A New {Dy₅} Single-Molecule Magnet Bearing the Schiff Base Ligand <i>N</i>-Naphthalidene-2-amino-5-chlorophenol

Abstract

A new {Dy5} cluster compound has been synthesized and structurally characterized from the initial use of the Schiff base ligand N-naphthalidene-2-amino-5-chlorophenol (nacpH2) in coordination chemistry. The 1:1 reaction between Dy(hpd)3∙2H2O and nacpH2, in a solvent mixture comprising CH2Cl2 and MeOH, afforded orange crystals of [Dy5(OH)2(hpd)3(nacp)5(MeOH)5] (1) in 70% yield, where hpd− is the anion of 3,5-heptadione. The {Dy5} complex can be described as two vertical {Dy3(μ3-OH)}8+ triangles sharing a common vertex; such a metal topology is unprecedented in 4f-metal cluster chemistry. Direct current (dc) magnetic susceptibility studies revealed the presence of some weak ferromagnetic exchange interactions between the five DyIII ions at low temperatures. Alternating current (ac) magnetic susceptibility measurements at zero applied dc field showed that complex 1∙3MeOH∙CH2Cl2 exhibits temperature- and frequency-dependent out-of-phase signals below ~20 K, characteristics of a single-molecule magnet (SMM). The resulting relaxation times were used to construct an Arrhenius-type plot and determine an effective energy barrier, Ueff, of 100 K for the magnetization reversal. The application of a small dc field of 200 Oe resulted in the surpassing of the quantum tunneling process and subsequently the increase of the Ueff to a value of 170 K. The reported results are part of a long-term program aiming at the preparation of structurally and magnetically interesting lanthanide complexes bearing various Schiff base chelating/bridging ligands.

Keywords

• dysprosium
• schiff bases
• cluster compounds
• single-molecule magnets
• crystal structures