Issue 3, 2018

New field-induced single ion magnets based on prolate Er(iii) and Yb(iii) ions: tuning the energy barrier Ueff by the choice of counterions within an N3-tridentate Schiff-base scaffold

Abstract

Lanthanides have relatively recently been recognized as ideal candidates for the construction of advanced magnetic materials that would allow for their future applications in spintronics and high-density data storage. Despite enormous progress that deals with the control of magnetic anisotropy and slow relaxation of magnetization in Single Molecule Magnets (SMMs), further improvements are still indispensable to go beyond the ultra-low temperature regime. We have thus prepared four lanthanide complexes ([ErL2(OTf)(MeOH)2](OTf)2 (1), [YbL2(OTf)2](OTf) (2), [ErL(NO3)3(H2O)](3) and [YbL(NO3)3(MeOH)]·MeCN (4)) with a tridentate Schiff-base ligand L, to unravel magneto-structural correlations in this new family of field-induced Single Ion Magnets (SIMs). Interestingly, as revealed by the single crystal X-ray diffraction, their structures are synthetically tuned by the choice of the applied counterion. The static and dynamic magnetic properties of 1–4 were investigated revealing that all compounds behave as field-induced Single Ion Magnets (SIMs). Their energy barriers Ueff decrease in the sequence: 4, 2, 3, 1, with an order of magnitude difference between the highest and the lowest value. To correlate the observed magnetic properties with spectroscopic data, low-temperature absorption spectroscopy was performed. This has allowed the determination of the energy levels of the Ln(III) ions and the exact composition of the state vectors for the Ln(III) ground multiplets via crystal-field analysis (CFA) and semiempirical superposition model (SPM) approach. Theoretical and magneto-structural correlation studies indicate that one can modulate the heterotopic coordination spheres around the prolate Er(III) and Yb(III) solely with the counterions. This leads to rarely observed high-coordinate SIM species with the LnNxOy first coordination sphere (where Ln – Er or Yb, x = 3 or 6, y = 2, 3 or 6). Their performance can be related to the intricate interactions between the electron density on the Ln ion and the crystal field created by the surroundings.

Graphical abstract: New field-induced single ion magnets based on prolate Er(iii) and Yb(iii) ions: tuning the energy barrier Ueff by the choice of counterions within an N3-tridentate Schiff-base scaffold

Supplementary files

Article information

Article type
Research Article
Submitted
19 Nov 2017
Accepted
20 Dec 2017
First published
03 Jan 2018
This article is Open Access
Creative Commons BY license

Inorg. Chem. Front., 2018,5, 605-618

New field-induced single ion magnets based on prolate Er(III) and Yb(III) ions: tuning the energy barrier Ueff by the choice of counterions within an N3-tridentate Schiff-base scaffold

A. Gorczyński, D. Marcinkowski, M. Kubicki, M. Löffler, M. Korabik, M. Karbowiak, P. Wiśniewski, C. Rudowicz and V. Patroniak, Inorg. Chem. Front., 2018, 5, 605 DOI: 10.1039/C7QI00727B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements