Modulating the Magnetic Interaction in New Triple-Decker Dysprosium(III) Single-Molecule Magnets

A new type of dinuclear dysprosium(III) complex based on phthalocyanine and salicylaldehyde derivatives (HL-R), [Dy₂(Pc)₂(L-R)₂(H₂O)]·2THF (R = OCH₃ (1), OC₂H₅ (2); H₂Pc = phthalocyanine; HL-OCH₃ = 2-hydroxy-3-methoxybenzaldehyde; HL-OC₂H₅ = 3-ethoxy-2-hydroxybenzaldehyde), was successfully synthesized and structurally characterized. Complex 1 features a sandwich-type triple-decker structure, where two coplanar L-OCH₃ ligands lie in the middle layer shared by two eight-coordinated Dy^III ions and two Pc ligands are located in the outer layer. In 2, the introduction of an ethoxy group generates a noncoordination mode for the O_alkoxy atom. Magnetic studies indicate that complex 1 behaves as a zero-field single-molecule magnet with a higher energy barrier, while 2 exhibits a fast tunneling relaxation process. Theoretical calculations revealed that changes in the ligand field environment around Dy^III ions can significantly affect the arrangement of the main magnetic axes and further result in distinct magnetic interactions as well as different relaxation behaviors.