Engineering macrocyclic high performance pentagonal bipyramidal Dy(iii) single-ion magnets.

Angelos B Canaj,Oscar Céspedes,Mark Murrie,Claire Wilson,Gopalan Rajaraman,Sourav Dey

doi:10.1039/d0cc04559d

Abstract

We generate a new air-stable pseudo-D5h Dy(iii) Single-Molecule Magnet (Ueff = 1108 K, TB = 14 K) by combining a weak equatorial ligand field from a macrocyclic LN5 ligand with a strong axial ligand field. Based on our synthetic blueprint, we use ab initio calculations to show the vast scope for macrocyclic engineering of magnetic anisotropy.

Highlights

Based on our synthetic blueprint, we use ab initio calculations to show the vast scope for macrocyclic engineering of magnetic anisotropy
Lanthanide-based Single-Molecule Magnets (SMMs) are often associated with large magnetic moments and large magnetic anisotropy
Monometallic complexes with axial symmetry such as square antiprismatic,[3] trigonal bipyramidal,[4] pentagonal bipyramidal,[5,6] and hexagonal bipyramidal,[7,8] are an effective way to favour slower relaxation of the magnetisation

Summary

Introduction

We generate a new air-stable pseudo-D5h Dy(III) Single-Molecule Magnet (Ueff = 1108 K, TB = 14 K) by combining a weak equatorial ligand field from a macrocyclic LN5 ligand with a strong axial ligand field. Compound 1 shows out-ofphase peaks in the ac susceptibility up to 80 K under zero dc field, a high magnetization reversal barrier of 1108 K and hysteresis, M(H), loops open up to 14 K, measured at an average sweep rate of 0.01 T sÀ1 (see Table S1, ESI†).

Results

Conclusion