There is nothing wrong with being soft: using sulfur ligands to increase axiality in a Dy(iii) single-ion magnet.

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

doi:10.1039/c9cc07292f

Abstract

A new air-stable sulfur-ligated Dy(iii) single-ion magnet has been successfully isolated with Ueff = 638 K and hysteresis loops open up to 7 K. In silico studies show that the S co-ligands significantly boost the axiality and that Te- and Se-donors have the potential to further enhance the magnetic properties.

Highlights

A new air-stable sulfur-ligated Dy(III) single-ion magnet has been successfully isolated with Ueff = 638 K and hysteresis loops open up to 7 K
Lanthanide SMMs are often associated with large magnetic moments and large magnetic anisotropy, with Dy(III) being a key component of single-ion magnets (SIMs).[3]
We report for the first time the synthesis, structure, magnetic characterisation and ab initio studies of [DyIIILON3(C5H10NS2)2]Á0.5THF (1) (Fig. 1) which is a S-ligated single-ion magnet with hysteresis loops open up to 7 K and a magnetisation reversal barrier of Ueff = 638 K, which is unprecedented in the very small family of S-ligated Dy(III) singleion magnets.[14,15,16,17,18,19,20]

Summary

Introduction

We report for the first time the synthesis, structure, magnetic characterisation and ab initio studies of [DyIIILON3(C5H10NS2)2]Á0.5THF (1) (Fig. 1) which is a S-ligated single-ion magnet with hysteresis loops open up to 7 K and a magnetisation reversal barrier of Ueff = 638 K, which is unprecedented in the very small family of S-ligated Dy(III) singleion magnets (see Table 1).[14,15,16,17,18,19,20] Compound 1 was isolated by using the cage-like ligand N-(3,5-di-tert-butyl-2-hydroxybenzyl)N,N-bis(2-pyridylmethyl)amine (HLON3) (see ESI†).[21] Our synthetic strategy generates one short Dy–O bond, to direct the magnetic anisotropy,[22] and three longer Dy–N bonds.[23] The rest of the coordination sphere is completed with soft S-donor groups, by using diethyldithiocarbamate co-ligands, (Fig. 1) giving longer Dy–S bonds (Fig. S1 and Table S2, ESI†).

Results

Conclusion