A simple change of the substituents in the bridging ligand allows tuning of the ordering temperatures, Tc, in the new family of layered chiral magnets A[M(II)M(III)(X2An)3]·G (A = [(H3O)(phz)3](+) (phz = phenazine) or NBu4(+); X2An(2-) = C6O4X2(2-) = 2,5-dihydroxy-1,4-benzoquinone derivative dianion, with M(III) = Cr, Fe; M(II) = Mn, Fe, Co, etc.; X = Cl, Br, I, H; G = water or acetone). Depending on the nature of X, an increase in Tc from ca. 5.5 to 6.3, 8.2, and 11.0 K (for X = Cl, Br, I, and H, respectively) is observed in the MnCr derivative. Furthermore, the presence of the chiral cation [(H3O)(phz)3](+), formed by the association of a hydronium ion with three phenazine molecules, leads to a chiral structure where the Δ-[(H3O)(phz)3](+) cations are always located below the Δ-[Cr(Cl2An)3](3-) centers, leading to a very unusual localization of both kinds of metals (Cr and Mn) and to an eclipsed disposition of the layers. This eclipsed disposition generates hexagonal channels with a void volume of ca. 20% where guest molecules (acetone and water) can be reversibly absorbed. Here we present the structural and magnetic characterization of this new family of anilato-based molecular magnets.

The Scotch tape method has been used for the exfoliation of layered coordination compounds formed by a 2D bimetallic anilate-based anionic network and Fe(iii) cationic complexes placed between or within the layers.

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 [(HO)(HO)(phenazine)][FeFe(COX)]·12HO [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.