However, lanthanide-only SMMs are rare. The majority of reported SMMs have been prepared with transition-metal ions, although the recent application of a mixed transition-metal/ lanthanide strategy also yielded many structurally and magnetically interesting systems. The scarcity of lanthanide-only SMMs results from the difficulty in promoting magnetic interactions between the lanthanide ions. The interactions can, however, be enhanced by overlapping bridging ligand orbitals. In addition, fast quantum tunneling of the magnetization (QTM), which is common for lanthanide systems, generally prevents the isolation of SMMs with high anisotropic energy barriers. Our recent work suggests that dysprosium(III) ions may hold the key to obtaining high-blocking-temperature lanthanide-only SMMs. When an appropriate ligand system is employed, it is possible to exploit the large intrinsic magnetoanisotropy, high spin, and reduced QTM that dysprosium(III) ions offer. Recently, we have focused our attention towards the synthesis of dysprosium(III) cluster complexes with 1,2bis(2-hydroxy-3-methoxybenzylidene) hydrazone (H2bmh) and 3-methoxysalicylaldehyde hydrazone (Hmsh) as chelating agents (see Figure S1 in the Supporting Information). This strategy has proven to be successful and has led to a polynuclear lanthanide SMM with a record anisotropic barrier. Herein, we report the synthesis, structure, and magnetism of a tetranuclear dysprosium(III) SMM that exhibits the largest relaxation barrier seen for any polynuclear SMM to date. A suspension of DyCl3·6H2O and o-vanillin (2:1 ratio) in DMF/CH2Cl2 (1:5 ratio) was treated with 4 equivalents of Et3N. The solution was stirred for 1 minute, and then 4 equivalents of N2H4·H2O was added. The resulting yellow solution yielded rectangular, orange-yellow crystals of the tetranuclear complex [Dy4(m3-OH)2(bmh)2(msh)4Cl2] (1) in 19.1% yield after 2 days. The msh and bmh ligands were formed in situ by the reaction of o-vanillin and hydrazine. The slight excess of hydrazine is essential for the formation of both ligands; when an excess of o-vanillin was used instead, no product was isolated. The basic conditions promote the deprotonation of the ligands and the formation of bridging hydroxide anions. Single-crystal X-ray analysis revealed the centrosymmetric complex 1 (Figure 1), which has a defect-dicubane central core. The four coplanar Dy ions are bridged by two m3-OH ligands displaced above and below (0.922 ) the Dy4 plane with Dy O bond lengths of 2.362(6), 2.302(6), and 2.447(6) andDy O Dy angles of 106.5(2), 107.7(2), and 105.7(2)8, and also by a combination of four phenoxide oxygen atoms [Dy O 2.312(2), 2.298(6), 2.448(6), 2.345(6) ] and two diaza bridging groups [Dy N 2.508(8), 2.564(8) ]. Close inspection of the packing arrangement reveals stacking of the [*] P.-H. Lin, Dr. T. J. Burchell, Dr. M. Murugesu Chemistry Department, University of Ottawa and Centre for Catalysis Research and Innovation D’Iorio Hall, 10 Marie Curie, Ottawa, ON, K1N6N5 (Canada) Fax: (+1)613-562-5170 E-mail: m.murugesu@uottawa.ca Homepage: http://www.science.uottawa.ca/~mmuruges/