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

• Published in: Dalton transactions : an international journal of inorganic chemistry 2024-06, Vol.53 (23), p.9933-9941
• Main Authors: Ferraz Lobato, Lúcio, Ciattini, Samuele, Gallo, Angelo, Allão Cassaro, Rafael A, Sorace, Lorenzo, Poneti, Giordano
• Format: Article
• Language: English
• Subjects: Acetonitrile; Cobalt compounds; Crossovers; Crystal lattices; Electron paramagnetic resonance; Ligands; Magnetic measurement; NMR; Nuclear magnetic resonance; Single crystals; Spectra; Spintronics; Temperature dependence; Thermodynamics
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d4dt00574k

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 ](PF 6 ) 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, 1 H-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. A new cobalt( ii ) complex featuring a terpyridine ligand functionalized with a thioether group has been prepared, structurally and magnetically characterized, and the thermodynamics of its spin crossover behaviour investigated in solution.