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Redox and guest tunable spin-crossover properties in a polymeric polyoxometalate

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Redox and guest tunable spin-crossover properties in a polymeric polyoxometalate

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dc.contributor.author	Palacios Corella, Mario
dc.contributor.author	García López, Víctor
dc.contributor.author	Waerenborgh, João C.
dc.contributor.author	Vieira, Bruno J. C.
dc.contributor.author	Mínguez Espallargas, Guillermo
dc.contributor.author	Clemente León, Miguel
dc.contributor.author	Coronado Miralles, Eugenio
dc.date.accessioned	2023-04-05T08:20:10Z
dc.date.available	2023-04-05T08:20:10Z
dc.date.issued	2023
dc.identifier.citation	Palacios Corella, Mario García López, Víctor Waerenborgh, João C. Vieira, Bruno J. C. Mínguez Espallargas, Guillermo Clemente León, Miguel Coronado Miralles, Eugenio 2023 Redox and guest tunable spin-crossover properties in a polymeric polyoxometalate Chemical Science 14 3048 3055
dc.identifier.uri	https://hdl.handle.net/10550/86042
dc.description.abstract	A bifunctionalized polyoxometalate (POM), [V6O19(C16H15N6O)2]2−, which contains a redox active hexavanadate moiety covalently linked to two tridentate 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) ligands, has been prepared and characterized. Reaction of this hybrid molecule with Fe(II) or Zn(II) ions produces crystalline neutral 1D networks of formula Fe[V6O19(C16H15N6O)2]·solv (2) and Zn[V6O19(C16H15N6O)2]·solv (3) (solv = solvent molecules). Magnetic properties of 2 show an abrupt spin-crossover (SCO) with the temperature, which can be induced by light irradiation at 10 K (Light-Induced Excited Spin-State Trapping, LIESST effect). Interestingly, this porous and flexible structure enables reversible exchange of solvents in 2, which allows tuning the temperature of the thermal SCO. In 2 and 3, the hexavanadate unit can be reduced by electrochemical or chemical means in a reversible way. Chemical reduction and reoxidation by a postsynthetic method is accompanied by the insertion in the structure of the reductant and oxidant molecules (cobaltocene and tribromide, respectively), which provokes drastic changes in the spin state of Fe(II). This leads to an elegant switching multifunctional material in which SCO properties of the Fe(II) complexes coexist with the redox properties of the POM and can be tuned by a variety of stimuli such as temperature, light, solvent exchange or electron transfer. During the reduction process, 3 undergoes a single-crystal-to-single-crystal one-electron reduction, which confirms the presence of cobaltocenium cations by single crystal X-ray diffraction.
dc.language.iso	eng
dc.relation.ispartof	Chemical Science, 2023, vol. 14, p. 3048-3055
dc.subject	Química
dc.subject	Indústria química
dc.title	Redox and guest tunable spin-crossover properties in a polymeric polyoxometalate
dc.type	journal article	es_ES
dc.date.updated	2023-04-05T08:20:11Z
dc.identifier.doi	10.1039/D2SC05800F
dc.identifier.idgrec	157254
dc.rights.accessRights	open access	es_ES