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

Abstract

A new type of dinuclear dysprosium(III) complex based on phthalocyanine and salicylaldehyde derivatives (HL-R), [Dy(Pc)(L-R)(HO)]·2THF (R = OCH (1), OCH (2); HPc = phthalocyanine; HL-OCH = 2-hydroxy-3-methoxybenzaldehyde; HL-OCH = 3-ethoxy-2-hydroxybenzaldehyde), was successfully synthesized and structurally characterized. Complex 1 features a sandwich-type triple-decker structure, where two coplanar L-OCH ligands lie in the middle layer shared by two eight-coordinated Dy 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 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 ions can significantly affect the arrangement of the main magnetic axes and further result in distinct magnetic interactions as well as different relaxation behaviors.

Effect of Bridging Ligands on Magnetic Behavior in Dinuclear Dysprosium Cores Supported by Polyoxometalates

“…However, such strategies have a finite ceiling for polynuclear or extended systems, owing to the poor radial extension of the 4f orbitals results in the complicated and weak exchange interactions between lanthanide ions. To our knowledge, magnetic interactions can be strongly influenced by any subtle alterations of the coordination geometry and the ligand field of the lanthanide ion . Furthermore, the choice of the bridging group in the case of lanthanide systems is also a key component in controlling the core nature of 4f orbitals and mediating the magnetic coupling between the paramagnetic centers.…”

Rationally Designing Metal–Organic Frameworks Based on [Ln2] Magnetic Building Blocks Utilizing 2-Hydroxyisophthalate and Fine-Tuning the Magnetic Properties of Dy Analogues by Terminal Coordinated Solvents

“…Most notably, the angle made by the individual magnetic axis and the Dy1···Dy1′ line in the [Dy 2 ]-MBBs of 4 is nearly 0°. This case could not only result in strong anisotropy of the systems but affect the tunneling gap of the individual Dy III centers by the dipolar field and significantly reduce the efficiency of QTM. , However, it was rarely achieved in previously reported Dy-SMM systems − and has not been observed in any Dy-MOFs based on MBBs yet to our knowledge. In addition, it has been demonstrated that the Dy III ···Dy III interactions are very sensitive to the arrangements of the main magnetic axes because these arrangement fashions most likely affect the overlap between the Dy III and valency orbitals of the bridging atoms .…”

Magnetic Relaxation Dynamics of a Binuclear Diluted Er(III)/Y(III) Compound Influenced by Lattice Solvent

“…In addition to magnetic interactions, the configuration of the coordination environment as well as the ligand field around the metal center decisively affect the intrinsic magnetic property of lanthanide SMMs . Herein, in order to comparatively discuss our results, we performed a simply analysis of some relevant structural parameters according to the available crystal data.…”