A Pseudo-Octahedral Cobalt(II) Complex with Bispyrazolylpyridine Ligands Acting as a Zero-Field Single-Molecule Magnet with Easy Axis Anisotropy

The homoleptic mononuclear compound [Co(bpp‐COOMe)2](ClO4)2 (1) (bpp‐COOMe=methyl 2,6‐di(pyrazol‐1‐yl)pyridine‐4‐carboxylate) crystallizes in the monoclinic C2/c space group, and the cobalt(II) ion possesses a pseudo‐octahedral environment given by the two mer‐coordinated tridentate ligands. Direct‐...

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Detalles Bibliográficos
Autores: Rigamonti, Luca, Bridonneau, Nathalie, Poneti, Giordano, Tesi, Lorenzo, Sorace, Lorenzo, Pinkowicz, Dawid, Jover Modrego, Jesús, Ruiz Sabín, Eliseo, Sessoli, Roberta, Cornia, Andrea
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/142929
Acceso en línea:https://hdl.handle.net/2445/142929
Access Level:acceso abierto
Palabra clave:Anisotropia
Lligands (Bioquímica)
Propietats magnètiques
Anisotropy
Ligands (Biochemistry)
Magnetic properties
Descripción
Sumario:The homoleptic mononuclear compound [Co(bpp‐COOMe)2](ClO4)2 (1) (bpp‐COOMe=methyl 2,6‐di(pyrazol‐1‐yl)pyridine‐4‐carboxylate) crystallizes in the monoclinic C2/c space group, and the cobalt(II) ion possesses a pseudo‐octahedral environment given by the two mer‐coordinated tridentate ligands. Direct‐current magnetic data, single‐crystal torque magnetometry, and EPR measurements disclosed the easy‐axis nature of this cobalt(II) complex, which shows single‐molecule magnet behavior when a static field is applied in alternating‐current susceptibility measurements. Diamagnetic dilution in the zinc(II) analogue [Zn(bpp‐COOMe)2](ClO4)2 (2) afforded the derivative [Zn0.95Co0.05(bpp‐COOMe)2](ClO4)2 (3), which exhibits slow relaxation of magnetization even in zero field thanks to the reduction of dipolar interactions. Theoretical calculations confirmed the overall electronic structure and the magnetic scenario of the compound as drawn by experimental data, thus confirming the spin‐phonon Raman relaxation mechanism, and a direct quantum tunneling in the ground state as the most plausible relaxation pathway in zero field.