Issue 29, 2024

A highly anisotropic family of hexagonal bipyramidal Dy(iii) unsaturated 18-crown-6 complexes exceeding the blockade barrier over 2700 K: a computational exploration

Abstract

In the present work, we have explored a series of unsaturated hexa-18-crown-6 (U18C6) ligands towards designing highly anisotropic Dy(III) based single-ion magnets (SIMs) with the general formula [Dy(U18C6)X2]+ (where U18C6 = [C12H12O6] (1), [C12H12S6] (2), [C12H12Se6] (3), [C12H12O4S2] (4), [C12H12O4Se2] (5) and X = F, Cl, Br, I, OtBu and OSiPh3). By analysing the electronic structure, bonding and magnetic properties, we find that the U18C6 ligands prefer stabilising the highly symmetric eight-coordinated hexagonal bipyramidal geometry (HBPY-8), which is the source of the near-Ising type anisotropy in all the [Dy(U18C6)X2]+ complexes. Moreover, the ability of sulfur/selenium substituted U18C6 ligands to stabilize the highly anisotropic HBPY-8 geometry makes them more promising towards engineering the equatorial ligand field compared to substituted saturated 18C6 ligands where the exodentate arrangement of the S lone pairs results in low symmetry. Magnetic relaxation analysis predicts a record barrier height over 2700 K for [Dy(C12H12O6)F2]+ and [Dy(C12H12S6)X2]+ (where X = F, OtBu and OSiPh3) complexes, nearly 23% higher than those of the top performing Dy(III) based SIMs in the literature.

Graphical abstract: A highly anisotropic family of hexagonal bipyramidal Dy(iii) unsaturated 18-crown-6 complexes exceeding the blockade barrier over 2700 K: a computational exploration

Supplementary files

Article information

Article type
Paper
Submitted
02 Mar 2024
Accepted
09 May 2024
First published
15 May 2024

Dalton Trans., 2024,53, 12073-12079

A highly anisotropic family of hexagonal bipyramidal Dy(III) unsaturated 18-crown-6 complexes exceeding the blockade barrier over 2700 K: a computational exploration

S. Moorthy, I. Tarannum, K. Kumari and S. K. Singh, Dalton Trans., 2024, 53, 12073 DOI: 10.1039/D4DT00632A

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