Taming salophen in rare earth metallocene chemistry
Title | Taming salophen in rare earth metallocene chemistry |
Publication Type | Journal Article |
Year of Publication | 2022 |
Authors | Castellanos, E, Benner, F, Demir, S |
Journal | Inorg. Chem. Front. |
Pagination | - |
Date Published | 01/2022 |
Abstract | A series of multinuclear metallocenes composed of a tBusalophen dianion bound to two rare earth metal ions{,} where each is encased in a bis-pentamethylcyclopentadienyl scaffold{,} was realized. The isolated molecules (Cp*2RE)2(μ-tBusalophen){,} where RE = Gd (1){,} Dy (2){,} and Y (3){,} constitute the first salophen-bridged metallocene complexes for any metal ion. 1–3 were characterised by X-ray crystallography{,} cyclic voltammetry{,} IR{,} NMR{,} and UV-Vis-NIR spectroscopy. Cyclic voltammograms of 1–3 excitingly exhibit quasi-reversable features attributed to the (tBusalophen2−/tBusalophen3−˙) redox couple. DFT calculations on 3 uncovered the highest occupied molecular orbital to be primarily localized on the metallocene and phenolate moieties of the tBusalophen ligand. Furthermore{,} the nuclear spin I = ½ for yttrium allowed the collection of 89Y NMR spectra for 3. Magnetic studies revealed slow magnetic relaxation{,} placing 2 among dysprosocenium-based single-molecule magnets containing a doubly anionic ligand in the equatorial plane. |
URL | http://dx.doi.org/10.1039/D1QI01331A |
DOI | 10.1039/D1QI01331A |