Nanosheets of Two-Dimensional Magnetic and Conducting Fe(II)/Fe(III) Mixed-Valence Metal-Organic Frameworks

Samia Benmansour; Alexandre Abhervé; Patricia Gómez-Claramunt; Cristina Vallés-García; Carlos J Gómez-García

doi:10.1021/acsami.7b08322

Nanosheets of Two-Dimensional Magnetic and Conducting Fe(II)/Fe(III) Mixed-Valence Metal-Organic Frameworks

ACS Appl Mater Interfaces. 2017 Aug 9;9(31):26210-26218. doi: 10.1021/acsami.7b08322. Epub 2017 Jul 28.

Authors

Samia Benmansour¹, Alexandre Abhervé¹, Patricia Gómez-Claramunt¹, Cristina Vallés-García¹, Carlos J Gómez-García¹

Affiliation

¹ Departamento de Química Inorgánica, Instituto de Ciencia Molecular (ICMol), Parque Científico, Universidad de Valencia , Catedrático José Beltrán, 2, 46980 Paterna Valencia, Spain.

PMID: 28715894
DOI: 10.1021/acsami.7b08322

Abstract

We report the synthesis, magnetic properties, electrical conductivity, and delamination into thin nanosheets of two anilato-based Fe(II)/Fe(III) mixed-valence two-dimensional metal-organic frameworks (MOFs). Compounds [(H₃O)(H₂O)(phenazine)₃][Fe^IIFe^III(C₆O₄X₂)₃]·12H₂O [X = Cl (1) and Br (2)] present a honeycomb layered structure with an eclipsed packing that generates hexagonal channels containing the water molecules. Both compounds show ferrimagnetic ordering at ca. 2 K coexisting with electrical conductivity (with room temperature conductivities of 0.03 and 0.003 S/cm). Changing the X group from Cl to Br leads to a decrease in the ordering temperature and room temperature conductivity that is correlated with the decrease of the electronegativity of X. Despite the ionic charge of the anilato-based layers, these MOFs can be easily delaminated in thin nanosheets with the thickness of a few monolayers.

Keywords: anilato-type ligands; magnetic MOFs; metal−organic frameworks; multifunctional MOFs; nanostructures.