Issue 7, 2022

Taming salophen in rare earth metallocene chemistry

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.

Graphical abstract: Taming salophen in rare earth metallocene chemistry

Supplementary files

Article information

Article type
Research Article
Submitted
21 okt. 2021
Accepted
04 jan. 2022
First published
21 jan. 2022

Inorg. Chem. Front., 2022,9, 1325-1336

Author version available

Taming salophen in rare earth metallocene chemistry

E. Castellanos, F. Benner and S. Demir, Inorg. Chem. Front., 2022, 9, 1325 DOI: 10.1039/D1QI01331A

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