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An in solution adsorption characterization technique based on the response to an external magnetic field of porous paramagnetic materials: application on supramolecular metal-adenine frameworks containing heterometallic heptameric clusters

Abstract: Herein we explore the opportunities arising from combining magnetic properties and porosity in metal-organic materials. In this sense, we have prepared an adenine based homometallic wheel-shaped heptameric [Cu7(n-adeninato)6(n3-OH)6(n-OH2)4]2+ entity containing two metal coordination environments: CuO6 at the core of the wheel with an unusually modest Jahn-Teller distortion and six peripheral CuN2O4 with a more pronounced elongation. The difference in the coordination environments of this compound facilitates the selective replacement of the central metal position by other metal centers (ZnII, NiII, CoII and CrIII) and boosts the magnetic properties of the homometallic heptameric entity. The nature of the central metal modulates the complex net of ferro- and antiferromagnetic superexchange pathways within the heptameric entity to tune the total spin (ST = 3 (Cu6Zn), 5/2 (Cu6Cu), 2 (Cu6Ni), 3/2 (Cu6Co), and 9/2 (Cu6Cr)). No evidence of single-molecule magnet behavior has been observed at 2 K, but at room temperature, where these compounds are still in the paramagnetic regime, the attraction force exerted by an external magnetic field (H) on particles immersed in a liquid is enough to keep them attached to an electromagnet pole. The 4S(S + 1) value of the central metal follows a linear dependence with respect to the 1/[H·?(H)] value at which the particles are detached from the pole of the electromagnet. There is also a linear dependence of the H·?(H) term with respect to the adsorbate mass incorporated inside the pores of the paramagnetic adsorbent which has allowed performing straightforward sorption selectivity experiments on Cu6Cu directly in solution, which are based on a property of the adsorbent and not as usually based on an indirect assessment of the adsorbate remaining in solution.

 Autoría: Pascual-Colino J., Pérez-Aguirre R., Beobide G., Castillo O., de Pedro I., Luque A., Mena-Gutiérrez S., Pérez-Yáñez S.,

 Fuente: Inorganic Chemistry Frontiers, 2023, 10(8), 2250-2261 - (ERRATUM), 2023, 10(7), 2206-2206

Editorial: Royal Society of Chemistry

 Fecha de publicación: 01/04/2023

Nº de páginas: 12

Tipo de publicación: Artículo de Revista

 DOI: 10.1039/d2qi01994a

ISSN: 2052-1553,2052-1545

 Proyecto español: PID2019-108028GB-C21

Url de la publicación: https://doi.org/10.1039/D2QI01994A

Autoría

PASCUAL-COLINO, JON

RUBEN PEREZ AGUIRRE

BEOBIDE, GARIKOITZ

CASTILLO, OSCAR

LUQUE, ANTONIO

MENA-GUTIÉRREZ, SANDRA

PÉREZ-YÁÑEZ, SONIA