Self-Assembled Lanthanide Phosphinate Square Grids (Ln = Er, Dy, and Tb): Dy4 Shows SMM/SMT and Tb4 SMT Behavior
Résumé
Tetranuclear [2 × 2] square-grid-like LnIII clusters have been synthesized by reacting LnCl3·6H2O salts with bis[α-hydroxy(p-bromophenyl)methyl]phosphinic acid [R2PO2H, where R = CH(OH)PhBr] and pivalic acid. Single-crystal X-ray diffraction studies show the formation of [Me4N]2[Ln4(μ2-η1:η1-PO2R2)8(η2-CO2But)4(μ4-CO3)] [Ln = Er (1), Dy (2), and Tb (3)]. Direct-current studies reveal significant ferromagnetic interactions between DyIII in 2 and TbIII in 3 and an antiferromagnetic interaction between ErIII in 1. Dynamic magnetic susceptibility measurements confirm a single-molecule magnet (SMM) behavior in both 0 and 1200 Oe applied magnetic fields for 2. Complexes 2 and 3 show single molecular toroic (SMT) behavior with a mixed magnetic moment.