Heterometallic clusters based on an uncommon asymmetric “V-shaped” [Fe3+(μ-OR)Ln3+(μ-OR)2Fe3+]6+ (Ln = Gd, Tb, Dy, Ho) structural core and the investigation of the slow relaxation of the magnetization behaviour of the [Fe2Dy] analogue

Abstract

The synthesis, crystal structures, Mössbauer spectra and variable temperature dc and ac magnetic susceptibility studies of a new family of trinuclear heterometallic Fe³⁺/Ln³⁺ complexes, [Fe₂Ln(PhCO₂)₃((py)₂CO₂)((py)₂C(OMe)O)₂(NO₃)Cl] (Ln = Gd (1/Gd), Tb (1/Tb), Dy (1/Dy), and Ho (1/Ho)), where (py)₂CO₂²⁻ and (py)₂C(OMe)O⁻ are the anions of the gem-diol and hemiketal derivatives of di-2-pyridyl ketone, are reported. Compounds 1/Ln are based on an asymmetric “V-shaped” [Fe³⁺(μ-OR)Ln(μ-OR)₂Fe³⁺]⁶⁺ structural core formed from the connection of the two terminal Fe³⁺ centers to the central Ln³⁺ ion either through one or two alkoxide groups originating from the alkoxide-type bridging ligands. Direct current magnetic susceptibility studies reveal the presence of weak antiferromagnetic interactions between the Fe³⁺ ions. Alternating current magnetic studies indicate the presence of a slow-magnetic relaxation process in 1/Dy with an energy barrier U_eff = 6.7 (±0.3) K and a pre-exponential factor, τ₀ = 2.2 (±0.4) × 10⁻⁷ s. The electronic, magnetic and relaxation properties of the complexes were further monitored by variable temperature ⁵⁷Fe Mössbauer spectroscopy. At T > 80 K the spectra from the complexes comprise two quadrupole doublets the hyperfine parameters of which reflect the distinct coordination environment of the two Fe³⁺ terminal sites. At T < 20 K, the Mössbauer spectra for 1/Dy are affected by magnetic relaxation effects. At 1.5 K, the spectrum of 1/Dy comprises well defined magnetic sextets indicating relaxation times slower than the characteristic time of the Mössbauer technique (10⁻⁷ s) in agreement with the dynamic magnetic measurements. 1/Gd exhibits broad unresolved magnetic sextets at 1.5 K indicating that the spin relaxation time is of the order of the Mössbauer characteristic time at this temperature. For 1/Tb, 1/Ho the Mössbauer spectra exhibit slight broadening even at the lowest available temperature consistent with magnetic relaxation times less than 10⁻⁷ s.