Slow Magnetic Relaxation in a Palladium–Gadolinium Complex Induced by Electron Density Donation from the Palladium Ion

Abstract

Incorporating palladium in the first coordination sphere of acetato-bridged lanthanoid complexes, [Pd₂ Ln₂ (H₂ O)₂ (AcO)₁₀ ]⋅2 AcOH (Ln=Gd (1), Y (2), Gd_0.4 Y_1.6 (3), Eu (4)), led to significant bonding interactions between the palladium and the lanthanoid ions, which were demonstrated by experimental and theoretical methods. We found that electron density was donated from the d⁸ Pd²⁺ ion to Gd³⁺ ion in 1 and 3, leading to the observed slow magnetic relaxation by using local orbital locator (LOL) and X-ray absorption near-edge structure (XANES) analysis. Field-induced dual slow magnetic relaxation was observed for 1 up to 20 K. Complex 3 and frozen aqueous and acetonitrile solutions of 1 showed only one relaxation peak, which confirms the role of intermolecular dipolar interactions in slowing the magnetic relaxation of 1. The slow magnetic relaxation occurred through a combination of Orbach and Direct processes with the highest pre-exponential factor (τ_o =0.06 s) reported so far for a gadolinium complex exhibiting slow magnetic relaxation. The results revealed that transition metal-lanthanoid (TM-Ln) axial interactions indeed could lead to new physical properties by affecting both the electronic and magnetic states of the compounds.