Issue 23, 2024

Thermodynamics of spin crossover in a bis(terpyridine) cobalt(ii) complex featuring a thioether functionality

Abstract

In this contribution, a terpyridine-based ligand bearing a thioether functionality is used to prepare a new cobalt(II) spin crossover complex: [Co(TerpyPhSMe)2](PF6)2 (1), where TerpyPhSMe is 4′-(4-methylthiophenyl)-2,2′:6′,2′′-terpyridine. Its structure, determined by single crystal X-ray diffraction, reveals a mer coordination of the tridentate terpyridine ligands, leading to a tetragonally compressed octahedron. Intermolecular interactions in the crystal lattice freeze the complex in the high spin state in the solid state at all temperatures, as indicated by magnetometry and Electron Paramagnetic Resonance (EPR) spectra. When dissolved in acetonitrile, however, temperature dependent electronic, 1H-NMR and EPR spectra highlight an entropy-driven spin crossover transition, whose thermodynamics parameters have been determined. This is the first report of a cobalt(II) SCO complex featuring a thioether group, allowing its implementation in chemically grown bistable monolayers and may open important perspectives for the use of such systems in molecular spintronics.

Graphical abstract: Thermodynamics of spin crossover in a bis(terpyridine) cobalt(ii) complex featuring a thioether functionality

Supplementary files

Article information

Article type
Paper
Submitted
26 Feb 2024
Accepted
21 Mai 2024
First published
21 Mai 2024
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2024,53, 9933-9941

Thermodynamics of spin crossover in a bis(terpyridine) cobalt(II) complex featuring a thioether functionality

L. Ferraz Lobato, S. Ciattini, A. Gallo, R. A. Allão Cassaro, L. Sorace and G. Poneti, Dalton Trans., 2024, 53, 9933 DOI: 10.1039/D4DT00574K

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