Tuning symmetry and magnetic blocking of an exchange-coupled lanthanide ion in isomeric, tetrametallic complexes: [LnCl6(TiCp2)3]

Abstract

The synthesis and magnetic properties of two pairs of isomeric, exchange-coupled complexes, [LnCl₆(TiCp₂)₃] (Ln = Gd, Tb), are reported. In each isomeric pair, the central lanthanide ion adopts either a pseudo-octahedral (O-Ln) or trigonal prismatic geometry (TP-Ln) yielding complexes with C₁ or C_3h molecular symmetry, respectively. Ferromagnetic exchange coupling is observed in TP-Ln as indicated by the increases in χ_mT below 30 K. For TP-Gd, a fit to the susceptibility reveals ferromagnetic coupling between the Gd³⁺ ion and the Ti³⁺ ions (J = 2.90(1) cm⁻¹). In contrast to O-Tb, which shows no single-molecule magnetic behavior, the TP-Tb complex presents slow magnetic relaxation with a 100s-blocking temperature of 2.3 K and remanent magnetization at zero field up to 3 K. The calculated electronic structures of both compounds imply that trigonal prismatic geometry of TP-Tb is critical to the observed magnetic behavior.