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Dominance of Cyclobutadienyl Over Cyclopentadienyl in the Crystal Field Splitting in Dysprosium Single-Molecule Magnets.
- Source :
-
Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2022 Apr 19; Vol. 61 (17), pp. e202200525. Date of Electronic Publication: 2022 Feb 26. - Publication Year :
- 2022
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Abstract
- Replacing a monoanionic cyclopentadienyl (Cp) ligand in dysprosium single-molecule magnets (SMMs) with a dianionic cyclobutadienyl (Cb) ligand in the sandwich complexes [(η <superscript>4</superscript> -Cb'''')Dy(η <superscript>5</superscript> -C <subscript>5</subscript> Me <subscript>4</subscript> <superscript>t</superscript> Bu)(BH <subscript>4</subscript> )] <superscript>-</superscript> (1), [(η <superscript>4</superscript> -Cb'''')Dy(η <superscript>8</superscript> -Pn <superscript>†</superscript> )K(THF)] (2) and [(η <superscript>4</superscript> -Cb'''')Dy(η <superscript>8</superscript> -Pn <superscript>†</superscript> )] <superscript>-</superscript> (3) leads to larger energy barriers to magnetization reversal (Cb''''=C <subscript>4</subscript> (SiMe <subscript>3</subscript> ) <subscript>4</subscript> , Pn <superscript>†</superscript> =1,4-di(tri-isopropylsilyl)pentalenyl). Short distances to the Cb'''' ligands and longer distances to the Cp ligands in 1-3 are consistent with the crystal field splitting being dominated by the former. Theoretical analysis shows that the magnetic axes in the ground Kramers doublets of 1-3 are oriented towards the Cb'''' ligands. The theoretical axiality parameter and the relative axiality parameter Z and Z <subscript>rel</subscript> are introduced to facilitate comparisons of the SMM performance of 1-3 with a benchmark SMM. Increases in Z and Z <subscript>rel</subscript> when Cb''' replaces Cp signposts a route to SMMs with properties that could surpass leading systems.<br /> (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Details
- Language :
- English
- ISSN :
- 1521-3773
- Volume :
- 61
- Issue :
- 17
- Database :
- MEDLINE
- Journal :
- Angewandte Chemie (International ed. in English)
- Publication Type :
- Academic Journal
- Accession number :
- 35108431
- Full Text :
- https://doi.org/10.1002/anie.202200525