Tuning symmetry and magnetic blocking of an exchange-coupled lanthanide ion in isomeric, tetrametallic complexes: [LnCl(TiCp)].

The synthesis and magnetic properties of two pairs of isomeric, exchange-coupled complexes, [LnCl(TiCp)] (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 or molecular symmetry, respectively. Ferromagnetic exchange coupling is observed in TP-Ln as indicated by the increases in below 30 K. For TP-Gd, a fit to the susceptibility reveals ferromagnetic coupling between the Gd ion and the Ti ions ( = 2.90(1) cm). 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.