Slow Magnetic Relaxation in Mono- and Bimetallic Lanthanide Tetraimido-Sulfate S(NtBu)4 2- Complexes

Chemistry. 2021 Aug 25;27(48):12310-12319. doi: 10.1002/chem.202101076. Epub 2021 Jun 24.

Abstract

Lanthanide ions are particularly well-suited for the design of single-molecule magnets owing to their large unquenched orbital angular momentum and strong spin-orbit coupling that gives rise to high magnetic anisotropy. Such nanoscopic bar magnets can potentially revolutionize high-density information storage and processing technologies, if blocking temperatures can be increased substantially. Exploring non-classical ligand scaffolds with the aim to boost the barriers to spin-relaxation are prerequisite. Here, the synthesis, crystallographic and magnetic characterization of a series of each isomorphous mono- and dinuclear lanthanide (Ln=Gd, Tb, Dy, Ho, Er) complexes comprising tetraimido sulfate ligands are presented. The dinuclear Dy complex [{(thf)2 Li(NtBu)2 S(tBuN)2 DyCl2 }2 ⋅ ClLi(thf)2 ] (1c) shows true signatures of single-molecule magnet behavior in the absence of a dc field. In addition, the mononuclear Dy and Tb complexes [{(thf)2 Li(NtBu)2 S(tBuN)2 LnCl2 (thf)2 ] (2b,c) show slow magnetic relaxation under applied dc fields.

Keywords: SN complexes; lanthanide complexes; single-molecule magnets; slow magnetic relaxation; tetraimido sulfate.